JP3303549B2 - Antimicrobial polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antimicrobial linear polymer having a biguanide group and a polysiloxane (more specifically, polydimethylsiloxane) chain in the chain. By surface treatment using the polymer of the present invention, fibers and fabrics,
It can impart antimicrobial properties such as antibacterial, fungicidal, and algae-proof to various inorganic, organic, and natural materials including paper, building materials such as wood and concrete, glass, metals, synthetic resins and natural resins. it can. The present invention also relates to a surface treating agent containing such a polymer as an active ingredient for imparting antimicrobial properties to a material.

[0002]

2. Description of the Related Art It has been proposed that a powder in which an antibacterial metal such as silver is supported on an inorganic carrier such as zeolite is kneaded into a synthetic fiber or the like to impart a continuous antibacterial property. But,
In this method, most of the drug enters the inside of the material, so that the antibacterial effect is reduced and the efficiency is low compared to the amount of the drug used. In addition, there is a problem that the material that can be applied by the kneading method is limited, and cannot be applied to natural fibers and the like. Furthermore, since silver ions are harmful to the human body, it is not preferable that they elute and exhibit an antibacterial effect.

On the other hand, organic antibacterial agents such as quaternary ammonium compounds are also known. Organic antibacterial agents have low thermal stability and are difficult to knead into molten resin. Accordingly, antibacterial properties are imparted to the material by surface treatment such as coating. However, since the compound is a water-soluble compound, its effect is low and its use is limited in terms of toxicity.

As another organic antibacterial and antifungal agent, a biguanide group [-NH-C (= N
H) -NH-C (= NH) -NH-]-mediated polymers containing biguanide groups and acid addition salts thereof are known (JP-A-50-48).
No. 134). Although this polymer has been developed for fungicides on crops, it has no toxicity and is easily soluble in water in the form of a salt. Therefore, it is currently used as an aqueous solution for disinfection of equipment.

[0005]

However, the polymer containing a biguanide group is not suitable for surface treatment for imparting antibacterial and antifungal properties to the material. That is, even if the material is surface-treated (eg, coated) using the polymer solution, the effect is not persistent. This biguanide group-containing polymer is mainly composed of polymethylene chains such as trimethylene and hexamethylene.
(However, part of the polymethylene chain may be a group such as -phenyl-CH ₂ -phenyl-) A relatively low molecular weight polymer having a structure in which a biguanide group is interposed in the chain, and a free base Is relatively high in water solubility. Therefore, even if a material such as a fiber is subjected to surface treatment with this polymer, the formed film is immediately lost by water, and the effect is not persistent.

An object of the present invention is to provide a novel antimicrobial polymer which can efficiently impart antimicrobial properties to various materials by surface treatment, does not elute harmful drug components, and has a long lasting effect. It is to provide.

[0007]

According to the present invention, there is provided according to the present invention, a biguanide group [-NH-C (= NH) -NH-C (= NH) -NH-] and a polysiloxane chain in a chain. This is achieved by a novel linear polymer having antimicrobial properties having a stable structure.

The antimicrobial polymer of the present invention comprises (a) only a repeating unit represented by the following general formula (1) or (b) a repeating unit represented by the following general formula (1) and combination of a repeating unit represented by 2), consists of the total number of repeating units is 2 to 50, a polymer having a biguanide groups and a polysiloxane chain in the chain.

[0009]

Embedded image

In the above formula, 1 is 3 to 12, m is 5 to 100, n
And p are each an integer of 3 to 8, and l, m,
The values of n and p may be different for each repeating unit. Accordingly, the values of l, m, n, and p are sometimes represented by average values.

Preferably, the total number of recurring units is from 2 to 30, with 1 on average 3 to 6, m 5 to 50 and n 3 to 5. Further, when a repeating unit represented by the general formula (2) is contained, the proportion of the repeating unit is preferably 80% or less, particularly preferably 60% or less, of the total number of the repeating units.

[0012] In the polymer of the present invention, at the same time when both ends of the molecule are identical or Ru different from each other, respectively formula (A)
Or a cyanoguanidyl group represented by the formula (B) or a biguanidyl group represented by the formula (C).

[0013]

Embedded image

In the above formula, R ¹ is hydrogen or a substituted or unsubstituted aliphatic, alicyclic or aromatic hydrocarbon group having 18 or less carbon atoms, and R ² is a substituted or unsubstituted having 18 or less carbon atoms. It is an aliphatic, alicyclic or aromatic hydrocarbon group.

Examples of the aliphatic, alicyclic or aromatic hydrocarbon groups for R ¹ and R ² include aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl and octadecyl. And alicyclic hydrocarbon groups such as cyclopentyl and cyclohexyl, and aromatic hydrocarbon groups such as phenyl, phenethyl and tolyl. These hydrocarbon groups may have one or more substituents such as a hydroxyl group, a halogen, a nitro group, a methoxy group, and a trifluoromethyl group.

The polymer having a terminal group of the amino group of the formula (A) and / or the cyanoguanidyl group of the formula (B) among the biguanide group-containing polymers of the present invention can be prepared, for example, by any of the following methods: Can be manufactured.

A compound having a polysiloxane chain represented by the general formula (3) (hereinafter simply referred to as a polysiloxane compound) is homopolymerized: ZXZ (3) (where X is the same as defined above) , Z is a mixture of the amino group represented by the formula (A) and the cyanoguanidyl group represented by the formula (B)).

The raw material polysiloxane compound represented by the general formula (3) is a compound represented by the following general formula (4): NH ₂ -X-NH ₂ (4) (wherein X has the same meaning as described above) Can be produced by reacting NC-N = C (SCH ₃ ) or NaN (CN) ₂ with a polysiloxane compound having an amino group as a starting material to partially cyanoguanidify the amino group. . The product of this cyanoguanidylation reaction is generally an amino group at both ends (both ends unreacted)
, Cyanoguanidyl group at both ends (react at both ends)
And a mixture of three types of polysiloxane compounds, one of which is an amino group and the other of which is a cyanoguanidyl group (reacts only at one end). Therefore,
The reaction product represented by the general formula (3) used as a raw material in the polymerization reaction can be defined by the cyanoguanidyl group content.

The raw materials used for the above homopolymerization include:
Among the polysiloxane compounds represented by the general formula (3), those having a cyanoguanidyl group content of 5 to 95% (compounds having a terminal group of an amino group of 5 to 95% and a cyanoguanidyl group of 5 to 95%) are preferred. . In this preferred homopolymerization of the raw material, the amino group present at the end of the raw material polysiloxane compound reacts with the cyanoguanidyl group to form a biguanide group, whereby the polymerization proceeds and the repeating unit represented by the general formula (1) Thus, a biguanide group-containing polymer of the present invention consisting of only the above is obtained. However, when one of the amino group and the cyanoguanidyl group present at the terminal is 5% or less, the polymerization by the above-described reaction is difficult to proceed.

The polysiloxane compound represented by the general formula (4) is copolymerized with the polysiloxane compound represented by the general formula (5): NH ₂ -X-NH ₂ (4) Z ¹ -XZ ¹ (5 (Wherein X is as defined above, and Z ¹ is a cyanoguanidyl group [—NH—C (= NH) —NH—CN] represented by the above formula (B)). The polysiloxane compound represented by the general formula (4)
It is a starting material used for producing the raw material represented by the general formula (3), and is a diamine-type polysiloxane compound having a cyanoguanidyl group content of 0%. On the other hand, the compound represented by the general formula (5) is a product in which the amino group of the starting material is completely cyanoguanidylated, that is, a dicyanoguanidyl-type polysiloxane compound having a cyanoguanidyl group content of 100%. Since these polysiloxane compounds have only an amino group or only a cyanoguanidyl group at the end, polymerization does not occur alone. However, when the two are copolymerized, the polymerization proceeds due to the formation of a biguanide group by the reaction between the amino group and the cyanoguanidyl group, and the general formula
The biguanide group-containing polymer of the present invention comprising only the repeating unit represented by (1) is obtained.

The polysiloxane compound represented by the general formula (4) and / or the polysiloxane compound represented by the general formula (5) is copolymerized with the polysiloxane compound represented by the general formula (3). The biguanide group-containing polymer of the present invention comprising only the repeating unit represented by the general formula (1) can be obtained.

At least one of the polysiloxane compounds represented by the general formulas (3) to (5) is copolymerized with at least one of the polymethylene compounds represented by the general formulas (6) to (8): ZX -Z (3) NH ₂ -X-NH ₂ (4) Z ¹ -X-Z ¹ (5) Z-YZ (6) NH ₂ -Y-NH ₂ (7) Z ¹ -YZ ¹ (8) (wherein X, Y, Z, and Z ¹ are the same as described above). The product of this copolymerization reaction is composed of the repeating unit (1) and the repeating unit
(2) a biguanide group-containing polymer of the present invention comprising: Since this reaction is also a reaction between an amino group and a cyanoguanidyl group, if one of the reaction components (for example, a polysiloxane compound) is a compound containing only an amino group or a cyanoguanidyl group at the terminal, the other reaction component (for example, a polysiloxane compound) is used. ,
As the polymethylene compound), it is necessary to use a compound containing a cyanoguanidyl group or an amino group, respectively. Polymethylene compounds having a cyanoguanidyl group at the terminal represented by the general formulas (6) and (8) are represented by the general formula
It can be produced by the above-described cyanoguanidylation reaction using a polymethylene compound having a terminal amino group represented by (7) as a starting material.

For reference, the above repeating unit (1)
And (2), and more specific structures of the general formulas (3) to (8) are shown below.

[0024]

Embedded image

In the formula, 1 is an integer of 3 to 12, m is an integer of 5 to 100, n and p are integers of 3 to 8, and the values of l, m, n, and p are different for each repeating unit. Good. In that case, these values can be defined as average values of the entire material. Z is a mixture of an amino group (—NH ₂ ) and a cyanoguanidyl group [—NH—C (= NH) —NH—CN], and Z ¹ is a cyanoguanidyl group.

That is, in either case, the polymerization or copolymerization proceeds through the formation of a biguanide group by the reaction between the amino group present at the terminal of the raw material reaction component and the cyanoguanidyl group. The reaction component containing a terminal amino group is
It is preferably used in the reaction in the form of an acid addition salt (particularly hydrochloride). The reaction does not proceed sufficiently with the free base, or the reaction rate is extremely slow.

The reaction temperature is 50-250 ° C., especially 120-200 ° C.
Is preferred, the reaction time is usually 1 to 30 hours,
Preferably, it is 3 to 20 hours. A solvent need not be used, but when used, alcohols such as tert-butanol and 2-ethoxyethanol and hydrocarbons such as toluene and xylene are suitable. The reaction is usually carried out at atmospheric pressure, but the reaction pressure can be raised for the purpose of raising the reaction temperature to promote the reaction.

The terminal of the polymer of the present invention produced by the above method is an amino group (preferably an acid addition salt) and / or a cyanoguanidyl group. Since the ratio between the amino group and the cyanoguanidyl group in the terminal group depends on the ratio between the amino group and the cyanoguanidyl group in the reaction component used as the raw material, the ratio can be arbitrarily changed by this ratio.

In order to introduce the biguanidyl group represented by the above (C) into the terminal of the polymer, an addition reaction of a monoamine compound represented by the following general formula (9) to the cyanoguanidyl group is used: R ¹ R ² NH ( 9) (wherein, R ¹ and R ² have the same meanings as described above). Specifically, in any of the above methods,
By causing the monoamine compound represented by (9) to coexist in the reaction system, a polymer containing a biguanidyl group can be obtained. Alternatively, when the polymer obtained by the method has a cyanoguanidyl group at the terminal, the obtained polymer is reacted with a monoamine compound represented by the above general formula (9), and the polymer is terminated at the polymer terminal. Biguanidyl groups can also be introduced. Also in this case, the monoamine compound is an acid addition salt.
It is preferably used for the reaction in the form of (particularly hydrochloride). The amount of the introduced biguanidyl group can be freely adjusted by the amount of the monoamine compound used. Thereby, the polymer of the present invention can be obtained in which the terminal is composed of a biguanidyl group and / or one or both of an amino group and a cyanoguanidyl group.

The resulting acid addition salt type biguanide group-containing polymer of the present invention can be neutralized with a suitable base to be converted into a free base type polymer. Further, the free base type polymer of the present invention containing a biguanide group can be reacted with an acid to convert it into another acid addition salt.

The properties of the polymer having a polysiloxane chain and a biguanide group in the chain according to the present invention may be solid or rubbery (solid), depending on the degree of polymerization of the polysiloxane chain and its ratio. This polymer is generally insoluble in water, and is often insoluble in water-miscible organic solvents such as acetone and methanol. However, toluene, xylene,
It is soluble in water-immiscible organic solvents such as hexane.

The biguanide group-containing polymer (free base or acid addition salt) of the present invention is useful for surface treatment for imparting antimicrobial properties (antibacterial, antifungal, antialgal, etc.) to the material. . That is, according to the present invention, there is also provided a surface treating agent containing the polymer as an active ingredient for imparting antimicrobial properties to a material. This surface treatment agent usually comprises a solution in which the biguanide group-containing polymer of the present invention is dissolved in a suitable organic solvent.

Unlike the biguanide group-containing polymer described in Japanese Patent Application Laid-Open No. 50-48134, the biguanide group-containing polymer of the present invention is a dimethylpolyamide present in the repeating unit represented by the general formula (I). It has a siloxane chain. The dimethylpolysiloxane chain is a repeating unit constituting a polymer known as silicone, as is well known. It is well known that silicone-based polymers can be used for surface treatment of various materials for the purpose of imparting water repellency and antifouling properties, and can form a coating having high durability.

According to the present invention, by introducing a dimethylpolysiloxane chain into a biguanide group-containing polymer molecule, the polymer becomes insoluble in water, and when a material is surface-treated, it is derived from a silicone polymer. High durability can be obtained. Therefore, the durability of the antimicrobial property imparted by the biguanide group is increased, and the effect can be exerted for a long time.

The surface treatment of the material can be carried out, for example, by adhering a surface treating agent comprising a solution of the polymer of the present invention in an organic solvent to the surface of the material by an appropriate method such as immersion, spraying or coating. . After the treatment, when the solvent is removed by natural drying or heat drying, a film made of the polymer of the present invention is formed on the surface of the material.

Examples of usable solvents include ethers such as diethyl ether and isopropyl ether, ketones such as methyl isobutyl ketone, cyclohexanone and isophorone, ethanol, isopropanol, tert-butanol, 2-methoxyethanol, 2-ethoxyethanol and the like. Alcohols, toluene, xylene, hexane, hydrocarbons such as cyclohexane are exemplified,
It is not limited to these. One or more solvents can be used, and it is natural that the solvent is selected so as to dissolve the polymer containing a biguanide group as an active ingredient. The concentration of the active ingredient in the solution is not particularly limited.
A range of about 20% by weight is suitable.

The surface treatment with the polymer of the present invention is applicable to various inorganic, organic and natural materials including fibers, fabrics, paper, wood, concrete, glass, metals, synthetic resins and natural resins. Since the film formed on the surface of the material after the surface treatment has high transparency, this surface treatment can be applied to a material requiring transparency such as glass.

In the film thus formed on the surface of the material, since each repeating unit represented by the general formulas (1) and (2) has one biguanide group, a large number of biguanide groups are present in the molecule. Contains. Therefore, the antimicrobial properties (antibacterial properties, antifungal properties, antialgal properties, etc.) derived from the biguanide group are extremely high. Moreover, in addition to this antimicrobial property, it also has functions such as heat resistance, weather resistance, water repellency, glazing, surface protection, and electrical properties of the polysiloxane chain (silicone resin). Therefore, it is possible to provide these functions simultaneously with antimicrobial properties.

As another advantage, the membrane is water-insoluble due to the nature of the polysiloxane chains and is firmly bound to the material surface, so that the antimicrobial effect is highly persistent. Therefore, even if the surface-treated material is left in water, the antimicrobial property is not lost, and the durability to washing is significantly increased. Furthermore, safety is high because no harmful components are eluted.

The antimicrobial polymer of the present invention is also used for the purpose of imparting antimicrobial properties by being mixed into a material, such as being mixed into a sealing material in which the generation of microorganisms such as molds is a problem. Can be used.

[0041]

【Example】

[0042]

[Example 1] In a eggplant-shaped flask with a capacity of 100 mL, the general formula
20 g of the polysiloxane compound (3) (cyanoguanidyl group content: 50%, average m = 20, n = p = 3)
The compound was homopolymerized by heating at 0 ° C. for 12 hours.
The resulting polymer is a brown rubber with a softening temperature of 100 ° C.
It was insoluble in water, acetone and methanol.
This polymer is composed of only the repeating unit represented by the general formula (1), the average number of repeating units per molecule is about 10, and the terminal is an amino group and a cyanoguanidyl group.

2 g of this polymer was dissolved in 100 mL of xylene to prepare a treatment solution for surface treatment, and the antibacterial property was tested by the test method described below. As a result, no viable bacteria were found. That is, this polymer was able to impart antibacterial properties to the material by the surface treatment.

[Test method for antibacterial activity] 2 g of the treatment liquid was applied to 25 x 65 x 2 mm
And dried at 100 ° C. for 2 hours for surface treatment. Place the glass plate in a sterilized container and place the bacterial suspension [Test strain: Staphylococcus
s aureus) ATCC 6538] 0.1 mL (the number of bacteria: about 2.0 × 10 ⁷ ), and incubate at 35 ° C. for 18 hours in a thermostat incubator. Next, add 10 mL of sterilized water to the container, shake, and check the number of viable bacteria dispersed in the water.

[0045]

[Example 2] In a 100 mL eggplant-shaped flask, a general formula was used.
10 g of the diamine-type polysiloxane compound (4) (cyanoguanidyl group content: 0%, average m = 20, n = p = 3) and the dicyanoguanidyl-type polysiloxane compound of general formula (5) (cyanoguanidyl group content: 100%, average m = 20,
n = p = 3) 10 g and heated at 150 ° C. for 16 hours to copolymerize these compounds. The resulting polymer was a brown rubber having a softening temperature of 120 ° C. and was insoluble in any of water, acetone and methanol. This polymer is composed of only the repeating units of the general formula (1), the number of repeating units per molecule is about 5 on average, and the terminal is an amino group and a cyanoguanidyl group.

2 g of this polymer was dissolved in 100 mL of xylene to prepare a treatment solution for surface treatment, and the antibacterial effect was tested by the method described in Example 1. As a result, no viable bacteria were found.

[0047]

[Example 3] In a eggplant-shaped flask having a capacity of 200 mL, the general formula
(4) 10 g of a diamine-type polysiloxane compound (cyanoguanidyl group content: 0%, average m = 20, n = p = 3)
Dicyanoguanidyl-type polymethylene compound of general formula (8)
(Cyanoguanidyl group content 100%, l = 6) 10 g and 2-ethoxyethanol (50 mL) as a solvent were charged.
The mixture was heated at 0 ° C. for 18 hours to copolymerize the starting compounds. The polymer obtained after distilling off the solvent was a brown rubber having a softening temperature of 80 ° C., and was insoluble in any of water, acetone and methanol. This polymer comprises about 13% of the repeating unit of the general formula (1) and about 87% of the repeating unit of the general formula (2).
The total number of recurring units per molecule averages about 10, terminating in amino and cyanoguanidyl groups.

2 g of this polymer was dissolved in isopropyl ether 10
A solution for surface treatment was prepared by dissolving in 0 mL, and the antibacterial effect was tested by the method described in Example 1. As a result, no viable bacteria were observed.

[0049]

[Example 4] In a 100 mL eggplant-shaped flask, a general formula was used.
10 g of the polysiloxane compound of (3) (cyanoguanidyl group content 80%, average m = 20, n = p = 3), general formula (7)
Of diamine-type polymethylene compound (cyanoguanidyl group content: 0%, l = 3) and 40 mL of tert-butanol as a solvent were charged and heated at 90 ° C. for 20 hours to copolymerize the raw material compound. The polymer obtained after the solvent was distilled off was a brown rubber having a softening temperature of 60 ° C., and was insoluble in any of water, acetone and methanol. This polymer has about 4% of the repeating unit of the general formula (1) and about 4% of the repeating unit of the general formula (2).
Consisting of 96%, the total number of repeating units per molecule is about 10 on average, and the terminal is an amino group and a cyanoguanidyl group.

2 g of this polymer was dissolved in 100 mL of hexane to prepare a treatment solution for surface treatment, and the antibacterial effect was tested by the method described in Example 1. As a result, no viable bacteria were found.

[0051]

[Example 5] In a eggplant-shaped flask with a capacity of 100 mL, the general formula
20.0 g of the polysiloxane compound (3) (cyanoguanidyl group content 50%, average m = 20, n = p = 3), p-hydrochloric acid
Chloroaniline 0.2g and solvent isopropanol
20 mL was charged and heated at 80 ° C. for 16 hours to polymerize the polysiloxane compound, and at the same time, an amine was added to the terminal cyanoguanidyl group for biguanidylation. The polymer obtained after distilling off the solvent was a brown rubber having a softening temperature of 80 ° C., which was insoluble in any of water, acetone and methanol. This polymer comprises only the repeating units of the general formula (1), the total number of repeating units per molecule is about 5, and the terminals are mainly amino groups and biguanidyl groups.

2 g of this polymer was dissolved in 100 mL of xylene to prepare a treatment solution for surface treatment, and the antibacterial effect was tested by the method described in Example 1. As a result, no viable bacteria were found.

[0053]

Example 6 2 g of the treatment liquid prepared in Example 1 was applied to 25 × 65 ×
After spraying on a 2 mm glass plate, it was dried at 100 ° C. for 2 hours to perform surface treatment. The surface-treated glass plate was immersed in a 60 ° C. water bath for 3 days.

When the glass plate immersed in a hot water bath for 3 days after this surface treatment was tested for the antibacterial effect by the method described in Example 1, no viable bacteria were observed.

[0055]

Comparative Example 1 A polysiloxane polymer having a terminal biguanidyl group (silicone oil) represented by the following formula (wherein
Average m number = 20, n = p = 3, A is a mixture of 50% of biguanidyl groups and 50% of amino groups) 2 g of isopropanol 100
The resultant was dissolved in mL to prepare a treatment solution for comparison.

[0056]

Embedded image

This treatment liquid was tested in the same manner as in Example 6.
That is, 2 g of the treatment liquid was sprayed on a glass plate of 25 × 65 × 2 mm, dried at 100 ° C. for 2 hours to perform surface treatment, and then the glass plate was immersed in a 60 ° C. water bath for 3 days. When the antibacterial property of the glass plate after immersion was examined by the antibacterial property test method described in Example 1, the number of viable bacteria dispersed in water was 4.3 × 10 ⁴ cells / mL. That is, when the surface treatment was performed with a polymer having a biguanide group and a polysiloxane chain in the chain of the present invention, the antimicrobial property was not lost even when immersed in warm water. When the surface was treated with a biguanidyl group-containing polysiloxane polymer, the water resistance of the film was poor, and the antimicrobial properties were significantly reduced.

[0058]

Example 7 10 mL of the treatment solution prepared in Example 1 was
It was sprayed on a square cotton cloth and dried at 80 ° C. for 1 hour. This surface-treated cotton cloth was repeatedly washed according to the JIS 217-103 method. The antibacterial property after washing a predetermined number of times was placed in a sterilized container, and inoculation, culture, and measurement of the number of viable bacteria were performed in the same manner as described in the antibacterial test of Example 1. Table 1 shows the results.

[0059]

[Comparative Example 2] Apply 10 mL of the treatment solution prepared in Comparative Example 1 to 20 cm.
It was sprayed on a square cotton cloth and dried at 80 ° C. for 1 hour. This treated cotton cloth was washed and tested as in Example 6. The results are shown in Table 1. As can be seen from Table 1, since the polymer of the present invention has water resistance, it was also excellent in washing resistance.

[0060]

[Table 1]

[0061]

The polymer of the present invention exhibits high antimicrobial properties, and forms a water-insoluble antimicrobial film firmly adhered to the surface of the material by treating the surface of the material with a solution containing the polymer. This film is water-resistant, has high durability of antimicrobial properties, does not lose its antimicrobial properties even when left in water, and has extremely high durability against washing. Furthermore, safety is high because no harmful components are eluted. Furthermore, the polymer of the present invention has heat resistance, weather resistance, water repellency, glazing property, surface protection, and polysiloxane chains (silicone resin) present in the molecule.
It also has functions such as electrical characteristics, and it is possible to impart these functions to the material simultaneously with antimicrobial properties by surface treatment of the material.

Claims (3)

(57) [Claims] 1. A chain-like polymer consisting of repeating units represented by the following general formula (1), the total number of repeating units is 2 to 50, both ends of the molecule are the mutually identical or Ru different same
Sometimes a polymer having a biguanide group and a polysiloxane chain in the chain, each being a group represented by the following formula (A), (B) or (C) . Embedded image Wherein, m is 5 to 100, n and p are integers each 3 to 8, m, n, the value of p may be different for each repeating unit; R ¹ is the number of hydrogen or carbon 18 The following substituted or unsubstituted aliphatic, alicyclic or aromatic hydrocarbon groups, and R ² is a substituted or unsubstituted aliphatic, alicyclic or aromatic hydrocarbon group having 18 or less carbon atoms. 2. A chain polymer comprising a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), wherein the total number of the repeating units is 2 to 50, at the same time when both ends of the molecule are identical or Ru different from one another, each of the following formula (a), (B), or a group represented by (C), a polymer having a biguanide groups and polysiloxane chains in the chain . Embedded image Wherein l is 3-12, m is 5-100, n and p are 3-8
And the values of l, m, n and p may be different for each repeating unit; R ¹ is hydrogen or a substituted or unsubstituted aliphatic, alicyclic or R ² is a substituted or unsubstituted aliphatic, alicyclic or aromatic hydrocarbon group having 18 or less carbon atoms. 3. A surface treating agent for imparting antimicrobial properties to a material, comprising a polymer having a biguanide group in the chain according to claim 1 or an acid addition salt thereof as an active ingredient.