JP2017206441A - Bactericidal composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bactericidal composition that prevents bactericidal performance from deteriorating due to the adsorption of a bactericidal compound to a wall surface.SOLUTION: A bactericidal composition contains a polymer selected from a water-soluble polymer I having a hydrophilic repeating unit (A) and a hydrophobic repeating unit (B) with an HLB value of 1-14, and a water-soluble polymer II having a repeating unit (C) having an acidic group, and a repeating unit (D) derived from a (meth) acrylamide monomer, and a bactericidal compound having a cationic group.SELECTED DRAWING: None

Description

  The present invention relates to a bactericidal composition.

  Bactericides are used in various fields such as daily necessities and medical supplies. For example, it is used for coating materials for medical and hygiene products, cleaning compositions for clothes, disinfectants and interior paints in food factories and hospitals. In addition, materials such as fibers, plastics and films imparted with bactericidal properties by blending bactericides are also widely used. In such a bactericidal agent, a bactericidal compound having a cationic group such as a cationic polymer described in Patent Document 1 is blended.

Special table 2003-509546 gazette

However, since the bactericidal compound having a cationic group generally comprises a cationic partial structure and a highly hydrophobic partial structure, for example, when the storage container is filled as an aqueous solution, the storage container Depending on the material, it adsorbs to the wall surface, and as a result, the concentration of the bactericidal compound may be lowered. Thus, when content of the bactericidal compound contained in a composition reduces, there exists a possibility that bactericidal performance may reduce.
The problem to be solved by the present invention is to provide a bactericidal composition in which a reduction in bactericidal performance due to adsorption of a bactericidal compound to a wall surface is suppressed.

  Thus, as a result of intensive studies, the present inventors have included a specific copolymer in the composition together with a bactericidal compound having a cationic group, thereby suppressing a reduction in bactericidal performance due to adsorption of the bactericidal compound. The present invention has been completed.

  Therefore, the present invention provides a water-soluble polymer I having a hydrophilic repeating unit (A) and a hydrophobic repeating unit (B) having an HLB value of 1 to 14 (hereinafter also referred to as the polymer I of the present invention). And a water-soluble polymer II having a repeating unit (C) having an acidic group and a repeating unit (D) derived from a (meth) acrylamide monomer (hereinafter also referred to as the polymer II of the present invention). The present invention provides a bactericidal composition (hereinafter also referred to as the bactericidal composition of the present invention), which comprises a polymer and a bactericidal compound having a cationic group.

  ADVANTAGE OF THE INVENTION By this invention, the bactericidal composition in which the reduction | decrease of the bactericidal performance by adsorption | suction to the wall surface of a bactericidal compound was suppressed can be provided.

  The bactericidal composition of the present invention comprises a polymer selected from the polymer I of the present invention and the polymer II of the present invention, and a bactericidal compound having a cationic group. Hereinafter, the bactericidal composition of the present invention will be described in detail.

<Polymer I>
The polymer I of the present invention is a water-soluble polymer having a hydrophilic repeating unit (A) and a hydrophobic repeating unit (B) having an HLB value of 1 to 14.

[Repeating unit (A)]
The polymer I of the present invention has a hydrophilic repeating unit (A). The polymer I of the present invention may have one or more repeating units corresponding to the repeating unit (A).
In the present specification, the term “hydrophilic” means having a strong affinity for water. Specifically, when a homopolymer consisting of only one type of repeating unit (having a number average molecular weight of about 10,000 to 1,000,000 according to the measurement method in Examples) is used at 100 ° C. pure water at room temperature (25 ° C.). When 1 g or more is dissolved, the repeating unit is hydrophilic.

The HLB (Hydrophile-Lipophile Balance) value of the hydrophilic repeating unit (A) is preferably 10 or more, more preferably 15 or more, particularly preferably from the viewpoint of imparting hydrophilicity and the prevention of adsorption of the bactericidal compound. It is 17 or more, preferably 70 or less, more preferably 50 or less.
Further, in this specification, the HLB value means a value calculated from the ratio of the organic value and the inorganic value of the compound (Oda equation), and “Formation Design with Organic Concept Diagram” [1998, NIHON]. EMULSION CO. , LTD].

  In the present invention, the hydrophilic repeating unit (A) is preferably a hydrophilic repeating unit represented by the formula (A0).

[In the formula (A0),
R ¹ represents a hydrogen atom or a methyl group,
R ² represents —O—, * — (C═O) —O—, * — (C═O) —NR ⁴ —, or * —NR ⁴ — (C═O) — (R ⁴ represents a hydrogen atom Or an organic group having 1 to 10 carbon atoms, and * represents a position bonded to the carbon atom to which R ¹ in the formula (A0) is bonded.
R ³ represents an organic group having 1 to 30 carbon atoms.
However, R ² is, * - (C = O) -NR 4 -, or ^{* -NR 4 - (C = O} ) - and is, and R ⁴ is, if an organic group having 1 to 10 carbon atoms , R ³ and R ⁴ may be combined to form a ring. ]

  Furthermore, as the hydrophilic repeating unit (A), the repeating unit (A1) represented by the formula (A1), the repeating unit (A2) represented by the formula (A2), and the repeating unit represented by the formula (A3) One selected from (A3), a repeating unit (A4) represented by formula (A4), a repeating unit (A5) represented by formula (A5) and a repeating unit (A6) represented by formula (A6) The above is preferable. Among these, the repeating units (A2) to (A6) are preferable, the repeating units (A2) and (A4) to (A6) are more preferable, and a composition that is resistant to hydrolysis and excellent in storage stability can be obtained. And repeating units (A4) to (A6) are particularly preferred.

[In the formula (A1),
R ^a represents a hydrogen atom or a methyl group,
R ^b is —O—, * — (C═O) —O—, * — (C═O) —NR ^e —, or * —NR ^e — (C═O) — (R ^e is a hydrogen atom. Or an organic group having 1 to 10 carbon atoms, and * represents a position bonded to the carbon atom to which R ^a in the formula (A1) is bonded;
R ^c represents a polyoxyalkylene group,
R ^d represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[In the formula (A2),
R ¹⁹ represents a hydrogen atom or a methyl group,
R ²⁰ represents an alkylene group having 2 to 4 carbon atoms,
R ²¹ represents an alkylene group having 1 to 10 carbon atoms,
R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
q represents an integer of 1 to 10. ]

[In the formula (A3),
Y ^{is, - (C = O) O} -, - (O = S = O) O -, -O (O = S = O) O -, - (S = O) O -, -O (S = O ) O ⁻ , —O (P═O) (OR ³⁰ ) O ⁻ , —O (P═O) (R ³⁰ ) O ⁻ , — (P═O) (OR ³⁰ ) O ⁻ or — (P═O) ) (R ³⁰⁾ O ^- shows the (R ³⁰ represents an alkyl group having 1 to 3 carbon atoms),
R ²⁵ represents a hydrogen atom or a methyl group,
R ²⁶ and R ²⁷ each independently represent a divalent organic group having 1 to 10 carbon atoms,
R ²⁸ and R ²⁹ each independently represent an alkyl group having 1 to 10 carbon atoms. ]

[In the formula (A4),
R ³¹ represents a hydrogen atom or a methyl group,
R ³² and R ³³ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms. ]

[In the formula (A5),
R ³⁴ represents a hydrogen atom or a methyl group,
R ³⁵ and R ³⁶ each independently represents an alkylene group having 1 to 2 carbon atoms. ]

[In the formula (A6),
R ³⁷ represents a hydrogen atom or a methyl group,
R ³⁸ represents an alkylene group having 1 to 3 carbon atoms. ]

  Here, each symbol in the above formulas (A1) to (A6) will be described in detail.

  (Formula (A1))

R ^a represents a hydrogen atom or a methyl group.
R ^b represents —O—, * — (C═O) —O—, * — (C═O) —NR ^e —, or * —NR ^e — (C═O) —. Among these, *-(C = O) -O- is preferable.
R ^e represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The alkyl group may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
R ^c represents a polyoxyalkylene group, and a group represented by — (R ^f O) _p — is preferable. R ^f is an alkylene group having 2 to 6 carbon atoms, and preferably an alkylene group having 2 to 4 carbon atoms. The alkylene group may be linear or branched, and examples thereof include an ethylene group, a trimethylene group, a propylene group, and a tetramethylene group. The p R ^{f s} may be the same or different. Moreover, p is an integer of 2-100.
R ^d represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. .

  (Formula (A2))

R ¹⁹ represents a hydrogen atom or a methyl group.
R ²⁰ represents an alkylene group having 2 to 4 carbon atoms. The alkylene group may be linear or branched, and examples thereof include an ethylene group, a trimethylene group, a propylene group, and a tetramethylene group.
R ²¹ represents an alkylene group having 1 to 10 carbon atoms. The alkylene group preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms. The alkylene group may be linear or branched, and examples thereof include a methylene group, an ethylene group, a trimethylene group, a propylene group, and a tetramethylene group.
R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms. Carbon number of the alkyl group is preferably 1-6, more preferably 1-4. The alkyl group may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Can be mentioned.
Although q shows the integer of 1-10, the integer of 1-8 is preferable and the integer of 1-6 is more preferable.

  (Formula (A3))

Y ^{is, - (C = O) O} -, - (O = S = O) O -, -O (O = S = O) O -, - (S = O) O -, -O (S = O ) O ⁻ , —O (P═O) (OR ³⁰ ) O ⁻ , —O (P═O) (R ³⁰ ) O ⁻ , — (P═O) (OR ³⁰ ) O ⁻ or — (P═O) ) (R ³⁰⁾ O ^- it shows a. Among these, — (C═O) O 2 ^— is preferable. The alkyl group having 1 to 3 carbon atoms represented by R ³⁰ may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
R ²⁵ represents a hydrogen atom or a methyl group.
R ²⁶ and R ²⁷ each independently represent a divalent organic group having 1 to 10 carbon atoms. The organic group is preferably a divalent aliphatic hydrocarbon group, and more preferably an alkylene group. Carbon number of an alkylene group becomes like this. Preferably it is 1-8, More preferably, it is 1-6. The alkylene group may be linear or branched, and examples thereof include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.
R ²⁸ and R ²⁹ each independently represent an alkyl group having 1 to 10 carbon atoms. Carbon number of the alkyl group is preferably 1-6, more preferably 1-4. The alkyl group may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Can be mentioned.

  (Formula (A4))

R ³¹ represents a hydrogen atom or a methyl group.
R ³² and R ³³ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms. The carbon number of the alkyl group represented by R ³² and R ³³ is preferably 1 to 3, and the carbon number of the hydroxyalkyl group is preferably 1 to 4. The alkyl group and hydroxyalkyl group may be linear or branched. Moreover, the substitution position of the hydroxy group contained in the hydroxyalkyl group is not particularly limited. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. Examples of the hydroxyalkyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group.

  (Formula (A5))

R ³⁴ represents a hydrogen atom or a methyl group.
R ³⁵ and R ³⁶ each independently represents an alkylene group having 1 to 2 carbon atoms. The alkylene group may be linear or branched, but is preferably linear. Examples of the alkylene group include a methylene group and an ethylene group.

  (Formula (A6))

R ³⁷ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
R ³⁸ represents an alkylene group having 1 to 3 carbon atoms. The alkylene group may be linear or branched, but is preferably linear. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group.

  Examples of the hydrophilic repeating unit (A) include (meth) acrylate polymer species, (meth) acrylamide polymer species, and other vinyl polymer species. As monomers for deriving the hydrophilic repeating unit (A), hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene Glycol polypropylene glycol (meth) acrylate, polyethylene glycol polytetramethylene glycol (meth) acrylate, polypropylene glycol polytetramethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, 2- (meta ) Acryloyloxyethyl-2 '-(trimethylammonio) ethyl phosphate, N- (Meth) acrylate monomers such as (meth) acryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl ( (Meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N-ethylol (meth) acrylamide, N-methylolpropane (meta) ) Acrylamide, N-methoxymethyl (meth) acrylamide, N- (2-hydroxy) ethyl (meth) acrylamide, N- (meth) acryloylmorpholine, (meth) acryloylpyrrolidine, (meth) acryloylpiperidine, etc. ) Acrylamide monomer; vinyl compounds such as N-vinyl-2-pyrrolidone are included. You may use 1 type in said monomer individually or in combination of 2 or more types.

  Among the above monomers, in the present invention, since the composition has excellent storage stability, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N -Isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N-ethylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N- (2-hydroxy) ethyl ( (Meth) acrylamide monomers such as (meth) acrylamide, N- (meth) acryloylmorpholine, (meth) acryloylpyrrolidine and (meth) acryloylpiperidine; N-vinyl-2-pyrrolidone and the like are preferable.

As content of the hydrophilic repeating unit (A) in the polymer I of this invention, 65 mass% or more is preferable with respect to all the repeating units contained in the polymer I, 75-99 mass% is more preferable, 85-98 mass% is especially preferable. Within the above numerical range, the polymer I is easily dissolved in water, and the adsorption of the bactericidal compound to a substrate such as a container is further suppressed.
The content of the hydrophilic repeating unit (A) can be measured by ¹ H-NMR or the like.

[Repeating unit (B)]
The polymer I of the present invention has a hydrophobic repeating unit (B) having an HLB value of 1 to 14. The repeating unit (B) of the polymer I used in the present invention is a hydrophobic repeating unit having an HLB value of 1 to 14, and has one or more repeating units corresponding to the repeating unit (B). It may be.

  The HLB of the repeating unit (B) is 1 to 14, but the polymer I is easily adsorbed on a base material such as a container, and the bactericidal compound is less likely to be adsorbed on the base material. It is preferably 10 or less, particularly preferably 8 or less, and preferably 2 or more. When such an HLB value exceeds 14, it becomes difficult for the polymer I to be adsorbed on the base material, and the bactericidal compound becomes easy to adsorb on the base material.

  In the present invention, it has excellent adsorptivity to a substrate having high hydrophobicity, for example, excellent adsorbability to a polyolefin-based substrate such as polypropylene, that is, a highly hydrophobic group such as a polyolefin-based substrate. The hydrophobic repeating unit (B) is preferably a hydrophobic repeating unit represented by the formula (B1) or (B2) because the adsorption between the material and the bactericidal compound is easily suppressed.

[In the formula (B1),
R ⁵ represents a hydrogen atom or a methyl group,
R ⁶ represents —O—, * — (C═O) —O—, * — (C═O) —NR ⁸ —, or * —NR ⁸ — (C═O) — (R ⁸ represents a hydrogen atom Or an organic group having 1 to 10 carbon atoms, and * represents a position bonded to the carbon atom to which R ⁵ in the formula (B1) is bonded.
R ⁷ represents an organic group having 4 to 30 carbon atoms. ]

[In the formula (B2),
R ⁹ represents a hydrogen atom or a methyl group,
R ¹⁰ is —O—, * — (C═O) —O—, * — (C═O) —NR ¹⁷ —, * —NR ¹⁷ — (C═O) — (R ¹⁷ is a hydrogen atom or An organic group having 1 to 10 carbon atoms, * represents a position bonded to the carbon atom to which R ⁹ in the formula (B2) is bonded) or a phenylene group;
R ¹¹ represents a divalent organic group having 1 to 10 carbon atoms,
R ¹² and R ¹³ each independently represents an organic group having 1 to 10 carbon atoms,
R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently —OSi (R ¹⁸ ) ₃ (R ¹⁸ is independently a hydrogen atom or an organic group having 1 to 8 carbon atoms) or 1 carbon atom. 10 to 10 organic groups
n represents an integer of 0 to 200. ]

In formula (B1), R ⁶ represents —O—, * — (C═O) —O—, * — (C═O) —NR ⁸ —, or * —NR ⁸ — (C═O) —. Show. Among these, *-(C = O) -O- and *-(C = O) -NR < ⁸ >-are preferable, and *-(C = O) -NR < ⁸ >-is more preferable.
R ⁸ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Carbon number of the alkyl group is preferably 1-5, more preferably 1-3. The alkyl group may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

In formula (B1), R ⁷ represents an organic group having 4 to 30 carbon atoms. Examples of the organic group include a hydrocarbon group and a group having one or more selected from an ether bond, an imino group, an amide bond, and an ester bond between carbon-carbon atoms of the hydrocarbon group. Such an organic group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms.
The “hydrocarbon group” in R ⁷ is a concept including an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and an aliphatic hydrocarbon group is preferable. The aliphatic hydrocarbon group may be linear or branched. In addition, the aliphatic hydrocarbon group is preferably an alkyl group. Carbon number of an alkyl group becomes like this. Preferably it is 4-24, More preferably, it is 4-18. For example, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc. Can be mentioned.
In addition, as a group having one or more selected from an ether bond, an imino group, an amide bond and an ester bond between the carbon-carbon atoms of the “hydrocarbon group” as described above, the carbon-carbon atom of the hydrocarbon group A group having an ether bond is preferred.

In the formula (B2), R ¹⁰ represents —O—, * — (C═O) —O—, * — (C═O) —NR ¹⁷ —, * —NR ¹⁷ — (C═O) — or phenylene. Indicates a group. Among these, * — (C═O) —O— and * — (C═O) —NR ¹⁷ — are preferable.
R ¹⁷ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Carbon number of the alkyl group is preferably 1-5, more preferably 1-3. The alkyl group may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

In formula (B2), R ¹¹ represents a divalent organic group having 1 to 10 carbon atoms. The organic group is preferably a divalent aliphatic hydrocarbon group, and more preferably an alkylene group. Carbon number of an alkylene group becomes like this. Preferably it is 1-8, More preferably, it is 1-6. The alkylene group may be linear or branched, and examples thereof include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.

In formula (B2), R ¹² and R ¹³ each independently represent an organic group having 1 to 10 carbon atoms.
In the formula (B2), R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent —OSi (R ¹⁸ ) ₃ or an organic group having 1 to 10 carbon atoms.
The organic group represented by R ^{12 to} R ¹⁶ is preferably a hydrocarbon group, and more preferably an aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be linear or branched. In addition, the aliphatic hydrocarbon group is preferably an alkyl group. Carbon number of an alkyl group becomes like this. Preferably it is 1-6, More preferably, it is 1-4. Examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a pentyl group.
R ¹⁸ represents a hydrogen atom or an organic group having 1 to 8 carbon atoms. As the organic group, a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is more preferable. The aliphatic hydrocarbon group may be linear or branched. In addition, the aliphatic hydrocarbon group is preferably an alkyl group. Carbon number of an alkyl group becomes like this. Preferably it is 1-6, More preferably, it is 1-4, Especially preferably, it is 1-3. For example, methyl group, ethyl group, n-propyl group, isopropyl group and the like can be mentioned.

  In formula (B2), n represents an integer of 0 to 200, preferably an integer of 0 to 100, more preferably an integer of 0 to 50, and still more preferably an integer of 0 to 25.

  Examples of the hydrophobic repeating unit (B) include (meth) acrylate polymer species, (meth) acrylamide polymer species, olefin-based, styrene-based, and vinyl ether-based polymer species. In these, since it is excellent in the storage stability of a composition, a (meth) acrylamide type polymer seed | species is preferable.

As monomers for deriving the hydrophobic repeating unit (B), methyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Octyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) Acrylate, 3- [tris (trimethylsiloxy) silyl] propyl (meth) acrylate, 3- [bis (trimethylsiloxy) (methyl) silyl] propyl (meth) acrylate, silicone (meth) acrylate (Meth) acrylate monomers such as X (22-22475 (manufactured by Shin-Etsu Silicone), FM-0711 (manufactured by JNC), etc.); N, N-di-n-propyl (meth) acrylamide, N, N -Diisopropyl (meth) acrylamide, N, N-di (n-butyl) (meth) acrylamide, N, N-di (tert-butyl) (meth) acrylamide, Nn-butyl (meth) acrylamide, N-tert -Butyl (meth) acrylamide, Nn-hexyl (meth) acrylamide, Nn-octyl (meth) acrylamide, N-tert-octyl (meth) acrylamide, N-dodecyl (meth) acrylamide, N, N-diglycidyl (Meth) acrylamide, N- (4-glycidoxybutyl) (meth) acrylamide, N- (5-g Sidoxypentyl) (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, N-tert-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-phenyl (meth) acrylamide, etc. (Meth) acrylamide monomers; olefin monomers such as acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, ethylene, propylene, butene; styrene monomers such as styrene, α-methylstyrene, butadiene, isoprene Etc.
You may use 1 type in the said monomer individually or in combination of 2 or more types.

  Among the above monomers, a (meth) acrylamide monomer is preferable, and particularly preferable specific examples include N, N-di-n-propyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, and N, N-. Di (n-butyl) (meth) acrylamide, N, N-di (tert-butyl) (meth) acrylamide, Nn-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, Nn- Hexyl (meth) acrylamide, Nn-octyl (meth) acrylamide, N-tert-octyl (meth) acrylamide, N-dodecyl (meth) acrylamide, N, N-diglycidyl (meth) acrylamide, N- (4-glycyl) Sidoxybutyl) (meth) acrylamide, N- (5-glycidoxypentyl) (me ) Acrylamide, N-n-butoxymethyl (meth) acrylamide, N-tert-butoxymethyl (meth) acrylamide, N- isobutoxymethyl (meth) acrylamide, and N- phenyl (meth) acrylamide.

As content of the hydrophobic repeating unit (B) in the polymer I of this invention, 0.1 mass% or more is preferable with respect to all the repeating units contained in the polymer I, 0.1-35 mass% Is more preferable, 0.1 to 25% by mass is still more preferable, and 2 to 15% by mass is particularly preferable. Within the above numerical range, the water-soluble property and the adsorptivity to the substrate surface are excellent.
The content of the hydrophobic repeating unit (B) can be measured by ¹ H-NMR or the like.

The polymer I of the present invention may contain other repeating units in addition to the repeating units (A) and (B) as long as the effects of the present invention are not impaired. In addition, it is preferable that the polymer I does not contain substantially the repeating unit which has an acidic group as another repeating unit. When such a repeating unit is contained, the bactericidal compound is captured and adsorbed to the base material by the repeating unit (A), and the bactericidal property may be lowered.
In the present invention, in the polymer I of the present invention, the total amount of the repeating unit (A) and the repeating unit (B) is 80% by mass or more with respect to all the repeating units contained in the polymer I. Is more preferable, 90 mass% or more is more preferable, and 95 mass% or more is further preferable.

  The polymer I of the present invention may be any of a block copolymer, a graft copolymer, a random copolymer, and an alternating copolymer.

The weight average molecular weight (M _w ) of the polymer I is such that the polymer I is easily adsorbed on a base material such as a container, and the bactericidal compound is difficult to adsorb on the base material. Is preferably 10,000 to 5,000,000, more preferably 10,000 to 3,000,000, still more preferably 10,000 to 2,000,000, and particularly preferably 10,000 to 500,000. Moreover, as molecular weight distribution ( _Mw / _Mn ), 1-10 are preferable, 1-7 are more preferable, and 1-5 are still more preferable.
In addition, what is necessary is just to measure a weight average molecular weight and molecular weight distribution according to the method as described in the Example mentioned later.

Moreover, although the polymer I of this invention is a water-soluble polymer, it is preferable that it is a polymer which melt | dissolves also in a C1-C4 lower alcohol. Here, in this specification, dissolving in water or lower alcohol means that when the polymer is added to and mixed with water or lower alcohol (25 ° C.) so that the polymer solid content is 0.5% by mass. It means to become transparent.
More specifically, when the composition containing the polymer I is used as a bactericidal composition, the HLB of the polymer I can be used as an adsorbing force to a substrate such as a container, or from the viewpoint of suppressing the adsorption of a bactericidal compound. Therefore, it is preferably 10 or more, more preferably 15 or more, particularly preferably 17 or more, and preferably 80 or less, more preferably 50 or less.

  The polymer I of the present invention is prepared, for example, as follows. That is, one or more monomers selected from the monomers for deriving each repeating unit are selected and mixed. This mixture is dissolved in a solvent such as water, acetonitrile, ethanol, 2-propanol, 1,4-dioxane as necessary. And the target polymer I can be obtained by adding a polymerization initiator and carrying out radical polymerization.

  In addition, the polymerization initiator used when performing radical polymerization is not particularly limited as long as it is a normal radical polymerization initiator. For example, benzoyl peroxide, lauroyl peroxide, diisopropyl peroxydicarbonate, tert. -Butylperoxy-2-ethylhexanoate, tert-butylperoxypivalate, tert-butylperoxydiisobutyrate, azobisisobutyronitrile, azobisisodimethylvaleronitrile, 2,2'-azobis [2- ( 2-Imidazolin-2-yl) propane] dihydrochloride, and persulfate and persulfate monosulfite-based polymerization initiators.

  Moreover, 0.001-10 mass parts is preferable with respect to 100 mass parts of monomer components, and, as for the usage-amount of a polymerization initiator, 0.01-5 mass parts is more preferable. The polymerization temperature is preferably 20 to 100 ° C., and the polymerization time is preferably 0.5 to 48 hours.

<Polymer II>
Next, the polymer II of the present invention will be described in detail. The polymer II of the present invention is a water-soluble polymer having a repeating unit (C) having an acidic group and a repeating unit (D) derived from a (meth) acrylamide monomer.

[Repeating unit (C)]
The polymer II of the present invention has a repeating unit (C) having an acidic group. The polymer II of the present invention may have one or more repeating units corresponding to the repeating unit (C).
The repeating unit (C) may be any repeating unit having an acidic group, but is preferably derived from a monomer containing an ethylenically unsaturated bond from the viewpoint of ease of introduction and safety. Moreover, as an acidic group, a carboxy group, a sulfo group, a phosphoric acid group, or these salts etc. are mentioned, These may have one and may have two or more. Examples of the salt include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt and calcium salt; ammonium salt; organic ammonium salt and the like.

Examples of the monomer for deriving such a repeating unit (C) include unsaturated dicarboxylic acids such as fumaric acid, maleic acid and itaconic acid or salts thereof; unsaturated carboxylic acids such as (meth) acrylic acid or salts thereof; Sulfo group-containing polymerizable unsaturated monomers such as acid, allyl sulfonic acid, methallyl sulfonic acid, 2-sulfoethyl (meth) acrylate, 2-acrylamido-2-methylpropane sulfonic acid, etc .; 2- (meth) acryloyloxy Examples thereof include phosphoric acid group-containing polymerizable unsaturated monomers such as ethyl acid phosphate and 2- (meth) acryloyloxypropyl acid phosphate, or salts thereof. Further, the monomer derived by modification includes hydrolyzate of acrylic ester; hydrolyzate of anhydride of unsaturated dicarboxylic acid such as maleic anhydride and itaconic anhydride; glycidyl methacrylate and (4-vinylbenzyl) Examples include adducts of acidic group-containing thiols to the epoxy group of glycidyl ether. These may be used alone or in combination of two or more.
Among these, acrylic acid and methacrylic acid are preferable from the viewpoint of ease of introduction and reactivity.

As content of the repeating unit (C) in the polymer II of this invention, 0.1-20 mass% is preferable with respect to all the repeating units contained in the polymer II, and a bactericidal compound and moderate interaction are preferable. From the viewpoint of suppressing adsorption of the bactericidal compound, 0.5 to 15% by mass is more preferable, 1 to 10% by mass is further preferable, and 1 to 5% by mass is particularly preferable.
The content of the repeating unit (C) can be measured by ¹ H-NMR, ¹³ C-NMR, electric conductivity, and the like.

[Repeating unit (D)]
The polymer II of the present invention has a repeating unit (D) derived from a (meth) acrylamide monomer. The polymer II of the present invention may have one or more repeating units corresponding to the repeating unit (D). The repeating unit (D) is preferably a repeating unit derived from a hydrophilic (meth) acrylamide monomer.
As described above, in this specification, hydrophilic means having a property of having a strong affinity for water. Specifically, when a homopolymer consisting of only one type of repeating unit (having a number average molecular weight of about 10,000 to 1,000,000 according to the measurement method in Examples) is used at 100 ° C. pure water at room temperature (25 ° C.). When 1 g or more is dissolved, the repeating unit is hydrophilic.
The HLB of the repeating unit (D) is preferably 10 or more, more preferably 15 or more, and still more preferably 17 or more, in order to suppress adsorption of the bactericidal compound to the substrate surface. When the HLB value of the repeating unit (D) is in the above range, the effect of preventing adsorption of the bactericidal compound to the substrate is excellent.
In addition, as described above, in this specification, the HLB value means a value calculated from the ratio of the organic value and the inorganic value of the compound (Oda equation), and “Formation Design with Organic Conception Diagram” [ In 1998, NIHON EMULSION CO. , LTD].

  In the present invention, the repeating unit (D) includes the repeating unit (D1) represented by the formula (D1), the repeating unit (D2) represented by the formula (D2), and the repeating unit represented by the formula (D3). 1 or more types chosen from a unit (D3) are preferable.

[In the formula (D1),
R ⁵¹ represents a hydrogen atom or a methyl group,
R ⁵² and R ⁵³ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms. ]

In formula (D1), R ⁵² and R ⁵³ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms.
The alkyl group represented by R ⁵² and R ⁵³ may be linear or branched, and examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
The number of carbon atoms of the hydroxyalkyl group represented by R ⁵² and R ⁵³ is preferably 1 or 2. The alkyl group contained in the hydroxyalkyl group may be linear or branched, and examples of the hydroxyalkyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxyisopropyl group. In addition, the substitution position of the hydroxy group in the hydroxyalkyl group is arbitrary.

  Examples of the monomer for deriving such a repeating unit (D1) include dimethyl (meth) acrylamide, diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- (hydroxymethyl) (meth) acrylamide, N- (2 -Hydroxyethyl) (meth) acrylamide and the like, and the repeating unit (D1) may be a single unit or a combination of two or more types.

[In the formula (D2),
R ⁵⁴ represents a hydrogen atom or a methyl group,
R ⁵⁵ and R ⁵⁶ each independently represent an alkylene group having 1 to 3 carbon atoms. ]

Wherein (D2), R ⁵⁵ and R ⁵⁶ each independently represent an alkylene group having 1 to 3 carbon atoms. The alkylene group preferably has 1 or 2 carbon atoms. The alkylene group may be linear or branched, but is preferably linear. Preferable specific examples include methane-1,1-diyl group and ethane-1,2-diyl group.

  Examples of the monomer for deriving such a repeating unit (D2) include 4- (meth) acryloylmorpholine.

[In the formula (D3),
R ⁵⁷ represents a hydrogen atom or a methyl group,
R ⁵⁸ represents an alkylene group having 1 to 5 carbon atoms. ]

In the formula (D3), R ⁵⁷ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
In the formula (D3), R ⁵⁸ represents an alkylene group having 1 to 5 carbon atoms. The alkylene group preferably has 3 to 5 carbon atoms. The alkylene group may be linear or branched, but is preferably linear. Preferable specific examples include a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group.

  Examples of the monomer for deriving such a repeating unit (D3) include 1-vinyl-2-pyrrolidone and N-vinyl-ε-caprolactam. The repeating unit (D3) may be used alone or in combination of two or more. It may be used in combination.

  Among these repeating units (D1) to (D3), from the viewpoint of hydrophilicity, the repeating units (D1) and (D2) are preferable, and the repeating unit (D1) is particularly preferable.

As content of the repeating unit (D) in the polymer II of this invention, 80-99.9 mass% is preferable with respect to all the repeating units contained in the polymer II, and 85-85 mass% from a hydrophilic viewpoint. 99.5 mass% is more preferable, 90-99 mass% is still more preferable, and 95-99 mass% is still more preferable.
The content of the repeating unit (D) can be measured by ¹ H-NMR, ¹³ C-NMR or the like.

  The polymer II of the present invention may be any of a block copolymer, a graft copolymer, a random copolymer, and an alternating copolymer.

Further, the weight average molecular weight (Mw) of the polymer II of the present invention is preferably 10,000 to 10,000,000, more preferably 10,000 to 5,000,000, still more preferably 10,000 to 3,000,000, and 10,000 to 2,000,000. More preferably, 10,000 to 500,000 are more preferable, 10,000 to 250,000 are more preferable, and 10,000 to 150,000 are particularly preferable. By setting the weight average molecular weight within such a range, both the interaction with the bactericidal compound and the handling property are improved.
The number average molecular weight (Mn) of the polymer II of the present invention is preferably 5,000 to 10,000,000, more preferably 5,000 to 5,000,000, still more preferably 5,000 to 3,000,000, and 5,000 to 2,000,000. More preferably, 5,000 to 500,000 are more preferable, and 5,000 to 100,000 are particularly preferable.
Moreover, as molecular weight distribution (Mw / Mn), 1-10 are preferable, 1-7 are more preferable, and 1-5 are especially preferable.
In addition, what is necessary is just to measure the said weight average molecular weight, number average molecular weight, and molecular weight distribution according to the method as described in the Example mentioned later.

  The polymer II of the present invention is a water-soluble polymer. Here, in this specification, to dissolve in water means that the polymer becomes transparent when added to and mixed with water (25 ° C.) so that the polymer solid content is 0.5% by mass. Say.

  The polymer II of the present invention is prepared, for example, as follows. That is, one or more monomers selected from the monomers for deriving each repeating unit are selected and mixed. This mixture is dissolved in a solvent such as water, acetonitrile, ethanol, 2-propanol, 1,4-dioxane as necessary. And the target polymer II can be obtained by adding a polymerization initiator and carrying out radical polymerization.

  In addition, the polymerization initiator used when performing radical polymerization is not particularly limited as long as it is a normal radical polymerization initiator. For example, benzoyl peroxide, lauroyl peroxide, diisopropyl peroxydicarbonate, tert. -Butylperoxy-2-ethylhexanoate, tert-butylperoxypivalate, tert-butylperoxydiisobutyrate, azobisisobutyronitrile, azobisisodimethylvaleronitrile, 2,2'-azobis [2- ( 2-Imidazolin-2-yl) propane] dihydrochloride, and persulfate and persulfate monosulfite-based polymerization initiators.

  Moreover, 0.001-10 mass parts is preferable with respect to 100 mass parts of monomer components, and, as for the usage-amount of a polymerization initiator, 0.01-5 mass parts is more preferable. The polymerization temperature is preferably 20 to 100 ° C., and the polymerization time is preferably 0.5 to 48 hours.

  The content of the polymer selected from the polymer I and the polymer II is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass with respect to the total amount of the bactericidal composition. It is more preferably from 01 to 3% by mass, and particularly preferably from 0.05 to 1% by mass. When the content of the polymer selected from the polymer I and the polymer II is within the above range, the composition has excellent bactericidal action and bacteriostatic action.

<Bactericidal compound having a cationic group>
The bactericidal composition of the present invention contains a bactericidal compound having a cationic group. Although the bactericidal compound having a cationic group is not particularly limited, for example, polyhexamethylene biguanide derivatives such as polyhexanide hydrochloride (polyhexamethylene biguanide, PHMB), polydronium chloride derivatives such as polydronium chloride, polyquaternium derivatives such as polyquaternium, chlorhexidine, etc. Chlorhexidine derivatives, benzalkonium chloride derivatives such as benzalkonium chloride, and benzethonium chloride derivatives such as benzethonium chloride. One of these may be contained alone or in combination of two or more.
Among these, polyhexamethylene biguanide derivatives, polydronium chloride derivatives, polyquaternium derivatives, and benzalkonium chloride derivatives are preferable, and polyhexanide hydrochloride and polydronium chloride are particularly preferable from the viewpoint of obtaining sufficient bactericidal performance.

  The content of the bactericidal compound having a cationic group in the present invention is preferably 0.1 to 1500 ppm, more preferably 0.5 to 1000 ppm, still more preferably 1 to 750 ppm, based on the total amount of the bactericidal composition. ˜500 ppm is particularly preferred. When the content of the bactericidal compound having a cationic group is within the above range, the bactericidal action and bacteriostatic action of the bactericidal composition are improved.

The bactericidal composition of the present invention comprises a polymer selected from the polymer I and the polymer II, a bactericidal compound, a bactericidal compound other than the above, a surfactant, a tonicity agent, a chelating agent, a pH Known additives such as regulators, buffers and thickeners; may contain a solvent.
Moreover, the bactericidal composition of the present invention may contain an appropriate amount of various pharmacologically active components and physiologically active components in addition to the above components. Such ingredients are not particularly limited, and various additives described in, for example, over-the-counter drug manufacturing (import) approval standard 2000 edition (supervised by the Pharmaceutical Affairs Research Group), Pharmaceutical Additives Encyclopedia 2007 (edited by the Japan Pharmaceutical Additives Association) It can be illustrated.

And according to the bactericidal composition of this invention, the reduction of the bactericidal performance by adsorption | suction of a bactericidal compound can be suppressed. The bactericidal composition of the present invention is particularly useful for inhibiting bacterial growth.
Examples of bacteria include gram positive bacteria and gram negative bacteria. Examples of the Gram-positive bacteria include staphylococci such as Staphylococcus aureus, Listeria bacteria, Bacillus bacteria, and Alicyclobacillus bacteria. Examples of Gram-negative bacteria include Escherichia bacteria such as Escherichia coli, Salmonella bacteria, Vibrio bacteria, and Pseudomonas bacteria.

  The bactericidal composition of the present invention contains a polymer selected from the polymer I and the polymer II and a bactericidal compound having a cationic group, and is used in combination with other components to provide a solution, a dispersion, It may be a material in the form of a gel, capsule, pellet, film, sheet, fiber or the like.

  For example, the bactericidal composition of the present invention comprises a solvent such as water or an organic solvent; a surfactant such as anionic, cationic or nonionic; a thickener such as gelatin, polysaccharide or cellulose; When used in combination with a curable monomer such as a functional epoxy compound, a coating material for sterilization can be obtained. Such coating materials include, for example, coating materials for medical equipment such as medical equipment and medical equipment; coating materials for daily goods such as toilet goods and kitchen goods; interior paints in hospitals, elderly facilities, food factories, etc., and hulls and touches. It can be used as a coating material for screen panels.

  In addition, the bactericidal composition of the present invention is used in combination with organic polymer materials such as polyolefin, polyurethane, ABS, polystyrene, polycarbonate, polyester, polyamide, acrylic polymer, vinyl chloride, silicone, cellulose, etc. Materials such as plastics, films, fibers, rubber, ceramics, and glass that have been given bactericidal properties by surface-treating molded products made from inorganic materials such as organic polymer materials, metals, and ceramics with a bactericidal composition It can be. Such materials include, for example, medical supplies such as masks, surgical clothes, surgical coverings, blood bags, wound dressings; daily items such as bed sheets, towels, trash cans, and triangular corners; smartphones, tablet terminals, car navigation systems, etc. It can be used for touch panel devices. It can also be used as a packaging material for building materials such as wallpaper and tiles; food and medical equipment.

  Moreover, the bactericidal composition of this invention can be used for the sterilization method. Although the method is not particularly limited, for example, a method of applying the bactericidal composition of the present invention as a liquid and applying it to the surface of the object can be mentioned, thereby imparting bactericidal properties to the object. it can. At this time, in addition to the polymer selected from the polymer I and the polymer II and the bactericidal compound having a cationic group, in addition to the solvent, a surfactant, a thickener, A curable monomer or the like can be blended. As the application means, usual application means such as spray coating, coater coating, dipping, brush coating, roll coating and the like can be employed. Examples of the object include base materials such as films, resin substrates, fibers, ceramics, metals, glass, and wood; interiors such as walls, floors, and ceilings; medical treatments such as catheters, infusion tubes, blood bags, and dressing materials. Examples include instruments.

  In addition, by applying the bactericidal composition of the present invention to an object using a spray or the like, it is possible to impart bactericidal properties to the object or to sterilize the object. At this time, in addition to the polymer selected from the polymer I and the polymer II and the bactericidal compound having a cationic group, in addition to the solvent, a surfactant, a fragrance, and the like are added to the bactericidal composition of the present invention. can do.

Moreover, a target object can also be sterilized and disinfected by impregnating the nonwoven fabric of this invention in a nonwoven fabric, and wiping off a target object. At this time, the bactericidal composition of the present invention includes, in addition to the polymer selected from the polymer I and the polymer II and the bactericidal compound having a cationic group, a surfactant, a fragrance, an enzyme, A buffer solution or the like can be blended.
Moreover, it can be set as materials, such as a plastic, a film, a fiber, and rubber | gum which provided the bactericidal property by mix | blending the bactericidal composition of this invention with the organic polymer material.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.

Each analysis condition in the examples is as follows.
<Molecular weight measurement>
The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using a TSKgel α-M column manufactured by Tosoh Corporation, flow rate: 0.5 ml / min, elution solvent: NMP solvent (H ₃ PO ₄ : 0.016M, LiBr: 0.030M), column temperature: Measured by gel permeation chromatography (GPC) using polystyrene as a standard under analysis conditions of 40 ° C.

<NMR spectrum>
The ¹ H-NMR spectrum, d _6-DMSO as solvent, using a Wako Pure Chemical Industries, Ltd. DSS-d6 as an internal standard substance, was measured by BRUKER Ltd. Model AVANCE 500 (500 MHz).

<Electrical conductivity measurement>
The content of the carboxy group was measured using an electric conductivity measurement method (Metrohm, 794 Basic Titrino).

<Materials Used in Synthesis Examples 1-7 and Comparative Synthesis Examples 1-3>
Hydrophilic monomer: N, N-dimethylacrylamide (hereinafter referred to as DMAA: manufactured by KJ Chemical), N- (2-hydroxy) ethylacrylamide (hereinafter referred to as HEAA: manufactured by KJ Chemical), N-vinyl-2 -Pyrrolidone (hereinafter referred to as NVP: manufactured by Wako Pure Chemical Industries), 2-methacryloyloxyethyl-2 '-(trimethylammonio) ethyl phosphate (hereinafter referred to as MPC: manufactured by NOF Corporation)
Hydrophobic monomer: N-dodecylacrylamide (hereinafter referred to as DDAA: manufactured by Tokyo Chemical Industry Co., Ltd.), N-butoxymethylacrylamide (hereinafter referred to as NBMA: manufactured by MRC Unitech), 3- [tris (trimethylsiloxy) methacrylate Silyl] propyl (hereinafter referred to as TRIS: manufactured by Chisso Corporation), 2-ethylhexyl acrylate (hereinafter referred to as EHA: manufactured by Wako Pure Chemical Industries, Ltd.)
Polymerization initiator: 2,2′-azobis (isobutyronitrile) (hereinafter referred to as AIBN: Wako Pure Chemical Industries, Ltd.), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] Dihydrochloride (hereinafter referred to as VA-044 manufactured by Wako Pure Chemical Industries, Ltd.)
Solvent: acetonitrile (hereinafter referred to as ACN: manufactured by Wako Pure Chemical Industries), ethanol (hereinafter referred to as EtOH: manufactured by Wako Pure Chemical Industries), water, 1,4-dioxane (hereinafter referred to as DOX: manufactured by Wako Pure Chemical Industries, Ltd.) )
Molecular weight regulator: 1-thioglycerol (hereinafter referred to as TG: manufactured by Asahi Chemical Co., Ltd.)
RAFT agent: 2- [dodecylthio (thiocarbonyl) thio] -2-methylpropionic acid (hereinafter referred to as DTMPA: Sigma-Aldrich)

(Synthesis Example 1 Synthesis of Copolymer (I-1))
DMAA (14.25 g) as a hydrophilic monomer, DDAA (0.75 g) as a hydrophobic monomer, AIBN (0.3 g) as a polymerization initiator, and ACN (61.2 g) as a solvent were mixed and placed in a flask. Nitrogen was blown into this, the temperature was raised to 70 ° C., polymerized for 8 hours, and then cooled to room temperature. The obtained solution was dialyzed with pure water to obtain a 0.5 mass% aqueous solution of copolymer (I-1).
In the obtained copolymer (I-1), the content of the repeating unit derived from DMAA was 95.0% by mass, and the content of the repeating unit derived from DDAA was 5.0% by mass. These contents were measured by ¹ H-NMR. The weight average molecular weight of the obtained copolymer (I-1) was 156,000, the number average molecular weight was 37,000, and the molecular weight distribution was 4.2.

(Synthesis Examples 2-6 Synthesis of Copolymers (I-2) to (I-6))
Under the polymerization conditions shown in Table 1, copolymers (I-2) to (I-6) were synthesized in the same manner as in Synthesis Example 1, and 0 of copolymers (I-2) to (I-6) were synthesized. A 5 mass% aqueous solution was obtained.

(Synthesis Example 7 Synthesis of Copolymer (I-7))
Nitrogen bubbling was carried out at 70 ° C. for 13 hours after 0.04 g of EHA as a hydrophobic monomer, 0.0326 g of DTMPA as a RAFT agent, 0.0007 g of AIBN as a polymerization initiator, and 10 mL of DOX as a solvent. Next, 7.60 g of DMAA as a hydrophilic monomer and 10 mL of DOX as a solvent were added, and the mixture was further stirred at 70 ° C. for 24 hours. After completion of the reaction, the reaction solution was poured into diethyl ether, washed three times with diethyl ether, and then vacuum dried to synthesize an AB type block copolymer (I-7). Then, it was made to melt | dissolve in water and the 0.5 mass% aqueous solution of copolymer (I-7) was obtained.

(Comparative Synthesis Examples 1 to 3 Synthesis of Polymers (N-1) to (N-3))
Under the polymerization conditions shown in Table 2, polymers (N-1) to (N-2) were synthesized in the same manner as in Synthesis Example 1, and 0.5 of polymers (N-1) to (N-2) were synthesized. A mass% aqueous solution was obtained.
Further, a polymer (N-3) was synthesized in the same manner as in Synthesis Example 1 under the polymerization conditions shown in Table 2. When the polymer (N-3) was added to water so as to have a concentration of 0.5% by mass, the polymer (N-3) became cloudy and an aqueous solution could not be prepared.

  The physical properties and the like of the polymers obtained in Synthesis Examples 1 to 7 and Comparative Synthesis Examples 1 to 3 are shown in Table 3 below. Copolymers (I-1) to (I-7) obtained in Synthesis Examples 1 to 7 correspond to the polymer I of the present invention.

(Synthesis Example 8 Synthesis of Copolymer (II-1))
1-4.7 g of N- (2-hydroxy) ethylacrylamide (HEAA (manufactured by KJ Chemicals), hereinafter referred to as HEAA) as a (meth) acrylamide monomer, and 80% acrylic acid ((Toagosei Co., Ltd.) as an acidic group-containing monomer Manufactured), hereinafter referred to as AA) 0.375 g, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride 0.6 g as a polymerization initiator, and pure water as a solvent 141 g was mixed and placed in a flask. Nitrogen was blown into this, the temperature was raised to 62 ° C., polymerized for 6 hours, and then cooled to room temperature. The obtained solution was neutralized with sodium hydroxide to pH 7, and then dialyzed with pure water to obtain a 0.5 mass% aqueous solution of copolymer (II-1).
In the obtained copolymer (II-1), the content of the repeating unit derived from HEAA was 98% by mass, and the content of the repeating unit derived from AA was 2% by mass. These contents were calculated by ¹ H-NMR and electrical conductivity measurement. The weight average molecular weight of the obtained copolymer (II-1) was 64,000, the number average molecular weight was 34,000, and the molecular weight distribution was 1.9.

(Synthesis Examples 9 to 11 Synthesis of Copolymers (II-2) to (II-4))
Copolymers (II-2) to (II-4) were synthesized in the same manner as in Synthesis Example 8 except that the monomer composition was changed to that shown in Table 4, and the copolymers (II-2) to (II-) were synthesized. 4) 0.5 mass% aqueous solution was obtained.

(Comparative Synthesis Examples 4 to 5 Synthesis of polymers (N-4) to (N-5))
Polymers (N-4) to (N-5) were synthesized in the same manner as in Synthesis Example 8 except that the monomer composition was changed to those shown in Table 4, and the polymers (N-4) to (N-5) were synthesized. Of 0.5% by mass was obtained.

  The physical properties and the like of each polymer obtained in Synthesis Examples 8 to 11 and Comparative Synthesis Examples 4 to 5 are shown in Table 5 below. Copolymers (II-1) to (II-4) obtained in Synthesis Examples 8 to 11 correspond to the polymer II of the present invention.

Example 1
0.5 parts by mass of the copolymer (I-1) obtained in Synthesis Example 1, 0.05 parts by mass of polyhexamethylene biguanide (hereinafter, PHMB), and 99.5 parts by mass of physiological saline were mixed. The obtained composition was stored in a polypropylene container and a glass container at room temperature (25 ° C.) for 24 hours. This is the composition of Example 1.

(Examples 2-7, Comparative Examples 1-2)
In Example 1, except that the copolymer (I-1) was changed to the copolymers (I-2) to (I-7) and the polymers (N-1) to (N-2). A composition was obtained in the same manner as in Example 1.

(Example 8)
0.5 parts by mass of the copolymer (II-1) obtained in Synthesis Example 8, 0.05 parts by mass of PHMB, and 99.5 parts by mass of physiological saline were mixed, and the resulting composition was mixed with polypropylene. Each container and glass container were stored at room temperature (25 ° C.) for 24 hours. This is the composition of Example 8.

(Examples 9-11, Comparative Examples 3-4)
In Example 8, except that the copolymer (II-1) was changed to the copolymers (II-2) to (II-4) and the polymers (N-4) to (N-5), it was carried out. A composition was obtained in the same manner as in Example 8.

(Test Example 1 Bactericidal Performance Confirmation Test -Evaluation by Micro Liquid Dilution Method)
<Preparation of liquid medium>
In an Erlenmeyer flask, 16.8 g of BD Difco Mueller-Hinton Bros medium was weighed and dissolved in 800 mL of sterile water. A liquid medium was prepared by covering the mouth of the Erlenmeyer flask with aluminum foil twice, attaching an indicator seal, and treating with an autoclave at 120 ° C. for 15 minutes.
<Preparation of bacterial solution>
To 10 mL of the liquid medium obtained in “Preparation of liquid medium” above, The OD600 was adjusted to 1.0 by suspending E. coli DH5α strain (Gram-negative bacterium). When OD600 is 1.0, the amount of bacteria is about 1.8 × 10 ⁸ cfu / mL. 8 mL of the above liquid medium was further added to prepare a bacterial solution having a bacterial amount of 1.0 × 10 ⁸ cfu / mL.
<Turbidity evaluation>
A measurement sample was prepared by mixing 10 μL of the composition of Example 1 and 90 μL of the liquid medium obtained in “Preparation of Liquid Medium” above. On the well plate, 5 μL of the bacterial solution obtained in the above “Preparation of bacterial solution” was added to 100 μL of the obtained measurement sample. After incubation at 37 ° C. for 16 hours, the turbidity of the wells was visually observed, and the growth state of the bacteria was evaluated according to the following criteria. Moreover, also about the case where the composition of Example 1 was changed into the composition of Examples 2-11 and Comparative Examples 1-4, the growth state of the microbe was evaluated similarly to the above.
These evaluation results are shown in Tables 6-7.
<Evaluation criteria>
-: Transparent and no turbidity was observed (growth of bacteria was suppressed)
+: Turbidity was observed (fungus grew)

(Test Example 2 PHMB adsorption suppression test)
In a 50 mL centrifuge tube, 2 mL of each of the compositions of Examples 1 to 11 and Comparative Examples 1 to 4 was measured, and one glass piece and one polypropylene piece were immersed in this, and a 35 ° C. thermostatic bath. It was allowed to stand for 24 hours. Thereafter, the glass piece and the polypropylene piece were taken out, 0.2 ml of 0.003 w / v% acetone solution of fluorescamine was added to 2 mL of the composition, mixed for 30 seconds, and then a spectrofluorometer FP-6200 manufactured by JASCO Corporation. Was used to measure fluorescence (excitation wavelength: 390 nm, wavelength region: 220 to 730 nm, measurement mode: Emission), and the presence or absence of PHMB adsorption was observed from the fluorescence intensity at the wavelength showing the maximum fluorescence intensity. The evaluation results are shown in Tables 6-7.

Claims (11)

Water-soluble polymer I having hydrophilic repeating unit (A) and hydrophobic repeating unit (B) having an HLB value of 1 to 14, and repeating unit (C) having an acidic group and (meth) acrylamide monomer A polymer selected from water-soluble polymers II having a repeating unit (D) derived from
Including a bactericidal compound having a cationic group,
Bactericidal composition. The composition according to claim 1, wherein the hydrophilic repeating unit (A) is a repeating unit represented by the formula (A0).

[In the formula (A0),
R ¹ represents a hydrogen atom or a methyl group,
R ² represents —O—, * — (C═O) —O—, * — (C═O) —NR ⁴ —, or * —NR ⁴ — (C═O) — (R ⁴ represents a hydrogen atom Or an organic group having 1 to 10 carbon atoms, and * represents a position bonded to the carbon atom to which R ¹ in the formula (A0) is bonded.
R ³ represents an organic group having 1 to 30 carbon atoms.
However, R ² is, * - (C = O) -NR 4 -, or ^{* -NR 4 - (C = O} ) - and is, and R ⁴ is, if an organic group having 1 to 10 carbon atoms , R ³ and R ⁴ may be combined to form a ring. ] The composition according to claim 1 or 2, wherein the hydrophobic repeating unit (B) is a repeating unit represented by the formula (B1) or (B2).

[In the formula (B1),
R ⁵ represents a hydrogen atom or a methyl group,
R ⁶ represents —O—, * — (C═O) —O—, * — (C═O) —NR ⁸ —, or * —NR ⁸ — (C═O) — (R ⁸ represents a hydrogen atom Or an organic group having 1 to 10 carbon atoms, and * represents a position bonded to the carbon atom to which R ⁵ in the formula (B1) is bonded.
R ⁷ represents an organic group having 4 to 30 carbon atoms. ]

[In the formula (B2),
R ⁹ represents a hydrogen atom or a methyl group,
R ¹⁰ is —O—, * — (C═O) —O—, * — (C═O) —NR ¹⁷ —, * —NR ¹⁷ — (C═O) — (R ¹⁷ is a hydrogen atom or An organic group having 1 to 10 carbon atoms, * represents a position bonded to the carbon atom to which R ⁹ in the formula (B2) is bonded) or a phenylene group;
R ¹¹ represents a divalent organic group having 1 to 10 carbon atoms,
R ¹² and R ¹³ each independently represents an organic group having 1 to 10 carbon atoms,
R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently —OSi (R ¹⁸ ) ₃ (R ¹⁸ is independently a hydrogen atom or an organic group having 1 to 8 carbon atoms) or 1 carbon atom. 10 to 10 organic groups
n represents an integer of 0 to 200. ] The hydrophilic repeating unit (A) is a repeating unit (A1) represented by formula (A1), a repeating unit (A2) represented by formula (A2), or a repeating unit (A3 represented by formula (A3)). ), A repeating unit (A4) represented by the formula (A4), a repeating unit (A5) represented by the formula (A5) and a repeating unit (A6) represented by the formula (A6). The composition according to any one of claims 1 to 3.

[In the formula (A1),
R ^a represents a hydrogen atom or a methyl group,
R ^b is —O—, * — (C═O) —O—, * — (C═O) —NR ^e —, or * —NR ^e — (C═O) — (R ^e is a hydrogen atom. Or an organic group having 1 to 10 carbon atoms, and * represents a position bonded to the carbon atom to which R ^a in the formula (A1) is bonded;
R ^c represents a polyoxyalkylene group,
R ^d represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[In the formula (A2),
R ¹⁹ represents a hydrogen atom or a methyl group,
R ²⁰ represents an alkylene group having 2 to 4 carbon atoms,
R ²¹ represents an alkylene group having 1 to 10 carbon atoms,
R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
q represents an integer of 1 to 10. ]

[In the formula (A3),
Y ^{is, - (C = O) O} -, - (O = S = O) O -, -O (O = S = O) O -, - (S = O) O -, -O (S = O ) O ⁻ , —O (P═O) (OR ³⁰ ) O ⁻ , —O (P═O) (R ³⁰ ) O ⁻ , — (P═O) (OR ³⁰ ) O ⁻ or — (P═O) ) (R ³⁰⁾ O ^- shows the (R ³⁰ represents an alkyl group having 1 to 3 carbon atoms),
R ²⁵ represents a hydrogen atom or a methyl group,
R ²⁶ and R ²⁷ each independently represent a divalent organic group having 1 to 10 carbon atoms,
R ²⁸ and R ²⁹ each independently represent an alkyl group having 1 to 10 carbon atoms. ]

[In the formula (A4),
R ³¹ represents a hydrogen atom or a methyl group,
R ³² and R ³³ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms. ]

[In the formula (A5),
R ³⁴ represents a hydrogen atom or a methyl group,
R ³⁵ and R ³⁶ each independently represents an alkylene group having 1 to 2 carbon atoms. ]

[In the formula (A6),
R ³⁷ represents a hydrogen atom or a methyl group,
R ³⁸ represents an alkylene group having 1 to 3 carbon atoms. ]   The composition according to any one of claims 1 to 4, wherein the hydrophobic repeating unit (B) is a repeating unit derived from a (meth) acrylamide monomer.   The composition according to any one of claims 1 to 5, wherein the polymer I contains 65 to 99 mass% of the repeating unit (A) and 0.1 to 35 mass% of the repeating unit (B).   The composition according to any one of claims 1 to 6, wherein the acidic group of the repeating unit (C) is a carboxy group, a sulfo group, a phosphoric acid group, or a salt thereof. The repeating unit (D) is a repeating unit (D1) represented by formula (D1), a repeating unit (D2) represented by formula (D2), or a repeating unit (D3) represented by formula (D3). The composition of any one of Claims 1-7 which is 1 or more types chosen from these.

[In the formula (D1),
R ⁵¹ represents a hydrogen atom or a methyl group,
R ⁵² and R ⁵³ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms. ]

[In the formula (D2),
R ⁵⁴ represents a hydrogen atom or a methyl group,
R ⁵⁵ and R ⁵⁶ each independently represent an alkylene group having 1 to 3 carbon atoms. ]

[In the formula (D3),
R ⁵⁷ represents a hydrogen atom or a methyl group,
R ⁵⁸ represents an alkylene group having 1 to 5 carbon atoms. ]   The composition according to any one of claims 1 to 8, wherein the polymer II contains 0.1 to 20% by mass of the repeating unit (C) and 80 to 99.9% by mass of the repeating unit (D). .   The bactericidal compound having a cationic group is one or more selected from a polyhexamethylene biguanide derivative, a polydronium chloride derivative, a polyquaternium derivative, and a benzalkonium chloride derivative. The composition as described.   The composition according to any one of claims 1 to 10, wherein the content of the polymer selected from the polymer I and the polymer II is 0.001 to 10% by mass.