JP3289055B2 - Polyelectrolyte complex antibacterial agent and antibacterial material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an antibacterial agent comprising a polyelectrolyte chain and an antibacterial material carrying the polyelectrolyte chain.

BACKGROUND ART It is known that an organic compound having a positive charge exhibits antibacterial properties, regardless of whether it is a low molecular compound or a high molecular compound. Applied technology utilizing this property has been widely used from the medical field to general clothing. For example,
Since quaternary ammonium compounds represented by benzalkonium chloride and the like are water-soluble, they are themselves used as sterilizing and disinfecting liquids. However, on the contrary, since it is water-soluble, the range of use as an antibacterial agent is limited.

In addition, by introducing an anionic group to the surface of the synthetic polymer molded article and subsequently treating it with a quaternary ammonium base, a material exhibiting long-lasting antibacterial properties can be obtained. It is also used as extra material. Furthermore, this technology is applied to textile materials and used as antibacterial clothing or wound protectants.

For example, Japanese Patent Application Laid-Open No. Sho 54-86584 discloses a method for introducing a quaternary ammonium into the surface of a polymer material to obtain a material having sustained antibacterial activity. A method is described for contacting a molecular substance with an aqueous solution of a quaternary ammonium base. Also, Japanese Unexamined Patent Publication No.
Japanese Patent No. 164342 discloses a method in which an anionic group-containing vinyl monomer is introduced onto the surface of a synthetic polymer molded article by, for example, graft polymerization and then treated with a quaternary ammonium base.

However, in the conventional method, the introduction rate of a quaternary ammonium base exhibiting antibacterial properties is not always sufficient, and the sustainability is not satisfactory. Furthermore, the manufacturing method was complicated.

The present inventor conducted intensive studies with the aim of obtaining a material having a solvent (especially water) insolubility while maintaining the antibacterial property of a positively charged organic compound and having a sustained antibacterial action. It has been found that these objects can be achieved by a polymer electrolyte complex obtained by reacting a specific anionic polymer with a specific cationic polymer. The present invention is based on this finding.

DISCLOSURE OF THE INVENTION Accordingly, the present invention provides (A) a cationic polymer containing an N ⁺ atom in a repeating unit, comprising: [Wherein, R ₁ and R ₄ are each independently an alkylene group having 1 to 10 carbon atoms; (Wherein, R ₁₁ and R ₁₂ are each independently an alkylene group having 1 or 2 carbon atoms) or an arylene group, wherein R ₂ , R ₃ , R ₅ and R ₆ Is each independently an alkyl group having 1 to 3 carbon atoms, or R ₁ is a group having two nitrogen atoms and R ₂ , R ₃ , R ₅ and R _{6 in} the formula Wherein R ₂ and R ₅ have the same meanings as described above, or a group represented by the formula: Wherein R ₃ and R ₆ have the same meanings as described above, and X ₁ ^- is a counter ion and m is a number of 5 or more. (A2) general formula (II) [Wherein A is a general formula (Wherein B is an alkylene group having 1 or 2 carbon atoms, R ₂₁ , R ₂₂ and R ₂₃ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X ₂ ^- is Or a group represented by the general formula (Wherein, R ₂₄ is an alkyl group or benzyl group having 1 to 3 carbon atoms, and X ₃ ^- is a counter ion) or a general formula: (Wherein R ₂₅ is an alkyl group having 1 or 2 carbon atoms;
₂₆ , R ₂₇ and R ₂₈ each independently represent a hydrogen atom or a carbon atom
And X ₃ ^- is a counter ion), and n is a number of 10 or more.] (A3) a compound represented by the general formula (III): (In the formula, v is 3 or 4, R ₉₁ is a hydrogen atom; an alkyl group having 1 to 4 carbon atoms; 1 carbon atom substituted by a hydroxy group, a mercapto group, or an alkylthio group having 1 to 3 carbon atoms. to 4 alkyl group; a or imidazolylmethyl group or indolylmethyl group, R ₉₂ is -N ⁺ H ₃ X ₅ ^- or _{^{-N + HC (NH) NH 2}} X 6 - a and, X ₅ ^- and X ₆ ^- are each independently a counter ion, t is 20 to 100, and r is 1
A compound represented by 0 or more integers), and (a4) selected from the group consisting of cationic polysaccharides, wherein the cationic polymer at least one and (B) -COO in the repeating units ^- group, --SO3 ^- group or -PO ₃ ^2-group or -PO ₃ H ^- a anionic polymer containing group, (b1) the general formula (IV) (In the formula, u is 1 or 2, R ₈₁ is a hydrogen atom; an alkyl group having 1 to 4 carbon atoms; 1 carbon atom substituted by a hydroxy group, a mercapto group, or an alkylthio group having 1 to 3 carbon atoms. A compound represented by the formula: (b2) a compound represented by the following formula: (V) alkyl groups; or an imidazolylmethyl group or an indolylmethyl group, s is 20 to 100, and q is an integer of 10 or more. ) (Wherein, R ₃₁ is a hydrogen atom or a methyl group, R ₃₂ is an alkyl group having 6 to 18 carbon atoms, Y is a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or A salt thereof, or a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, or an aryl group containing a phosphate group or a salt thereof, a is a number of 20 to 100, and p is a number of 10 or more. And (b3) an anionic polysaccharide selected from the group consisting of: a polyelectrolyte complex obtained by reacting at least one of the anionic polymers. Agent.

The present invention also relates to an antibacterial material comprising the above-mentioned polyelectrolyte complex supported on a carrier.

In the present invention, as the cationic polymer (A), (a1) the general formula (I) [Wherein, R ₁ and R ₄ each independently represent an alkylene group having 1 to 10 carbon atoms, preferably a linear or branched alkylene group having 2 to 8 carbon atoms; (Wherein, R ₁₁ and R ₁₂ are each independently an alkylene group having 1 or 2 carbon atoms, and preferably, R ₁₁ and R ₁₂ are p
R ₂ , R ₃ , R ₅ and R ₆ are each independently an alkyl group having 1 to 3 carbon atoms, or an arylene group represented by Or R ₁ together with the _two nitrogen atoms in the formula and R ₂ , R ₃ , R ₅ and R ₆ Wherein R ₂ and R ₅ have the same meanings as described above, or a group represented by the formula: Wherein R ₃ and R ₆ have the same meaning as described above, wherein R ₄ has the same meaning as described above, and X ₁ ^- is a counter ion, and m is A compound represented by the following general formula (II): [Wherein A is a general formula (Wherein B is an alkylene group having 1 or 2 carbon atoms, R ₂₁ , R ₂₂ and R ₂₃ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X ₂ ^- is Or a group represented by the general formula (Wherein, R ₂₄ is an alkyl group or benzyl group having 1 to 3 carbon atoms, and X ₃ ^- is a counter ion) or a general formula: (Wherein R ₂₅ is an alkyl group having 1 or 2 carbon atoms;
₂₆ , R ₂₇ and R ₂₈ each independently represent a hydrogen atom or a carbon atom
(Wherein X ₄ ^- is a counter ion), and n is a number of 10 or more] (ie, a quaternary ammonium salt polymer), a3) General formula (III) (In the formula, v is 3 or 4, R ₉₁ is a hydrogen atom; an alkyl group having 1 to 4 carbon atoms; 1 carbon atom substituted by a hydroxy group, a mercapto group, or an alkylthio group having 1 to 3 carbon atoms. Or 4 alkyl groups; or imidazolylmethyl group or indolylmethyl group; for example, methyl group, isopropyl group, isobutyl group, s-butyl group, hydroxymethyl group, hydroxyethyl group, methylthioethyl group,
Mercaptomethyl group, 5-imidazolylmethyl group or 3
- an imidazolylmethyl group, R ₉₂ is -N ⁺ H ₃ X ₅ ^- or -
_{^{N + H 2 C (NH)}} NH 2 X 6 - a and, X ₅ ^- and X ₆ ^- are each independently a counter ion, t is 20 to 100, and r is 10
And at least one compound selected from the group consisting of (a4) a cationic polysaccharide.

Further, as the anionic polymer (B), (b1) the general formula (IV) (In the formula, u is 1 or 2, R ₈₁ is a hydrogen atom; an alkyl group having 1 to 4 carbon atoms; 1 carbon atom substituted by a hydroxy group, a mercapto group, or an alkylthio group having 1 to 3 carbon atoms. Or 4 alkyl groups; or imidazolylmethyl group or indolylmethyl group; for example, methyl group, isopropyl group, isobutyl group, s-butyl group, hydroxymethyl group, hydroxyethyl group, methylthioethyl group,
Mercaptomethyl group, 5-imidazolylmethyl group or 3
-Imidazolylmethyl group, s is 20-100,
And q is an integer of 10 or more) (ie, an acidic amino acid polymer), (b2) a compound represented by the general formula (V): (Wherein, R ₃₁ is a hydrogen atom or a methyl group, R ₃₂ is an alkyl group having 6 to 18 carbon atoms, preferably a linear or branched alkyl group having 6 to 14 carbon atoms; Is a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, or a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, or an aryl group containing a phosphoric acid group or a salt thereof. Yes, a is 20-100,
(P is a number of 10 or more), and at least one selected from the group consisting of (b3) anionic polysaccharides Use compounds.

BEST MODE FOR CARRYING OUT THE INVENTION The polymer electrolyte complex (poly
electrolyte complex: may be referred to as PEC below)
Is a substance known per se. Polymer electrolyte complex (PE
C) is, for example, as described in Japanese Patent Application No. 49-8581, a solution of a cationic polymer which is a polymer electrolyte having a positive charge and a solution of an anionic polymer which is a polymer electrolyte having a negative charge. It can be formed instantly by mixing. The PEC thus obtained is a special 3
It is soluble in the original solvent (for example, water / acetone / low-molecular salt having a specific composition), but is insoluble in common solvents. PEC membranes can be used as dialysis membranes because they show high permeability to various low molecular weight compounds. PE
C can provide various materials with various properties depending on the type of starting polymer (polymer electrolyte), their mixing ratio, preparation conditions, etc., but it has been known that PEC has antibacterial properties. I didn't.

In the present specification, an alkyl group having 1 to 3 carbon atoms is
For example, a methyl group, an ethyl group, or an n- or i-propyl group. The alkyl group having 1 to 4 carbon atoms may be, for example, n- or i in addition to the alkyl group having 1 to 3 carbon atoms.
-, S-, or t-butyl group. The alkylene group having 1 or 2 carbon atoms is, for example, a methylene group, an ethylene group or an ethylidene group. Examples of the linear or branched alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and octamethylene. Group, hennamethylene group, decamethylene group, ethylethylene group, or ethyltrimethylene group. The linear or branched alkyl group having 6 to 18 carbon atoms is, for example, one linear or branched alkyl group having 6 to 18 carbon atoms, and one linear or branched alkyl group having 1 to 3 carbon atoms. Or an alkyl group having 6 to 15 carbon atoms substituted by more than
Particularly, it is an alkyl group having 6 to 10 carbon atoms substituted by one straight-chain alkyl group having 1 to 3 carbon atoms. The arylene group is, for example, a phenylene group or a naphthylene group. Salts of carboxylic, sulfonic or phosphoric acid groups include, for example, alkali metals (eg, sodium, potassium),
Or salts with alkaline earth metals (eg, calcium, magnesium). The aryl group containing a sulfonic acid group or a salt thereof is, for example, a sulfophenyl group.

The counter ion present in the starting cationic polymer (A) and anionic polymer (B) is absent in the PEC product as a result of both reactions. Therefore, any ion may be used as long as it does not inhibit the reaction between the two. Preferred counterions are halogen atom ions, especially chloride, bromide or iodine ions.

PEC obtained by the reaction between the cationic polymer (A) and the anionic polymer (B) is N ^{+ of} the cationic polymer.
It has a structure in which moieties and acid (eg, carboxylic acid, sulfonic acid, phosphoric acid) moieties of the anionic polymer are successively bonded by clonality. That is, the polymers are bridged by ionic bonds to form a solvent-insoluble gel.

For example, the cationic polymer (a1) represented by the general formula (I) and the anionic polymer (b) represented by the general formula (IV)
The PEC generated from 1) is represented by the following general formula (VI).

In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₈₁ , m, u, s and q have the same meaning as described above, provided that 0.25 ≦ 2 m / q ≦ 4.0
It is assumed that

Further, the cationic polymer (a) represented by the general formula (I)
Anionic polymer (b2) represented by 1) and general formula (V)
The PEC produced from is represented by the following general formula (VII).

Wherein a _{R 1, R 2, R 3} , R 4, R 5, R 6, R 31, R 32, m, a and p are as defined above, Y 'is -COO ^- group, -SO ₃ ^- group, or -PO ₃ ^2-group or PO ₃ H ^- group, or a -COO ^- group, -SO ₃ ^-
Group or -PO ₃ ^2-group or PO ₃ H ^- an aryl group containing a group, and it is assumed that 0.25 ≦ 2m / P ≦ 4.0.

Further, a cationic polymer represented by the general formula (II) (a
2) and an anionic polymer (b1) represented by the general formula (IV)
And the PEC produced from the following general formula (VIII) or (I
X).

In each of the above formulas (VIII) and (IX), B, R ₂₁ , R ₂₂ , R
₂₃ , R ₂₄ , R ₈₁ , n, u, s and q have the same meaning as described above, provided that 0.25 ≦ n / q ≦ 4.0.

PEC produced from the cationic polymer (a2) represented by the general formula (II) and the anionic polymer (b2) represented by the general formula (V) is represented by the following general formula (X) or (XI). You.

In each of the above formulas (X) and (XI), B, R ₂₁ , R ₂₂ ,
R ₂₃ , R ₂₄ , R ₃₁ , R ₃₂ , Y ′, n, a and p have the same meaning as described above, provided that 0.25 ≦ n / p ≦ 4.0.

PEC produced from the cationic polymer (a3) represented by the general formula (III) and the anionic polymer (b1) represented by the general formula (IV) is represented by the following general formula (XII).

In the formula, R ₉₁ , R ₈₁ , r, t, v, q, u and s have the same meanings as described above, and R ₉₃ is a —N ⁺ H ₃ X ₅ ^— group or —N ⁺ H ₂ C (NH) N
A H ₂ X ₆ ^— group, provided that 0.25 ≦ r / q ≦ 4.0.

Further, a cationic polymer represented by the general formula (III) (a
3) and an anionic polymer (b2) represented by the general formula (V)
The PEC generated from is represented by the following general formula (XIII).

In the formula, R ₉₁ , R ₉₃ , R ₃₁ , R ₃₂ , Y ′, r, t, v, a and p have the same meaning as described above, provided that 0.25 ≦ r / p ≦ 4.0.

PEC that can be used as an antibacterial agent in the present invention may be any solvent-insoluble solid, and its average molecular weight is not particularly limited, but is generally 10 to 1000, preferably, in terms of the number of ion sites. Is 20 to 100. The average molecular weights of the cationic polymers (a1) to (a4) and the anionic polymers (b1) to (b3), which are the starting materials, are not particularly limited, but a preferable average molecular weight range is represented by the formula (I). In the cationic polymer (a1), m is 5
To 500 (particularly 5 to 100), and in the cationic polymer (a2) represented by the general formula (II), n is 10 to 1000 (particularly
In the cationic polymer (a3) represented by the general formula (III), r is 10 to 1000 (particularly, 10 to 500). On the other hand, in the anionic polymer (b1) represented by the general formula (IV), q is 10 to 1000 (particularly 10 to 500), and the anionic polymer (b2) represented by the general formula (V)
In the formula, p is 10 to 1000 (particularly, 10 to 500).

Specific examples of the cationic polymer (a1) of the general formula (I) include quaternary polyethyleneimine chloride and poly (N, N, N ', N'-tetramethyl-alkylene-p-xylylenediammonium dichloride). , Poly (N, N, N ',
N'-tetramethyl-alkylene-diammonium dichloride), poly (N, N-dimethyl-3-hydroxypropylammonium chloride), poly (2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride), poly (2- Methacryloyloxyethyltrimethylammonium chloride), poly (glycidyltrimethylammonium chloride), poly [(dimethyliminio) ethylene (dimethyliminio) methylene-1,4-phenylenemethylene dichloride] [generally referred to as 2X], Poly [(dimethyliminio) hexamethylene (dimethyliminio) methylene-1,4-phenylenemethylene dichloride] [generally referred to as 6X], poly [(dimethyliminio) hexamethylene chloride] [generally, 6, Called 6 ], Poly (N- ethyl-4-vinyl-pyridinium bromide), poly (dimethyldiallylammonium chloride) and the like.

Specific examples of the cationic polymer (a2) of the general formula (II) include poly (vinylbenzyltrimethylammonium chloride), polyvinylpyridinium chloride, and poly (N-benzyl-4-vinylpyridinium chloride).

Specific examples of the cationic polymer (a3) of the general formula (III) include polylysine, polyarginine or a copolymer of monomers constituting these polymers, and further, these monomers and glycine, alanine, phenylalanine, tyrosine, Copolymers with valine, leucine, isoleucine, serine, threonine, methionine, cysteine, histidine, proline, and / or tryptophan.

Specific examples of the cationic polysaccharide (a4) are as follows.

(1) Chitosan and its derivatives: Wherein R ₆₆ is a hydrogen atom or an acetyl group, X ₇ ^- is a counter ion, the degree of deacetylation is 50-100%, preferably 70-100%, and q ₂₆ is 20-3000, preferably 50 ~ 1000. Note that the N ⁺ atom of the —N ⁺ H ₂ R ₆₆ group in the formula is bonded to the anion group of the anion polymer.

(2) Diethylaminoethyl derivative of neutral polysaccharide: Examples of the neutral polysaccharide include dextran, cellulose, mannan, starch, and agarose. The degree of substitution of these derivatives with diethylaminoethyl is 0.5 to 2.0 groups, preferably 0.7 to 1.5 groups per sugar residue, and the degree of polymerization is 50 to 5000, preferably 100 to 1000. Note that the nitrogen atom of the diethylaminoethyl group is bonded to the anion group of the anion polymer.

Specific examples of the anionic polymer (b1) of the general formula (IV) include polyglutamic acid, polyaspartic acid or a copolymer of monomers constituting these polymers, and further, these monomers and glycine, alanine, phenylalanine, Copolymers with tyrosine, valine, leucine, isoleucine, serine, threonine, methionine, cysteine, histidine, proline, and / or tryptophan.

The polyamino acids represented by the general formulas (III) and (IV) can be synthesized by a general acid anhydride monomer method, active esterification method, Maryfield method and the like.

Specific examples of the anionic polymer (b2) of the general formula (V) include polyacrylic acid, polymethacrylic acid, polyitaconic acid monoester, polymaleic acid monoester, polyvinylsulfonic acid, polystyrenesulfonic acid,
Copolymers of any two or more of the monomers constituting these polymers, and C6 to C18 bonded to the carboxyl groups of these monomers and the monomers by ester bonds.
It is a copolymer with a carboxylic acid derivative having three alkyl groups.

Specific examples of the anionic polysaccharide (b3) are as follows.

(1) Hyaluronic acid and its derivatives: Wherein R ₄₁ is a hydrogen atom or an alkali metal (e.g., sodium or potassium), but is at least partially absent in the PEC product by reaction with the cationic polymer, and q ₁ 100-12000, preferably 200-8000.

(2) Alginic acid and its derivatives: Wherein R ₄₂ is a hydrogen atom or an alkali metal (e.g., sodium or potassium), but is at least partially absent in the PEC product by reaction with the cationic polymer, and q ₂ is 100 to 10,000, preferably Is 200-5000.

(3) Chondroitin sulfate A: Wherein, q ₃ is 10 to 100, preferably 10 to 50, COO at least a portion of the COOH groups and / or SO ₃ H group in the formula by reaction with the cationic polymer ^- group and / or SO ₃ ^- Be the basis.

(4) Chondroitin sulfate C: Wherein, q ₄ is 10 to 100, preferably 10 to 50, COO at least a portion of the COOH groups and / or SO ₃ H group in the formula by reaction with the cationic polymer ^- group and / or SO ₃ ^- Be the basis.

(5) Chondroitin sulfate B (dermatan sulfate) and its derivatives: Wherein, q ₅ is from 20 to 100, preferably 40 to 50, COO at least a portion of the COOH groups and / or SO ₃ H group in the formula by reaction with the cationic polymer ^- group and / or SO ₃ ^- Be the basis.

(6) Chondroitin sulfate D and its derivatives: Wherein, q ₆ is 10 to 500, preferably 20 to 100, COO at least a portion of the COOH groups and / or SO ₃ H group in the formula by reaction with the cationic polymer ^- group and / or SO ₃ ^- Be the basis.

(7) Chondroitin sulfate E and its derivatives: Wherein, q ₇ 10 to 300, preferably 20 to 100, COO by reaction with at least a portion of the cationic polymer of COOH groups and / or SO ₃ H group in the formula ^- group and / or SO ₃ ^- Be the basis.

(8) Heparan sulfate and its derivatives: Wherein, q ₈ is 7-200, preferably 10 to 100, COO by reaction with at least a portion of the cationic polymer of COOH groups and / or SO ₃ H group in the formula ^- group and / or SO ₃ ^- Be the basis.

(9) Heparin and its derivatives: Wherein, q ₉ 100 to 500, preferably 100 to 300, COO by reaction with at least a portion of the cationic polymer of COOH groups and / or SO ₃ H group in the formula ^- group and / or SO ₃ ^- Be the basis.

(10) κ-carrageenan and its derivatives: In the formula, R ₅₀ is a hydrogen atom or an SO ₃ H group, and q ₁₀ is ₁₀₀ to 1
0000, preferably 100 to 500, wherein at least a part of the SO ₃ H group is converted to an SO ₃ ^- group by reaction with the cationic polymer.

(11) λ-carrageenan and derivatives thereof: In the formula, R ₅₁ is a hydrogen atom or a SO ₃ H group, and q ₁₁ is 100 to 1
0000, preferably 100 to 500, wherein at least a part of the SO ₃ H group is converted to an SO ₃ ^- group by reaction with the cationic polymer.

Further, a neutral natural polysaccharide can be used as an anionic polysaccharide (b3) by a treatment such as carboxymethylation, sulfation or phosphorylation. Examples of those modified polysaccharides are as follows. is there.

(12) Cellulose derivatives: Wherein R ₅₂ is a hydrogen atom, a carboxymethyl group, a sulfate group or a phosphate group, and q ₁₂ is 100 to 15,000, preferably 200
50005000, wherein a COOH group, a SO ₃ H group and / or a PO ₃ H ₂
At least a portion of the group may react with the cationic polymer, COO ^- group, SO ₃ ^- groups and / or PO ₃ ^2-group or PO ₃ H ^- underlying.

(13) Chitin derivatives: In the formula, R ₅₃ is a hydrogen atom, a carboxymethyl group, a sulfate group or a phosphate group, and q ₁₃ is 50 to 8000, preferably 100 to
5000, and at least a part of the COOH group, SO ₃ H group, and / or PO ₃ H ₂ group in the formula is obtained by reaction with the cationic polymer.
COO ^- groups, SO ₃ ^- groups and / or PO ₃ ^2- groups or PO ₃ H ^- groups.

(14) Carboxymethyl starch and its derivatives: Wherein R ₅₄ is a hydrogen atom, a carboxymethyl group, a sulfate group or a phosphate group, and q ₁₄ is 100 to 8000, preferably 200
50005000, wherein a COOH group, a SO ₃ H group and / or a PO ₃ H ₂
At least a portion of the group may react with the cationic polymer, COO ^- group, SO ₃ ^- groups and / or PO ₃ ^2-group or PO ₃ H ^- underlying.

(15) Amylose derivative: In the formula, R ₅₅ is a hydrogen atom, a carboxymethyl group, a sulfate group or a phosphate group, and q ₁₅ is 100 to 8000, preferably 100
50005000, wherein a COOH group, a SO ₃ H group and / or a PO ₃ H ₂
At least a portion of the group may react with the cationic polymer, COO ^- group, SO ₃ ^- groups and / or PO ₃ ^2-group or PO ₃ H ^- underlying.

(16) Amylopectin derivative: Wherein R ₅₆ is a hydrogen atom, a carboxymethyl group, a sulfate group or a phosphate group, and q ₁₆ is 100 to 100,000, preferably 10
0 to 10000, and a COOH group, a SO ₃ H group and / or a PO ₃ H
At least a portion of the ₂ groups react with the cationic polymer, COO ^- group, SO ₃ ^- groups and / or PO ₃ ^2-group or PO ₃ H ^- underlying.

(17) β-1,3′-glucan derivative (for example, curdlan): In the formula, R ₅₇ is a hydrogen atom, a carboxymethyl group, a sulfate group or a phosphate group, and q ₁₇ is 50 to 1000, preferably 100 to
300, and at least a part of the COOH group, SO ₃ H group and / or PO ₃ H ₂ group in the formula is converted to CO 2 by the reaction with the cationic polymer.
O ^- group, SO ₃ ^- groups and / or PO ₃ ^2-group or PO ₃ H ^- underlying.

(18) β-1,2′-glucan derivative: In the formula, R ₅₈ is a hydrogen atom, a carboxymethyl group, a sulfate group or a phosphate group, and q ₁₈ is 100 to 4000, preferably 100
Is 3500, COOH groups in the formula, SO ₃ H groups and / or PO ₃ H ₂
At least a portion of the group may react with the cationic polymer, COO ^- group, SO ₃ ^- groups and / or PO ₃ ^2-group or PO ₃ H ^- underlying.

(19) β-1,3′-; β-1,6′-glucan (eg, lentinan, schizophyllan, coriolan) derivatives: In the formula, R ₅₉ is a hydrogen atom, a carboxymethyl group, a sulfate group or a phosphate group, and q ₁₉ is 100 to 100,000, preferably 10
0 to 50000, wherein COOH group, SO ₃ H group and / or PO ₃ H
At least a portion of the ₂ groups react with the cationic polymer, COO ^- group, SO ₃ ^- groups and / or PO ₃ ^2-group or PO ₃ H ^- underlying.

(20) Dextran derivative: Wherein R ₆₀ is a hydrogen atom, a carboxymethyl group, a sulfate group or a phosphate group, and q ₂₀ is 100 to 300,000, preferably 20
0 to 100,000, a COOH group, a SO ₃ H group and / or a PO ₃
At least a portion of the H ₂ groups react with the cationic polymer, COO ^- group, SO ₃ ^- groups and / or PO ₃ ^2-group or PO ₃ H ^- underlying.

(21) Pullulan derivative: In the formula, R ₆₁ is a hydrogen atom, a carboxymethyl group, a sulfate group or a phosphate group, and q ₂₁ is 300 to 2000, preferably 500
COOH group, SO ₃ H group and / or PO ₃ H ₂
At least a portion of the group may react with the cationic polymer, COO ^- group, SO ₃ ^- groups and / or PO ₃ ^2-group or PO ₃ H ^- underlying.

(22) Agarose derivative: Wherein R ₆₂ is a hydrogen atom, a carboxymethyl group, a sulfate group or a phosphate group, and q ₂₂ is 20 to 200, preferably 20 to 20.
0, and at least a part of the COOH group, SO ₃ H group and / or PO ₃ H ₂ group in the formula is COO ⁻
Group, SO ₃ ^- groups and / or PO ₃ ^2-group or PO ₃ H ^- underlying.

(23) β-1,4′-galactan derivative: Wherein R ₆₃ is a hydrogen atom, a carboxymethyl group, a sulfate group or a phosphate group, and q ₂₃ is 50 to 200, preferably 50 to 20.
0, and at least a part of the COOH group, SO ₃ H group and / or PO ₃ H ₂ group in the formula is COO ⁻
Group, SO ₃ ^- groups and / or PO ₃ ^2-group or PO ₃ H ^- underlying.

(24) Mannan derivative: In the formula, R ₆₄ is a hydrogen atom, a carboxymethyl group, a sulfate group or a phosphate group, and q ₂₄ is 50 to 5000, preferably 100 to
3000, wherein at least a part of the COOH group, SO ₃ H group and / or PO ₃ H ₂ group in the formula is reacted with the cationic polymer,
COO ^- groups, SO ₃ ^- groups and / or PO ₃ ^2- groups or PO ₃ H ^- groups.

(25) Inulin derivative: In the formula, R ₆₅ is a hydrogen atom, a carboxymethyl group, a sulfate group or a phosphate group, and q ₂₅ is 20 to 100, preferably 20 to 80.
Wherein at least some of the COOH, SO ₃ H and / or PO ₃ H ₂ groups in the formula are reacted with a cationic polymer to form COO ⁻
Group, SO ₃ ^- groups and / or PO ₃ ^2-group or PO ₃ H ^- underlying.

The polymer electrolyte complex (PEC) used in the present invention can be prepared by a usual method. That is, the respective aqueous solutions (10 ⁻⁵ mol / L to 10 ⁻² mol / L) of the above-mentioned cationic polymer and anionic polymer were mixed with the concentration ratio between the cationic site of the cationic polymer and the anionic site of the anionic polymer (cation site / anionic site). ) Is reacted in an aqueous solution within the range of 0.25 to 4.0, preferably within the range of 0.4 to 2.5.
If the concentration ratio between the cation site and the anion site (cation site / anion site) is out of the range of 0.25 to 4.0, the formation of a polymer electrolyte complex (PEC) becomes difficult, which is not preferable. Since the reaction is relatively active, the pH, ionic strength, temperature, etc. of the solution can be in a relatively wide range,
Generally, it is carried out at pH 3-9, ionic strength 0-1.0 and 20-40 ° C.

The charge balance of the PEC used in the present invention is -6 to +6, preferably -4.5 to +4.5. Here, the charge balance expresses the charge state of PEC by the concentration ratio of the cationic and anionic sites of the cationic polymer and the anionic polymer as the starting materials. For example, if the concentration of the cationic site of the cationic polymer to be used is equal to the concentration of the anionic site of the anionic polymer, the resulting PEC
Is ± 0. If the concentration ratio is higher (i.e., the concentration at the cation site is higher), the charge balance is positive, and if it is lower (i.e., the concentration at the anion site is higher), the charge balance is negative. When the concentration ratio is 1.5, the charge balance is +2, and when the concentration ratio is 0.5, the charge balance is -3.3. Adjustment of charge balance
It can be easily carried out by changing the mixing amount of the aqueous solution of the cationic polymer and the aqueous solution of the anionic polymer at the same concentration. By adjusting the charge balance, a state of excess cation or excess anion can be obtained.

Since the polymer electrolyte complex (PEC) is obtained as a gel-like precipitate from the reaction solution, the gel-like precipitate remains as it is.
Or, it can be molded and processed directly from the gel-like precipitate to obtain an appropriate shape (eg, fibrous, film, sheet, lump,
Latex or gel), and can be used as it is as a wet or dry antibacterial material. Also, since PEC can be attached or adhered to almost any material, it can be coated on a suitable carrier to prepare an antimicrobial material. In some applications (when the liquid itself has antibacterial properties), the PEC reaction liquid can be used as it is (suspension).

Examples of the carrier made of an organic material include an organic polymer material, for example, a synthetic or natural resin, a synthetic or natural rubber, a synthetic or natural fiber, a biopolymer material, leather, wood, pulp, and paper.

As the synthetic resin, for example, a hydrocarbon polymer (for example, polyolefin, polyethylene, polypropylene,
Polybutene-1, poly-4-methylpentene-1, styrene resin, polyacetylene); halogenated hydrocarbon polymer (eg, polyvinyl chloride, polyvinylidene chloride, fluororesin); unsaturated alcohol or ether polymer (eg, Polyvinyl alcohol, polyvinyl ether, polyphenylene oxide, polyphenylene sulfide, acetal resin, polyether, polyvinyl butyral, polyether sulfone epoxy resin); unsaturated aldehyde or ketone polymer (for example, phenol resin,
Urea resin); unsaturated carboxylic acid polymer (eg, polyacrylate, acrylic resin); unsaturated ester polymer (eg, polyvinyl ester, polyarylate, wholly aromatic polyester, polyethylene terephthalate, polycarbonate, polybutylene diallyl phthalate, Unsaturated polyester resin); unsaturated nitrile polymer (eg, polyacrylonitrile, ABS resin, AAS resin, AES resin); unsaturated amine polymer (eg, polyvinylamine, polyimide, polyamide, melamine resin, polyethyleneimine, polyurethane); Other examples include silicone resins, the above-mentioned copolymers, blend resins, and thermoplastic elastomers. Examples of the natural resin include a cellulose derivative resin.

As synthetic rubber, for example, styrene-butadiene rubber, butadiene rubber, isoprene rubber, nitrilo rubber,
Examples include chloroprene rubber, butyl rubber, ethylene-propylene rubber, acrylic rubber, chlorinated polyethylene rubber, fluorine rubber, silicone rubber, urethane rubber, and polysulfide rubber.

Examples of the synthetic fibers include regenerated cellulose (viscose rayon, cupra) acetate, triacetate, polyamide, acrylic, vinylon, vinylidene, polyvinyl chloride, polyester, polyethylene, polypropylene, polybenzoate, polyclar, aramidphenol-based fiber, polyurethane Examples include system fibers, fluorine fibers, polyvinyl alcohol, carbon fibers, and silicon carbide fibers. As natural fibers, for example, cotton, silk,
Wool, hemp and wood can be mentioned.

As the carrier, inorganic materials such as glass, minerals (eg, asbestos), enamel, cement, ceramics, artificial stone,
Metals (eg, ferrous, steel, non-ferrous metals, alloys) can also be used. The shape and form of the carrier are not particularly limited, and may be fibrous, filamentous, film-like, sheet-like, woven, non-woven, rod-like, cord-like, spherical, powdery, granular, porous, hollow, or aggregated. , A foam, a gel, and the like.

The PEC can be supported on the carrier by any known method, for example, a method such as coating, spraying or dipping. The PEC solution may simply be brought into contact with the carrier.
For example, after mixing the aqueous solution of the cationic polymer and the aqueous solution of the anionic polymer in the reaction vessel, immediately transfer the reaction solution to a predetermined container, and leave it for about 24 hours to allow sufficient precipitation of PEC, and then remove the supernatant. And 1 with saline and distilled water
After washing about 3 times, drying at 60 to 100 ° C. for 6 to 12 hours and annealing, PEC can be firmly adhered to the bottom surface of the container. In order to coat the entire inner surface of the container, PEC is sufficiently precipitated by rotating and shaking for about 24 hours, then the supernatant is removed, washed as above, and annealed to firmly attach the PEC to the container surface. Can be done.

In the case of fibrous, beaded or woven fabric materials, those materials may be dipped in a PEC solution for about 24 hours, and then treated in the same manner as described above. Also, JP-A-50-63096
As described in the publication, PEC synthesis is carried out in the presence of a water-soluble organic solvent (for example, a mixture of water, acetone and sodium bromide), and the reaction solution is applied as it is as a paint, sprayed, or It can be immersed.

If the surface of the carrier supporting PEC is highly hydrophobic (for example, a polycarbonate carrier), a treatment to impart hydrophilicity to the surface (hypochlorous acid treatment, organic solvent treatment, plasma treatment, ultraviolet treatment, etc.) It is preferable to carry out in advance.

The PEC-supported carrier thus obtained can be used as it is as an antibacterial material, or various antibacterial products can be prepared using the antibacterial material. As the antibacterial material that can be used as it is, a material in which PEC is supported on at least a part (preferably the entirety) of the surface of a fiber material (for example, fiber, filament, woven fabric, or nonwoven fabric), for example, PEC is supported Gauze, absorbent cotton, and fabric (for aseptic clothing products for medical, hygiene, or beauty). From these PEC-loaded fiber materials, for example,
Masks, eye patches, bandages, sheets, absorbent pads (eg, ears, nose, oral or menstrual tampons), and napkins can be easily prepared.

Furthermore, various aseptic clothing, such as underwear (shirts, underwear, socks, etc.), baby linen products (eg, baby pants, bibs, garments, bodice, etc.), handkerchiefs, corsets, girdle, brassiere, seawater Clothes, surgical clothing, surgeons or patient aprons, rescuers, diving clothing, lab clothing, protective clothing (surgical gloves), masks, surgical hats can also be prepared.

The antibacterial product prepared using the PEC-supported antibacterial material is not particularly limited as long as it is a product that preferably suppresses the growth of microorganisms. For example, medical equipment, hygiene equipment (eg, hospital bedspread,
Sheets, sterile clothing, bandages, diapers, eye patch gauze, tampons, contact lenses, contact lens containers, pharmaceutical storage containers, blood transfusion containers), food-related equipment (eg, food packaging materials, food storage containers), life-related equipment (E.g., tableware, kitchenware, e.g. cupboard underlay sheets,
Sanitary products such as toilet seat covers), hairdressing and beauty tools,
Equipment that easily generates slime (eg, dialysis membrane, excess material), and other physicochemical equipment (eg, humidifiers, washing machines,
Thermostat) and the like.

Pharmaceutical equipment particularly preferred as an antibacterial product prepared using the PEC-supported antibacterial material of the present invention (preferably,
Disposable medical fee-related equipment) are listed below.
Also, their preferred carrier materials are shown in parentheses.

General medical and nursing tools include, for example, adapters (or connectors) (polyethylene, polypropylene,
Polyamide), irrigator (polyvinyl chloride), indicator (Japanese paper, paper), apron (non-woven fabric), diaper (polypropylene fiber, non-woven fabric, paper, cotton, polyamide,
Pulp), gauze (nonwoven fabric, paper, cotton, polyamide, acrylic, polyester), cup [sample holder] (polypropylene, polyethylene, polystyrene, paper), catheter [tube] (polyvinyl chloride, rubber, silicone, polyethylene, polypropylene) , Polyamide), cover (nonwoven fabric, polyethylene), cuff (polyvinyl chloride, rubber), eye patch (gauze, nonwoven fabric, synthetic fiber), enema (synthetic fiber), cap (nonwoven fabric, paper), suction device (polyvinyl chloride) , Plastic, rubber), clamp [clip] (sponge, rubber, metal, polyamide, polyvinyl chloride, acetal resin), inspection garment (nonwoven fabric), coil [for blood heating] (polyvinyl chloride, polypropylene),
Oxygen tent (polyethylene, polyvinyl chloride), stopcock [three-way] (polyamide, polyacetal, delrin, polyvinyl chloride, polymethylpentene, artificial nose (paper, polypropylene), stopper (polyethylene,
Polystyrene, polypropylene), blood transfusion set (polyethylene, polystyrene, polypropylene, rubber, polyvinyl chloride, metal), towel (nonwoven fabric), laparoscope (polyvinyl chloride), syringe (rubber, polypropylene, medical silicone oil, polymethylpentene) , Injection needle (polyethylene, stainless steel, polypropylene, polyvinyl chloride), stethoscope (polyvinyl chloride), rectoscope (polyvinyl chloride), tape [adhesive plaster] (acrylic, polyester, polyethylene, cotton, Japanese paper, polyvinyl chloride) , Polyamide, rayon), T-shaped belt (nonwoven fabric, paper), gloves (glove) (polyethylene, polyvinyl chloride, rubber), eyedroppers (polyethylene, polypropylene), trays (compressed pulp, paper), urinals (polyester, Polyethylene, polypropylene, polychlorinated Nyl, ABS, rubber), name band (polyvinyl chloride, polyethylene), pus bon (paper, pulp), bag (polyvinyl chloride, stainless steel, polyethylene, polystyrene, rubber, paper), pat [cotton] (cotton, Gauze, polyester beads, non-woven fabric,
Paper), tension treatment needle (stainless steel), splint (cine) (polyisoprene), abdominal band (spandex), casting bandage (cotton, gauze, knit, nonwoven fabric, plaster, polyamide), mouthpiece (polystyrene, paper), Mask (polypropylene, polyethylene, polyamide, polyvinyl chloride, non-woven fabric), mat (polyethylene, aluminum, adhesive), manometer [press column] (polystyrene), cotton ball (cotton), cotton swab (birch), finger sack (polyethylene) , Rubber), indwelling needles (stainless steel, polyvinyl chloride, ABS, rubber, metal, polyethylene, polypropylene, fluororesin), connecting pipes (polyvinyl chloride, polyethylene, rubber, metal polypropylene, polyamide), etc. .

Examples of anesthesia and operating room tools include intrafusers for vascular injection (polyvinyl chloride, ABS, polyethylene, polypropylene, rubber, metal, Teflon), airways (polyvinyl chloride, ethylene-vinyl acetate copolymer), eyelids Container (tantalum), gown (nonwoven fabric), catheter (polyvinyl chloride, silicone-mixed polyvinyl chloride, latex, stainless steel, Teflon), shoe cover (nonwoven fabric), cuff (latex), cap (nonwoven fabric, cellulose), suction (Suction tube) (polyvinyl chloride, polyamide, polypropylene), pharyngoscope (polyvinyl chloride), connector (polyethylene), vascular injection set (polyethylene, polypropylene, polyacetal, Teflon, polyvinyl chloride, metal, silicone), Towel (non-woven fabric), opposite electrode (Aluminum foil,
Copper, stainless steel foil, both paper, stainless steel plate), tape (nonwoven fabric, filament), gloves (rubber, polyethylene), drape [cloth] (polyvinyl chloride, polyethylene film, nonwoven fabric), drain (polyvinyl chloride, Rubber, silicone rubber), biopsy needles (stainless steel, ABS, polyvinyl chloride, polystyrene, metal), sutures (silk, polyamide, polypropylene, polyester, stainless steel, cut gut), masks (polyester, non-woven fabric, glass fiber, Polyethylene), scalpel (stainless steel, polyvinyl chloride, ABS) and the like.

Further, as inspection and laboratory equipment, for example, cover glass (glass), blood collection tube (glass, acrylic, polypropylene, natural rubber, synthetic rubber), blood collection bottle (polypropylene, polyethylene, polystyrene), test tube (polypropylene, polyethylene) , Styrene resin, glass),
Petri dish (polystyrene, paper, glass), Spitz tube (polypropylene, polystyrene, acetylcellulose, acrylic), dropper (polyethylene), slide glass (glass), tape (paper), electrode [electrocardiogram etc.] (synthetic fiber, paper, Lead wire, polyethylene, gel), incubator (polyethylene, glass, acrylic, synthetic rubber, polystyrene), beaker (polypropylene),
Pipettes (glass, polypropylene), labels (paper) and the like can be mentioned.

In addition, as artificial organs and artificial renal chamber tools, for example,
Catheter [cannula] (Teflon, silicone rubber, polyvinyl chloride, polyethylene, polypropylene,
Cotton), blood circuit (rubber, polyvinyl chloride, polypropylene, polyamide, cellulose), connector (polyamide, polyvinyl chloride, rubber, silicone, Teflon),
Artificial blood vessels (silicone, Dacron, Teflon), artificial lungs (polycarbonate, polypropylene, polyamide, urethane foam, polyvinyl chloride), dialyze (cuprophan, polypropylene, polystyrene, silicone rubber, polyvinyl chloride, nonwoven fabric, Japanese paper), dialysis membrane (Cuprophan, polyacrylonitrile), heat exchangers (silicone rubber, stainless steel), needles (polyethylene, stainless steel, polyvinyl chloride, polyamide, rubber, Teflon), filters (polycarbonate, dacron wool, polypropylene), etc. Can be. Further, it can be used for various facilities (walls, floors, fixtures, air filters, etc.) for maintaining a sterile atmosphere, and endoscopes and the like which are in direct contact with the human body.

In a cationic polyelectrolyte such as a cationic polymer, the supported counter ion is generally a low molecular weight counter ion (eg, a halogen ion), so that the counter ion is eliminated from the polymer to expose a cationic site in the polymer. It is relatively easy. On the other hand, in the PEC used in the present invention, since the counter ions are mutually high molecular compounds, the properties of the quaternary ammonium possessed by the starting cationic polymer are present in a somewhat neutralized form. ing.
It is surprising that PEC having such a structure exhibits antibacterial activity, for which the reason has not been elucidated at present, but the quaternary ammonium contained in the polymer body in a chemically tightly bound manner. The part appears to exhibit sustained antimicrobial activity. Furthermore, PEC generally exhibits remarkably various properties due to changes in hydrophilic microdomain structure, surface water structure change, charge balance, and the like. It is thought that it is doing.

Examples Hereinafter, the present invention will be described more specifically with reference to Examples, but these do not limit the scope of the present invention. The average molecular weight described in the following examples is a number average molecular weight measured by a vapor pressure drop method.

Preparation Example 1: Preparation of PEC (2X-CLA) Poly [(dimethyliminio) which is a cationic polymer
Ethylene (dimethyliminio) methylene-1,4-phenylenemethylene dichloride] (2X) (average molecular weight of about 600
0) 0.015 g (1 × 10 ^-4 mol as cationic sites) and 0.018 g of a random copolymer (CLA) of acrylic acid / lauryl acrylate (acrylic acid content: about 80 mol%; average molecular weight: about 10,000) as an anionic polymer ( 1 as anion seat
× 10 ^-4 mol) and physiological saline (pH 7.
4) Dissolve in 10 ml and obtain 5 ml of the two aqueous solutions thus obtained
Each was mixed at once in a beaker to form a polymer electrolyte complex gel (charge balance: ± 0).

7 ml of the cationic polymer aqueous solution and 3 ml of the anionic polymer aqueous solution prepared in the same manner as above were mixed at once in a beaker, and the mixture was mixed with a polyelectrolyte complex gel (charge balance: +
4) was formed.

Further, a cationic polymer aqueous solution prepared as described above
3 ml and 7 ml of an anionic polymer aqueous solution are mixed at once in a beaker, and then mixed with a polyelectrolyte complex gel (charge balance:
-4) was formed.

Preparation Example 2: Preparation of PEC (2X-COA) Poly [(dimethyliminio) which is a cationic polymer
Ethylene (dimethyliminio) methylene-1,4-phenylenemethylene dichloride] (2X) (average molecular weight of about 300
0) A random copolymer (COA) of 0.015 g (1 × 10 ^-4 mol as a cationic site) and acrylic acid / 2-ethylhexyl acrylate as an anionic polymer (acrylic acid content about 6
0.021 g (average molecular weight: about 8000) and 0.021 g (1 × 10 ⁻⁴ mol as anion sites) were separately added to distilled water (pH 8.
0) Dissolve in 10ml, 5ml of the two aqueous solutions thus obtained
Each was mixed at once in a beaker to form a polymer electrolyte complex gel (charge balance: ± 0).

7 ml of the cationic polymer aqueous solution and 3 ml of the anionic polymer aqueous solution prepared in the same manner as above were mixed at once in a beaker, and the mixture was mixed with a polyelectrolyte complex gel (charge balance: +
4) was formed.

Further, a cationic polymer aqueous solution prepared as described above
3 ml and 7 ml of an anionic polymer aqueous solution are mixed at once in a beaker, and then mixed with a polyelectrolyte complex gel (charge balance:
-4) was formed.

Preparation Example 3: Preparation of PEC (PVBMA-COA) A cationic polymer, poly (vinylbenzyltrimethylammonium chloride) (PVBMA) (average molecular weight: about 15000) 0.021 g (1 × 10 ^-4 mol as a cationic site) and an anionic polymer Separately, 0.021 g (1 × 10 ^-4 mol as an anion site) of a random copolymer (COA) of acrylic acid / 2-ethylhexyl acrylate (acrylic acid content: about 60 mol%; average molecular weight: about 8000) is separately distilled. The resulting solution was dissolved in 10 ml of water (pH 8.0), and 5 ml of each of the two aqueous solutions thus obtained was mixed at once in a beaker to form a polymer electrolyte complex gel (charge balance: ± 0).

7 ml of the cationic polymer aqueous solution and 3 ml of the anionic polymer aqueous solution prepared in the same manner as above were mixed at once in a beaker, and the mixture was mixed with a polyelectrolyte complex gel (charge balance: +
4) was formed.

Further, a cationic polymer aqueous solution prepared as described above
3 ml and 7 ml of an anionic polymer aqueous solution are mixed at once in a beaker, and then mixed with a polyelectrolyte complex gel (charge balance:
-4) was formed.

Preparation Example 4: Preparation of PEC (PVBMA-CLA) 0.106 g (average molecular weight: about 100,000) of a cationic polymer, poly (vinylbenzyltrimethylammonium chloride) (PVBMA) (5 × 10 ⁻⁴ mol as a cationic site) and an anionic polymer 0.090 g of random copolymer of acrylic acid lauryl acrylate (CLA) (acrylic acid content about 80 mol%; average molecular weight about 4000)
× 10 ^-4 mol) and physiological saline (pH 7.
4) Dissolve in 10 ml and obtain 5 ml of the two aqueous solutions thus obtained
Each was mixed at once in a beaker to form a polymer electrolyte complex gel (charge balance: ± 0).

7 ml of the cationic polymer aqueous solution and 3 ml of the anionic polymer aqueous solution prepared in the same manner as above were mixed at once in a beaker, and the mixture was mixed with a polyelectrolyte complex gel (charge balance: +
4) was formed.

Preparation Example 5: Preparation of PEC (2X-sodium alginate) Poly [(dimethyliminio) which is a cationic polymer
Ethylene (dimethyliminio) methylene-1,4-phenylenemethylene dichloride] (2X) (average molecular weight of about 600
0) 0.015 g (1 × 10 ^-4 mol as a cation site) and sodium alginate, an anionic polysaccharide (average molecular weight: approx.
500,000) and 0.020 g (1 × 10 ^-4 mol as anion sites) are separately dissolved in 10 ml of distilled water (pH 8.0),
5 ml of each of the two aqueous solutions thus obtained was mixed at once in a beaker to form a polymer electrolyte complex gel (charge balance: ± 0).

Similarly, 0.075 g of the cationic polymer (5 × 10 ⁻⁴ mol as a cation site) and 0.100 g of polysaccharide (5 × 10 ⁻⁴ mol as an anion site) were separately charged in distilled water (pH 8.0).
0 ml, and the cationic polymer aqueous solution 7 ml and the polysaccharide aqueous solution 3 ml were mixed at once in a beaker to form a polymer electrolyte complex gel (charge balance: +4).

Preparation Example 6: Preparation of PEC (PVBMA-sodium alginate) 0.106 g (average molecular weight of about 15,000) of a cationic polymer, poly (vinylbenzyltrimethylammonium chloride) (PVBMA) (5 × 10 ⁻⁴ mol as a cationic site) and anionic 0.100 g of sodium alginate (average molecular weight of about 100,000), which is a polysaccharide (5 × 10 ^-4 mol as an anion site), is separately dissolved in 10 ml of distilled water (pH 8.0), and the two aqueous solutions thus obtained are dissolved. Every 5 ml was mixed at once in a beaker to form a polymer electrolyte complex gel (charge balance: ± 0).

7 ml of the aqueous cationic polymer solution and 3 ml of the aqueous polysaccharide solution prepared in the same manner as described above were mixed at once in a beaker,
A polyelectrolyte complex gel (charge balance: +4) was formed.

Preparation Example 7: Preparation of PEC (2X-polyglutamic acid) Poly [(dimethyliminio) which is a cationic polymer
Ethylene (dimethyliminio) methylene-1,4-phenylenemethylene dichloride] (2X) (average molecular weight of about 600
0) Separately, 0.015 g (1 × 10 ^-4 mol as a cationic site) and 0.013 g (1 × 10 ^-4 mol as an anion site) of polyglutamic acid (PGA) (average molecular weight: about 4000) as an anionic polymer The resulting solution was dissolved in 10 ml of physiological saline (pH 7.4), and the resulting two aqueous solutions (5 ml each) were mixed at once in a beaker to obtain a polymer electrolyte complex gel [2X-PG
A] (charge balance: ± 0) was formed.

7 ml of the cationic polymer aqueous solution and 3 ml of the anionic polymer aqueous solution prepared in the same manner as above were mixed at once in a beaker, and the mixture was mixed with a polyelectrolyte complex gel (charge balance: +
4) was formed.

Preparation Example 8: Preparation of PEC (PVBMA-aspartic acid / alanine copolymer) 0.106 g of poly (vinylbenzyltrimethylammonium chloride) (PVBMA) (average molecular weight: about 15,000) as a cationic polymer (5 × 10 ⁻⁴ as a cationic site) Mol) and an anionic polymer of aspartic acid / alanine random copolymer [C (Asp / Ala)] (aspartic acid content of about 65 mol%; average molecular weight of about 8000) 0.090 g (5 × 10 ^-4 mol as anion site) ) And distilled water (pH
9.0) Dissolve in 10 ml and obtain the two aqueous solutions 5 thus obtained.
Each ml was mixed at a time in a beaker at room temperature to form a polymer electrolyte complex gel [PVBMA-C (Asp / Ala)] (charge balance: ± 0).

7 ml of the cationic polymer aqueous solution and 3 ml of the anionic polymer aqueous solution prepared in the same manner as above were mixed at once in a beaker, and the mixture was mixed with a polyelectrolyte complex gel (charge balance: +
4) was formed.

Preparation Example 9: Preparation of PEC [poly (L-lysine) -CLA] Cationic polymer poly (L-lysine) (PLL)
(Average molecular weight about 3000) 1.3mg (1 × 10
^-5 mol) and 1.8 mg of acrylic acid / lauryl acrylate random copolymer (CLA) (acrylic acid content: about 80 mol%; average molecular weight: about 5000) (1 × 10 ^-5 mol as an anion site) Are separately dissolved in 10 ml of a 0.5 mol / l sodium chloride aqueous solution (pH 6.5), and 5 ml of each of the two aqueous solutions thus obtained is mixed at once in a beaker at room temperature to give a polymer electrolyte complex gel [ PLL-CLA] (charge balance: ± 0).

A cationic polymer aqueous solution (7 ml) and an anionic polymer aqueous solution (3 ml) prepared in the same manner as described above were mixed at once in a beaker, and a polyelectrolyte complex gel (charge balance: +
4) was formed.

Preparation Example 10: Preparation of PEC (lysine / serine copolymer-polyglutamic acid) Random copolymer of lysine / serine [C (Lys / Ser)] (lysine content: about 70 mol%; average molecular weight: about 10,000) ) 0.019g (1 × 10 ^-4 for cationic seating)
Mol) and the anionic polymer polyglutamic acid (PG
A) (Average molecular weight approx. 2000) 0.013g (1 for anion seat)
× 10 ^-4 mol) and physiological saline (pH 7.
4) Dissolve in 10 ml and obtain 5 ml of the two aqueous solutions thus obtained
Each at once in a beaker, and polymer electrolyte complex gel [C (Lys / Ser) -PGA] (charge balance: ± 0)
Was formed. 7 ml of the aqueous cationic polymer solution and 3 ml of the aqueous anionic polymer solution prepared in the same manner as described above were mixed at once in a beaker to form a polymer electrolyte complex gel (charge balance: +4).

Preparation Example 11: Preparation of PEC [sodium poly (L-lysine) alginate] Cationic polymer poly (L-lysine) (PLL)
(Average molecular weight about 3000) 1.3mg (1 × 10
^-5 mol) and 1.8 mg of anionic polymer sodium alginate (Arg) (average molecular weight of about 40,000) (1 × 10 ^-5 mol as anion site) were separately added to a 0.5 mol / liter aqueous sodium chloride solution (pH 6. 5) The resulting solution was dissolved in 10 ml, and 5 ml each of the two aqueous solutions thus obtained was mixed at once in a beaker at room temperature to form a polymer electrolyte complex gel [PLL-Arg] (charge balance: ± 0).

7 ml of the cationic polymer aqueous solution and 3 ml of the anionic polymer aqueous solution prepared in the same manner as above were mixed at once in a beaker, and the mixture was mixed with a polyelectrolyte complex gel (charge balance: +
4) was formed.

Preparation Example 12: Preparation of PEC (Lysine / Serine Copolymer-Carboxymethyl Chitin) The cationic polymer lysine / serine [C (Lys / Se
r)] random copolymer (lysine content about 70 mol%)
(Average molecular weight about 10,000) 0.019 g (1 × 1 as a cation seat)
0 ^-4 moles) and carboxymethyl chitin (CM-Chn) (carboxymethylation degree about 0.65 / monosaccharide) (average molecular weight of about 5000 is an anionic polymer) 0.018 g (1 as an anion seat
× 10 ^-4 mol) and physiological saline (pH 7.
4) Dissolve in 10 ml and obtain 5 ml of the two aqueous solutions thus obtained
These were mixed at once in a beaker at room temperature to form a polymer electrolyte complex gel [C (Lys / Ser) -CM-Chn] (charge balance: ± 0).

7 ml of the aqueous solution of the cationic polymer and 3 ml of the aqueous solution of the anionic polymer prepared in the same manner as above were mixed at once with a beaker, and a polymer electrolyte complex gel (charge balance: +4)
Was formed.

Preparation Example 13: Preparation of PEC (chitosan-sodium alginate) Chitosan which is a cationic polysaccharide (degree of deacetylation: 10
0%; average molecular weight approx. 2000) 0.020 g (1 for cation seat)
× 10 ⁻⁴ mol) and 0.018 g of sodium alginate (Arg) (average molecular weight: about 4000) as an anionic polymer (1 × 10 ⁻⁴ mol as an anion site) separately in 10 ml of physiological saline (pH 7.4) And two 5 ml of each of the two aqueous solutions thus obtained are mixed at once in a beaker, and a polyelectrolyte complex gel (chitosan-Arg) (charge balance:
± 0).

7 ml of the aqueous solution of the cationic polysaccharide and 3 ml of the aqueous solution of the anionic polymer prepared in the same manner as described above were mixed at once in a beaker, and a polyelectrolyte complex gel (charge balance: +
4) was formed.

Preparation Example 14: Preparation of PEC (Chitosan-Sulfated Cellulose) A cationic polysaccharide, chitosan (degree of deacetylation: approx.
70%; average molecular weight approx. 5000) 0.102g (5 for cation seat)
× 10 ^-4 mol) and sulfated cellulose (S.cel) which is an anionic polymer (sulfation degree: about 0.8 / monosaccharide; average molecular weight: about 800)
0) 0.110 g (5 × 10 ^-4 mol as anion site) were separately dissolved in 10 ml of distilled water (pH 5.0), and 5 ml each of the two aqueous solutions thus obtained was placed in a beaker at room temperature. And mixed with a polyelectrolyte complex gel (chitosan-
S.cel) (charge balance: ± 0).

7 ml of the aqueous solution of the cationic polysaccharide and 3 ml of the aqueous solution of the anionic polymer prepared in the same manner as described above were mixed at once in a beaker, and a polyelectrolyte complex gel (charge balance: +
4) was formed.

Preparation Example 15: Preparation of PEC (diethylaminoethyldextran-carboxymethylchitin) A cationic polysaccharide, diethylaminoethyldextran (DEAE.Dex) (introduction rate: 60%; average molecular weight: about 300)
0) 2.0 mg (1 × 10 ^-5 mol as a cationic site) and carboxymethyl chitin (CM / Chn) as an anionic polymer
(Carboxymethylation degree about 0.65 / monosaccharide; average molecular weight about 500
0) 1.8 mg (1 × 10 ⁻⁵ mol as anion site) were separately dissolved in 10 ml of 0.5 mol / l sodium chloride aqueous solution (pH 8.0), and 5 ml each of the two aqueous solutions thus obtained was added at room temperature. To mix all at once in the beaker,
A polyelectrolyte complex gel (DEAE.Dex-CM.Chn) (charge balance: ± 0) was formed.

7 ml of the aqueous solution of the cationic polysaccharide and 3 ml of the aqueous solution of the anionic polymer prepared in the same manner as described above were mixed at once in a beaker, and a polyelectrolyte complex gel (charge balance: +
4) was formed.

Preparation Example 16: Preparation of PEC (chitosan-polyglutamic acid) Chitosan which is a cationic polymer (degree of deacetylation: 10
0%) (average molecular weight of about 2000) 0.020g (1 × 10 ^-4 mol) and the anionic polymer is a polyglutamic acid (PGA) (average molecular weight of about 4000) 0.013g (1 × 10 ^-4 mol as anionic seat as cationic seat ) Were separately dissolved in 10 ml of physiological saline (pH 7.4), and 5 ml of each of the two aqueous solutions thus obtained was mixed at once in a beaker at room temperature.
A polyelectrolyte complex gel (chitosan-PGA) (charge balance: ± 0) was formed.

7 ml of the aqueous solution of the cationic polymer and 3 ml of the aqueous solution of the anionic polymer prepared in the same manner as above were mixed at once with a beaker, and a polymer electrolyte complex gel (charge balance: +4)
Was formed.

Preparation Example 17: Preparation of PEC (Chitosan-CLA) Chitosan which is a cationic polymer (deacetylation degree 70
%) (Average molecular weight approx. 3000) 0.021 g (1 for cation seat)
× 10 ⁻⁴ mol) and an anionic polymer of acrylic acid / uralyl acrylate random polymer (CLA) (acrylic acid content: about 80 mol%) (average molecular weight: about 4000) 0.018 g (1 × 10 ⁻⁴ as anion seat) Mol) and
10 ml of 3 mol / l sodium chloride aqueous solution (pH 6.5)
And 5 ml each of the two aqueous solutions thus obtained was mixed at once in a beaker at room temperature to form a polyelectrolyte complex gel (chitosan-CLA) (charge balance: ± 0).

7 ml of the aqueous solution of the cationic polymer and 3 ml of the aqueous solution of the anionic polymer prepared in the same manner as above were mixed at once with a beaker, and a polymer electrolyte complex gel (charge balance: +4)
Was formed.

Fixing Example 1: Fixing to carrier (polyethylene tube) 2 ml of each of the PEC gel solutions prepared in Preparation Examples 1 to 17 was dispensed into a polyethylene tube (1.0 cm inner diameter), and rotated at 60 rpm for 8 hours with a rotor. . After coating the inner wall of the polyethylene tube with PEC, remove the supernatant, dry at 60 ° C for 4 hours, wash the inside of the tube three times with 10 ml of distilled water, further dry at 80 ° C for 4 hours, and fix PEC. A modified tube was obtained.

Fixing Example 2: Fixing to Carrier (Gauze) Cotton gauze (10 cm × 10 cm) was immersed in each of the PEC gel solutions prepared in Preparation Examples 1 to 8 for 8 hours. Take out the gauze, wash with 20 ml of distilled water, dry at 60 ° C for 4 hours,
Further, it is washed three times with 10 ml of distilled water and dried at 80 ° C. for 4 hours.
PEC immobilized gauze was obtained.

Fixing Example 3: Fixing to Carrier (Glass Beads) Glass beads (diameter 0.2 mm: manufactured by Toshiba Barotini) were immersed in each of the PEC gel solutions prepared in Preparation Examples 1 to 6 for 6 hours. After coating, the supernatant was removed, dried at 60 ° C for 4 hours, and distilled water 10ml.
Wash the beads three times with, then dry at 80 ℃ for 4 hours, PE
C-immobilized beads were obtained.

Fixing example 4: Fixing to carrier [contact lens material (polymethyl methacrylate)] A circular shape obtained by punching a polymethyl methacrylate plate of the same material as the contact lens into each PEC gel solution prepared in Preparation Examples 7 to 17 to a diameter of 8 mm A small piece (hereinafter also referred to as a circular small piece) was immersed at room temperature for 10 hours. After coating with PEC, remove the supernatant and dry at 60 ° C for 3 hours.
And twice with physiological saline, and further dried at 80 ° C. for 4 hours to obtain PEC-immobilized circular small pieces.

Pharmacological Test Example 1: Confirmation of antibacterial activity Antibacterial activity was examined using the following microorganisms.

Escherichia coli ATCC25932 Staphylococcus aureus ATCC25923 Serratia marcescens IFO3046 Pseudomonas aeruginosa ATCC10145 Brain heart infusion (BHI) medium at 37 ° C
Various bacterial liquids cultured for 16 hours at 0.85% salt-containing M / 15
Dilute with a phosphate buffer (PBS, pH 6.8), and add a bacterial concentration of about 1 × 10
A cell suspension of ⁴ cells / ml was prepared. PD medium (7.0 g dipotassium phosphate, 2.0 g monopotassium phosphate, 0.1 g magnesium sulfate)
g, ammonium sulfate 1.0 g, sodium citrate 0.5 g,
10.0 g glucose and 10.0 g bactopeptone purified water 1000
PEC prepared in the above fixation 1
The mixture was added to a coated polyethylene tube, and 0.1 ml of each of the above bacterial suspensions was added and mixed, and the mixture was kept at 30 ° C. Each tube was cultured with shaking at 30 ° C for 24 hours, and the turbidity of the medium was visually observed to confirm the antibacterial effect. Table 1 shows the results.

Pharmacological test example 2: Confirmation of antibacterial property Take 50 ml of PD medium into Sakaguchi flask and use PE obtained in fixed example 2
Three pieces of C-immobilized gauze (6 cm × 6 cm) were put in the flask, and about 1 × 10 ⁴ cells were inoculated using 1 ml of each bacterial suspension as in the pharmacological test example 1. Similarly, a blank test flask and P
Three pieces of gauze (6 cm × 6 cm) on which EC was not immobilized were placed in a flask, and those inoculated as described above were also prepared. Each flask was cultured with shaking at 30 ° C. for 16 hours, and the turbidity of the medium was visually observed to confirm the antibacterial effect. Table 2 shows the results.

Pharmacological test example 3: Confirmation of antibacterial activity Take 10 ml of PD medium into a sterile polyethylene tube, add 1 g of PEC-immobilized glass beads obtained in fixing example 3, and add 0.1 ml of each bacterial suspension as in pharmacological test example 1. Was added and mixed, and the mixture was kept at 30 ° C. Similarly, a blank test tube and PEC
Was added and 1 g of glass beads not immobilized was added, and the cells were inoculated in the same manner as described above. Each tube was cultured with shaking at 30 ° C. for 24 hours, and the turbidity of the medium was visually observed to confirm the antibacterial effect. Table 3 shows the results.

Pharmacological Test Example 4: Confirmation of antibacterial activity Take 10 ml of PD medium into a sterile polyethylene tube, add 2 g of PEC-immobilized circular small pieces obtained in Fixation Example 4, and add 0.1 ml of each bacterial suspension as in Pharmacological Test Example 1. Was added and mixed, and the mixture was kept at 30 ° C. Similarly, a blank test tube and PE
2 g of a small circular piece on which C was not fixed was added, and a cell inoculated in the same manner as described above was also prepared. Each tube was cultured with shaking at 30 ° C. for 24 hours, and the turbidity of the medium was visually observed to confirm the antibacterial effect. Table 4 shows the results.

Pharmacological test example 5: Confirmation of persistence of antibacterial effect Purified water 10m in each PEC immobilized tube prepared in fixed example 1
l was added and shaken for 2 minutes with a shaker, and then the washing solution was discarded. The same washing operation was further performed four times (a total of five times), and each tube was dried at 60 ° C. for 2 hours. Using the tube thus pretreated, the persistence of the antibacterial effect was examined using Escherichia coli (ATCC25932) in the same manner as in Pharmacological Test Example 1. Table 5 shows the results.

Pharmacological Test Example 6: Confirmation of persistence of antibacterial effect Put each PEC-immobilized gauze prepared in Fixation Example 2 in a 1000 ml beaker, add 500 ml of purified water, stir for 5 minutes using a magnetic stirrer, and discard the washing solution. Was. The same washing operation was further performed 4 times (total 5 times), and each gauze was taken out and dried at 60 ° C. for 4 hours. Using the gauze thus pretreated, the persistence of the antibacterial effect was examined using Escherichia coli (ATCC25932) in the same manner as in Pharmacological Test Example 2. Table 6 shows the results.

Pharmacological Test Example 7: Confirmation of persistence of antibacterial effect Each PEC-immobilized glass bead prepared in Fixation Example 3 was placed in a sterile polyethylene tube, 10 ml of purified water was added, and the mixture was shaken vigorously for 2 minutes with a shaker. Threw away. The same washing operation was further performed four times (total of five times), and each glass bead was taken out and dried at 60 ° C. for 4 hours. Using the glass beads pretreated in this manner, the persistence of the antibacterial effect was examined by Escherichia coli (ATCC25932) in the same manner as in Pharmacological Test Example 3. Table 7 shows the results.

Pharmacological Test Example 8: Confirmation of persistence of antibacterial effect Each round piece of PEC immobilized in Fixation Example 4 was placed in a sterile polyethylene tube, 10 ml of purified water was added, and the mixture was shaken vigorously with a shaker for 2 minutes. Threw away. The same washing operation was performed four more times (a total of five times), and a small circular piece was taken out.
Dry at 60 ° C. for 4 hours. Using the circular pieces pretreated in this manner, the persistence of the antibacterial effect was examined by Escherichia coli (ATCC25932) in the same manner as in Pharmacological Test Example 4. Table 8 shows the results.

Pharmacological Test Example 9: Confirmation of antibacterial property To each PEC gel solution prepared in Preparation Examples 1 to 17,
Paper (TOYO, No. 5B) was soaked for 8 hours. The paper was taken out, washed with 20 ml of distilled water, dried at 60 ° C. for 4 hours, further washed three times with 10 ml of distilled water, and dried at 80 ° C. for 4 hours. The obtained paper was cut out into a disk having a diameter of 13 mm and subjected to gas sterilization treatment to obtain a disc for an antibacterial effect test described later. on the other hand,
A similar disk-shaped paper which was not immersed in the PEC gel solution was similarly gas-sterilized to prepare a disk for lighting.

The four bacteria described in Pharmacological Test Example 1 were cultured in a BHI medium overnight with shaking in the same manner as in Pharmacological Test Example 1, centrifuged three times in the BHI medium, and then diluted with the BHI medium to obtain a bacterial concentration of about 4%. 1 × 1
0 ⁷ cells / ml of bacterial suspension was prepared. 20 μl of this bacterial suspension was brought into contact with the above-mentioned antimicrobial effect test disk and control disk, and kept at 37 ° C. for 2 hours, and then placed on a tryptosome agar plate so that the disk inoculated surface was in contact with the agar plate. After leaving at room temperature for 1 hour, each disk was removed. After further culturing at 37 ° C. for 24 hours, colony formation appeared on the plate was observed. Table 9 shows the results.

Examples 1 to 11 Various PECs were prepared in the same manner as in each of the above preparation examples, and the pharmacological actions were examined after immobilization on a carrier. That is, each cationic polymer shown in Table 10 and each anionic polymer shown in Table 11 were used in the amounts shown in the “collected amount” column of Table 10 and Table 11, respectively.
Was dissolved in 10 ml of the solvent shown in the column of “Solvent”, and 5 ml of each of the obtained solutions was mixed at once in a beaker to form a polymer electrolyte complex gel (charge balance: ± 0). Similarly, 7 ml of the cationic polymer solution and 3 of the anionic polymer solution
+4, and 3 ml of cationic polymer solution and 7 ml of anionic polymer solution.
Each of the polymer electrolyte complex gels No. 4 was formed. These were fixed on a carrier (gauze) in the same manner as in Fixation Example 2, and the antibacterial properties were confirmed in the same manner as in Pharmacological Test Example 2. Table 12 shows the results. In Tables 10 and 11, each polymer is indicated by an abbreviation. The meanings thereof are as follows (the abbreviations used in the above Preparation Examples have the same meanings, and therefore are not described).

6X: poly [(dimethyliminio) hexamethylene (dimethyliminio) methylene-1,4-phenylenemethylene dichloride] PAA: polyacrylic acid PSS: polystyrenesulfonic acid SLA65: random copolymer of styrenesulfonic acid / lauryl acrylate ( CSA74: random copolymer of acrylic acid / stearyl acrylate (about 74 mol% of acrylic acid) CLA66: random copolymer of acrylic acid / lauryl acrylate (about 66 mol% of acrylic acid) Mol%) QPAl · Am: quaternary polyallylamine In the following Tables 1 to 8 and Table 12, the symbols have the following meanings.

+++: strong turbidity, ++: turbid, +: slightly turbid, ±: unchanged,-: transparent.

In Table 9 below, the symbols indicate the degree of colony formation, and the degree is as follows.

+++: large, ++: medium, +: small, ±: extremely small,-: no change.

INDUSTRIAL APPLICABILITY The antimicrobial agent of the present invention is generally insoluble in solvents and can be used for a wide range of applications. Further, the antibacterial activity can be maintained for a long time. Further, various antibacterial agents having different antibacterial strengths can be easily provided.

Continuation of the front page (51) Int.Cl. ⁷ identification code FI A61L 9/01 A61L 9/01 C08G 81/00 C08G 81/00 (72) Inventor Masaharu Akimoto 1-11-4 Higashikanda, Chiyoda-ku, Tokyo (56) References JP-A-2-67210 (JP, A) JP-A-59-164342 (JP, A) JP-A-61-236702 (JP, A) JP-A-54-86584 (JP, A) JP-A-46-37497 (JP, A) JP-A-46-37498 (JP, A) JP-A-46-37499 (JP, A) JP-A-49-3992 (JP, A) 49-8581 (JP, A) JP-A-49-8599 (JP, A) JP-A-50-63096 (JP, A) JP-A-50-1022695 (JP, A) JP-A-50-160185 (JP, A) A) JP-A-53-34887 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A01N 61/00 A01N 33/12 A01N 43/40 A01N 43/60 A61L 2/16 A61L 9/01 C08G 81/00 CA (STN) JICST file (JOIS)

Claims (9)

(57) [Claims] 1. A cationic polymer containing (A) an N ⁺ atom in a repeating unit, comprising: (a1) a compound represented by the general formula (I): [Wherein, R ₁ and R ₄ are each independently an alkylene group having 1 to 10 carbon atoms; (Wherein, R ₁₁ and R ₁₂ are each independently an alkylene group having 1 or 2 carbon atoms) or an arylene group, wherein R ₂ , R ₃ , R ₅ and R ₆ Is each independently an alkyl group having 1 to 3 carbon atoms, or R ₁ is a group having two nitrogen atoms and R ₂ , R ₃ , R ₅ and R _{6 in} the formula Wherein R ₂ and R ₅ have the same meanings as described above, or a group represented by the formula: Wherein R ₃ and R ₆ have the same meanings as described above, and X ₁ ^- is a counter ion and m is a number of 5 or more. (A2) general formula (II) [Wherein A is a general formula (Wherein B is an alkylene group having 1 or 2 carbon atoms, R ₂₁ , R ₂₂ and R ₂₃ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X ₂ ^- is Or a group represented by the general formula (Wherein, R ₂₄ is an alkyl group or benzyl group having 1 to 3 carbon atoms, and X ₃ ^- is a counter ion) or a general formula: (Wherein R ₂₅ is an alkyl group having 1 or 2 carbon atoms;
₂₆ , R ₂₇ and R ₂₈ each independently represent a hydrogen atom or a carbon atom
And X ₃ ^- is a counter ion), and n is a number of 10 or more.] (A3) a compound represented by the general formula (III): (In the formula, v is 3 or 4, R ₉₁ is a hydrogen atom; an alkyl group having 1 to 4 carbon atoms; 1 carbon atom substituted by a hydroxy group, a mercapto group, or an alkylthio group having 1 to 3 carbon atoms. to 4 alkyl group; a or imidazolylmethyl group or indolylmethyl group, R ₉₂ is -N ⁺ H ₃ X ₅ ^- or _{^{-N + H 2 C (NH)}} NH 2 X 6 - a and, X ₅ ^- and X ₆ ^- are each independently a counter ion, t is 20 to 100, and r
Is an integer of 10 or more); and (a4) at least one cationic polymer selected from the group consisting of cationic polysaccharides; and (B) a —COO ⁻ group, SO3 ^- group or a -PO ₃ ^2-
Group or -PO ₃ H ^- a anionic polymer containing group, (b1) the general formula (IV) (In the formula, u is 1 or 2, R ₈₁ is a hydrogen atom; an alkyl group having 1 to 4 carbon atoms; 1 carbon atom substituted by a hydroxy group, a mercapto group, or an alkylthio group having 1 to 3 carbon atoms. A compound represented by the formula: (b2) a compound represented by the following formula: (V) alkyl groups; or an imidazolylmethyl group or an indolylmethyl group, s is 20 to 100, and q is an integer of 10 or more. ) (Wherein, R ₃₁ is a hydrogen atom or a methyl group, R ₃₂ is an alkyl group having 6 to 18 carbon atoms, Y is a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or A salt thereof, or a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, or an aryl group containing a phosphate group or a salt thereof, a is a number of 20 to 100, and p is a number of 10 or more. And (b3) an anionic polysaccharide selected from the group consisting of: a polyelectrolyte complex obtained by reacting at least one of the anionic polymers. Agent. 2. The antibacterial agent according to claim 1, wherein the concentration ratio of the cationic site of the cationic polymer to the anionic site of the anionic polymer (cation site / anion site) is 0.25 to 4.0. 3. In the general formula (I), R ₁ and R ₄ are each independently a linear or branched alkylene group having 2 to 8 carbon atoms, and R ₁₁ and R ₁₂ are bonded at the p-position. The antibacterial agent according to claim 1, wherein the compound (a1) represented by the general formula (I) is used. 4. In the general formula (III), R ₉₁ is a hydrogen atom, methyl group, isopropyl group, isobutyl group, s-butyl group, hydroxymethyl group, hydroxyethyl group, methylthioethyl group, mercaptomethyl group, 5- The antibacterial agent according to claim 1, wherein the compound (a3) represented by the general formula (III), which is an imidazolylmethyl group or a 3-imidazolylmethyl group, is used. 5. Chitosan as a cationic polysaccharide (a4),
The antibacterial agent according to claim 1, wherein a derivative of chitosan or a diethylaminoethyl derivative of a neutral polysaccharide is used. 6. In the above formula (IV), R ₈₁ is a hydrogen atom, methyl group, isopropyl group, isobutyl group, s-butyl group, hydroxymethyl group, hydroxyethyl group, methylthioethyl group, mercaptomethyl group, 5- 2. The compound (b1) represented by the general formula (IV), which is an imidazolylmethyl group or a 3-imidazolylmethyl group, is used.
Antibacterial agent as described. 7. In the above formula (V), R ₃₂ has 6 carbon atoms.
~ 14 linear or branched alkyl groups, wherein a is
The compound represented by the general formula (V) which is 50 to 100 (b
The antibacterial agent according to claim 1, wherein 2) is used. 8. Anionic polysaccharides such as hyaluronic acid and derivatives thereof, alginic acid and derivatives thereof, chondroitin sulfate A, chondroitin sulfate C, chondroitin sulfate B (dermatan sulfate) and derivatives thereof, chondroitin sulfate D and derivatives thereof, and chondroitin sulfate E. And its derivatives, heparan sulfate and its derivatives, heparin and its derivatives, κ-carrageenan and its derivatives, λ-carrageenan and its derivatives, carboxymethylated, sulfated or phosphorylated cellulose derivatives, carboxymethylated,
Sulfated or phosphorylated chitin derivatives, carboxymethyl starch and derivatives thereof, carboxymethylated, sulfated or phosphorylated amylose derivatives, carboxymethylated, sulfated or phosphorylated amylopectin derivatives,
Carboxymethylated, sulfated or phosphorylated β-1,3 ′
-Glucan derivatives, carboxymethylated, sulfated or phosphorylated β-1,2'-glucan derivatives, carboxymethylated, sulfated or phosphorylated β-1,3'-;β-1,6'-
Glucan derivatives, carboxymethylated, sulfated or phosphorylated dextran derivatives, carboxymethylated, sulfated or phosphorylated pullulan derivatives, carboxymethylated, sulfated or phosphorylated agarose derivatives, carboxymethylated, sulfated or phosphorylated At least one anionic selected from the group consisting of oxidized β-1,4′-galactan derivatives, carboxymethylated, sulfated or phosphorylated mannan derivatives, and carboxymethylated, sulfated or phosphorylated inulin derivatives The antibacterial agent according to claim 1, wherein a polysaccharide (b3) is used. 9. An antibacterial material comprising the polymer electrolyte complex according to claim 1 supported on a carrier.