JP2019178200A - Biofilm formation inhibiting coating agent and biofilm formation inhibiting laminate - Google Patents

Abstract

To provide a biofilm formation inhibiting coating agent that is excellent in safety, coating properties and water proofness and can inhibit biofilm formation for a long time, and a biofilm formation inhibiting laminate with a coating made of the coating agent.SOLUTION: The biofilm formation inhibiting coating agent comprises a vinyl polymer (a) having a mass average molecular weight from 2,000 to 10,000,000 and having in a side chain at least one of a betaine structure represented by general formula 1, a betaine structure having a vinylimidazole skeleton, and a betaine structure having a vinylpyridine skeleton.SELECTED DRAWING: None

Description

  The present invention relates to a biofilm formation-inhibiting laminate having a biofilm formation-inhibiting coating agent and a coating film comprising the coating agent.

  Biofilms are also called biofilms or slimes, and in general, microorganisms such as bacteria and mold adhere to and grow on the surface of substances in the aqueous system to produce macromolecular substances such as polysaccharides and proteins from the inside of microbial cells. It refers to what is formed. Comparing before and after the biofilm is formed, when the biofilm is formed once, it shows remarkably high resistance to washing / removal, antibiotics, drugs, heat, drying and the like. As a result, harm caused by microorganisms that have adhered and proliferated occurs, causing problems in various industrial fields.

  For example, bacteria adhere to the tube of a medical device such as a catheter to form a biofilm, which causes clogging and makes it impossible to perform treatment to be treated. In addition, the biofilm may peel off, and bacterial aggregates may enter the body, resulting in serious disease. When a biofilm is formed in the piping of a food plant, the biofilm peels off and leads to contamination by foreign substances in the product, and also causes food poisoning due to microorganism-derived toxins. Furthermore, biofilm formation on the metal surface causes metal corrosion and promotes aging of the equipment. Moreover, if a biofilm is formed on the inner surface of the water tank, it will adversely affect the organisms in the water tank.

  Thus, suppression of biofilm formation has been demanded, and various studies have been made on suppression of biofilm formation.

  Patent Document 1 discloses a biofilm treatment agent containing an amphoteric surfactant such as low molecular weight lauryldimethylaminoacetate betaine as a biofilm disintegrant. Once formed, the biofilm is treated with a low molecular weight surfactant. A method of cleaning is disclosed. However, it is difficult to remove the biofilm once formed, and the labor burden due to the cleaning work is large. In addition, a large amount of water is used in the cleaning operation, which causes treatment problems and environmental pollution problems.

  Patent Document 2 suppresses the formation of a biofilm characterized by a polymer compound having at least one group selected from an amino group and a quaternary ammonium group and derived from a vinyl monomer having an anionic group. A method is disclosed in which the polymer compound exhibits anti-microbial adhesion, sterilization, and antibacterial action and suppresses biofilm formation. However, the polymer compound has poor water resistance and insufficient biofilm formation inhibitory properties.

JP 2017-078029 A JP 2010-163429 A

  An object of the present invention is to provide a biofilm formation-inhibiting coating agent that is excellent in safety, coating properties, and water resistance, and that can suppress biofilm formation for a long period of time, and a biofilm comprising the coating agent. It is providing a film formation suppression laminated body.

  The present inventors have studied in order to solve the above-mentioned problems. As a result, the present invention has at least one of the structures represented by the general formulas 1 to 3 in the side chain, and has a mass average molecular weight of 2,000 to 10,000. The present inventors have found that a vinyl-based polymer having a molecular weight of 1,000 has a long-term biofilm formation inhibitory effect, leading to the present invention. That is, this invention relates to the biofilm formation suppression coating agent of following <1>-<5>, and the biofilm formation suppression laminated body of <6>.

<1> A vinyl polymer (a) having at least one structure represented by the following general formulas 1 to 3 in a side chain and having a mass average molecular weight of 2,000 to 10,000,000 is included. A biofilm formation inhibiting coating agent.
(In general formulas 1 to 3,
R ₁ is an alkylene group having 1 to 6 carbon atoms,
R ₂ and R ₃ are each independently an alkyl group having 1 to 4 carbon atoms,
R ₄ is an alkylene group having 1 to ₄ carbon atoms,
X is an oxygen atom or NH,
Y is COO ⁻ or SO ₃ ⁻ ,
R ₅ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ₆ is an alkylene group having 1 to 6 carbon atoms or a hydroxyalkylene group having 1 to 6 carbon atoms,
4 of R _{7 to} R ₁₁ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and one of R _{7 to} R ₁₁ represents a bonding position with the main chain of the vinyl polymer,
R ₁₂ is an alkylene group having 1 to 6 carbon atoms or a hydroxyalkylene group having 1 to 6 carbon atoms,
* Represents a bonding position with the main chain of the vinyl polymer (a). )

<2> The biofilm formation inhibiting coating agent according to <1>, wherein the polymer (a) contains a betaine structure in an amount of 0.25 to 4.5 mmol / g.

<3> The polymer (a) is represented by the general formulas 1 to 3 (provided that the bonding position with the main chain of the vinyl polymer in the general formulas 1 to 3 represents the bonding position with the monomer). A vinyl polymer obtained by polymerizing a monomer having the above structure with another monomer, or a vinyl polymer having at least one structure represented by the following general formulas 4 to 6 in the side chain and a betaine agent The biofilm formation inhibiting coating agent according to <1> or <2>, which is a reaction product of
(In general formulas 4-6,
R ₁₃ is an alkylene group having 1 to 6 carbon atoms,
R ₁₄ and R ₁₅ are each independently an alkyl group having 1 to 4 carbon atoms,
X is an oxygen atom or NH,
R ₁₆ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
4 of R _{17 to} R ₂₁ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and one of R _{17 to} R ₂₁ is a bonding position with the main chain of the vinyl polymer (a), Represents
* Indicates the bonding position with the main chain of the vinyl polymer,
** represents a reaction site with a betaine agent. )

<4> The biofilm formation inhibiting coating agent according to any one of <1> to <3>, wherein the polymer (a) has a crosslinkable group.

<5> The biofilm formation inhibiting coating agent according to any one of <1> to <4>, further including a crosslinking agent.

The biofilm formation suppression laminated body which has a coating film which consists of a biofilm formation suppression coating agent of any one of <1>-<5> on a <6> base material.

  According to the present invention, it is possible to provide a biofilm formation-inhibiting coating agent that is excellent in safety, coating property, and water resistance and that can suppress biofilm formation for a long period of time. The biofilm formation-suppressing coating agent of the present invention can be suitably used on the surface of a substance that is expected to form a biofilm by attaching microorganisms, such as a medical device, a manufacturing facility, or an inner surface of a water tank.

<Biofilm formation inhibiting coating agent>
The biofilm formation-inhibiting coating agent of the present invention has at least one structure represented by the following general formulas 1 to 3 in the side chain, and has a mass average molecular weight of 2,000 to 10,000,000. It contains a system polymer (a). By having this structure, an excellent effect of suppressing biofilm formation is exhibited. Among these, from the viewpoint of suppressing long-term biofilm formation, a structure represented by the following general formula 1 is preferable.

(In general formulas 1 to 3,
R ₁ is an alkylene group having 1 to 6 carbon atoms,
R ₂ and R ₃ are each independently an alkyl group having 1 to 4 carbon atoms,
R ₄ is an alkylene group having 1 to ₄ carbon atoms,
X is an oxygen atom or NH,
Y is COO ⁻ or SO ₃ ⁻ ,
R ₅ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ₆ is an alkylene group having 1 to 6 carbon atoms or a hydroxyalkylene group having 1 to 6 carbon atoms,
4 of R _{7 to} R ₁₁ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and one of R _{7 to} R ₁₁ represents a bonding position with the main chain of the vinyl polymer,
R ₁₂ is an alkylene group having 1 to 6 carbon atoms or a hydroxyalkylene group having 1 to 6 carbon atoms,
* Represents a bonding position with the main chain of the vinyl polymer (a). )

<Vinyl polymer (a)>
The polymer (a) of the present invention may have at least one of the structures represented by the general formulas 1 to 3 in the side chain and have a mass average molecular weight of 2,000 to 10,000,000. A well-known polymer can be used and 2 or more types may be used together.

In the present invention, examples of the vinyl polymer having a structure represented by the general formulas 1 to 3 in the side chain and having a mass average molecular weight of 2,000 to 10,000,000 include the following two.
(I) Monomer having at least one of the structures represented by general formulas 1 to 3 (however, the bonding position with the main chain of the vinyl polymer in general formulas 1 to 3 represents the bonding position with the monomer) And a vinyl polymer having a mass average molecular weight of 2,000 to 10,000,000 obtained by polymerizing other monomers.
(II) A mass-average molecular weight of 2,000 to 2,000, which is a reaction product of a vinyl polymer having a structure of at least any tertiary amino group represented by the general formulas 4 to 6 in the side chain and a betaine agent. 10,000,000 polymers. Specifically, a monomer having a structure of at least any tertiary amino group represented by the general formulas 4 to 6 (provided that the bonding position with the main chain of the vinyl polymer in the general formulas 4 to 6 is a monomer) Is a reaction product of a vinyl polymer obtained by polymerizing other monomers and a betaine agent.

A monomer having at least one of the structures represented by the general formulas 1 to 3 (however, the bonding position with the main chain of the vinyl polymer in the general formulas 1 to 3 represents the bonding position with the monomer), and A monomer having a structure of at least any tertiary amino group represented by the above general formulas 4 to 6, which is a precursor of at least any one structure represented by the general formulas 1 to 3 (provided that the above general formulas 4 to 6 In general, the bonding position with the main chain of the vinyl polymer in (represents the bonding position with the monomer) is the monomer (A).
The reaction of a tertiary amino group with a betaine agent is hereinafter also referred to as “betaine formation”.

  Although the monomer which comprises the vinyl polymer (a) of this invention is demonstrated below, it is not limited to these. In the present invention, “(meth) acryl” means both “acryl” and “methacryl”.

<Monomer (A)>
<Monomer (A1) having a structure represented by Formula 1>
Examples of the monomer having a betaine structure represented by the general formula 1 include N- (meth) acryloyloxymethyl-N, N-dimethylammoniummethyl-α-carboxybetaine, N- (meth) acryloyloxyethyl-N, N-dimethylammoniummethyl-α-carboxybetaine, N- (meth) acryloyloxypropyl-N, N-dimethylammoniummethyl-α-carboxybetaine, N- (meth) acryloyloxybutyl-N, N-dimethylammoniummethyl- α-carboxybetaine, N- (meth) acryloyloxymethyl-N, N-diethylammoniummethyl-α-carboxybetaine, N- (meth) acryloyloxyethyl-N, N-diethylammoniummethyl-α-carboxybetaine, N -(Meta) N- (meth) acryloyloxyalkyl- such as Royloxypropyl-N, N-diethylammoniummethyl-α-carboxybetaine, N- (meth) acryloyloxybutyl-N, N-diethylammoniummethyl-α-carboxybetaine, etc. N, N-dialkylammonium alkyl-α-carboxybetaine; N- (meth) acrylamidopropyl-N, N-dimethylammoniummethyl-α-carboxybetaine, N- (meth) acrylamidopropyl-N, N-diethylammoniummethyl- N- (meth) acrylamide alkyl-N, N-dialkylammonium alkyl-α-carboxybetaines such as α-carboxybetaine; N- (meth) acrylamidopropyl-N, N-dimethylammonium methyl-α-carboxybeta N- (meth) acrylamide alkyl-N, N-dialkylammonium alkyl-α-carboxybetaines such as N- (meth) acrylamidopropyl-N, N-diethylammonium methyl-α-carboxybetaine; ) Acrylyloxymethyl-N, N-dimethylammonium methyl-α-sulfobetaine, N- (meth) acryloyloxymethyl-N, N-dimethylammoniumethyl-α-sulfobetaine, N- (meth) acryloyloxymethyl-N , N-dimethylammoniumpropyl-α-sulfobetaine, N- (meth) acryloyloxymethyl-N, N-dimethylammoniumbutyl-α-sulfobetaine, N- (meth) acryloyloxyethyl-N, N-dimethylammoniummethyl -Α-Sulfobetai N- (meth) acryloyloxyethyl-N, N-dimethylammoniumethyl-α-sulfobetaine, N- (meth) acryloyloxyethyl-N, N-dimethylammoniumpropyl-α-sulfobetaine, N- (meth) Acryloyloxyethyl-N, N-dimethylammoniumbutyl-α-sulfobetaine, N- (meth) acryloyloxypropyl-N, N-dimethylammoniummethyl-α-sulfobetaine, N- (meth) acryloyloxypropyl-N, N-dimethylammoniumethyl-α-sulfobetaine, N- (meth) acryloyloxypropyl-N, N-dimethylammoniumpropyl-α-sulfobetaine, N- (meth) acryloyloxypropyl-N, N-dimethylammoniumbutyl- α-sulfobetaine N- (meth) acryloyloxybutyl-N, N-dimethylammonium methyl-α-sulfobetaine, N- (meth) acryloyloxybutyl-N, N-dimethylammoniumethyl-α-sulfobetaine, N- (meth) acryloyl N- (meth) acryloyloxyalkyl-N such as oxybutyl-N, N-dimethylammoniumpropyl-α-sulfobetaine, N- (meth) acryloyloxybutyl-N, N-dimethylammoniumbutyl-α-sulfobetaine, etc. , N-dimethylammoniumalkyl-α-sulfobetaine; N- (meth) acryloyloxymethoxymethoxy-N, N-dimethylammoniummethyl-α-sulfobetaine, N- (meth) acryloyloxymethoxymethoxy-N, N-dimethyl Ammonium ethyl-α- Ruphobetaine, N- (meth) acryloyloxymethoxymethoxy-N, N-dimethylammoniumpropyl-α-sulfobetaine, N- (meth) acryloyloxymethoxymethoxy-N, N-dimethylammoniumbutyl-α-sulfobetaine, N- (Meth) acryloyloxyethoxyethoxy-N, N-dimethylammonium methyl-α-sulfobetaine, N- (meth) acryloyloxyethoxyethoxy-N, N-dimethylammoniumethyl-α-sulfobetaine, N- (meth) acryloyl Oxyethoxyethoxy-N, N-dimethylammoniumpropyl-α-sulfobetaine, N- (meth) acryloyloxyethoxyethoxy-N, N-dimethylammoniumbutyl-α-sulfobetaine, N- (meth) acryloylo Cypropoxypropoxy-N, N-dimethylammonium methyl-α-sulfobetaine, N- (meth) acryloyloxypropoxypropoxy-N, N-dimethylammoniumethyl-α-sulfobetaine, N- (meth) acryloyloxypropoxypropoxy- N, N-dimethylammoniumpropyl-α-sulfobetaine, N- (meth) acryloyloxypropoxypropoxy-N, N-dimethylammoniumbutyl-α-sulfobetaine, N- (meth) acryloyloxybutoxybutoxy-N, N- Dimethylammonium methyl-α-sulfobetaine, N- (meth) acryloyloxybutoxybutoxy-N, N-dimethylammoniumethyl-α-sulfobetaine, N- (meth) acryloyloxybutoxybutoxy-N, N-di N- (meth) acryloyloxyalkoxyanalkoxy-N, N-, such as methylammoniumpropyl-α-sulfobetaine, N- (meth) acryloyloxybutoxybutoxy-N, N-dimethylammoniumbutyl-α-sulfobetaine, etc. Dimethylammonium alkyl-α-sulfobetaine; N- (meth) acrylamidepropyl-N, N-dimethylammoniumpropyl-α-sulfobetaine, N- (meth) acrylamidopropyl-N, N-dimethylammoniumbutyl-α-sulfobetaine N- (meth) acrylamide alkyl-N, N-dialkylammonium alkyl-α-sulfobetaine and the like.

<Monomer (A2) having a structure represented by Formula 2>
Examples of the monomer having a betaine structure represented by the general formula 2 include 1-vinyl-3- (3-sulfopropyl) imidazolium inner salt, 1-vinyl-3- (3-sulfobutyl) imidazolium inner salt, 1-vinyl-2-alkyl- such as 1-vinyl-2-methyl-3- (3-sulfopropyl) imidazolium inner salt, 1-vinyl-2-methyl-3- (4-sulfobutyl) imidazolium inner salt 3- (4-sulfoalkyl) imidazolium inner salt, and the like.

<Monomer (A3) having structure represented by general formula 3>
Examples of the monomer having a betaine structure represented by the general formula 2 include 2-vinyl-1- (3-sulfopropyl) pyridinium inner salt, 2-vinyl-1- (3-sulfobutyl) pyridinium inner salt, and the like. 4-vinyl-1- (3-sulfoalkyl) pyridinium inner salt; 4-vinyl-1- (3-sulfopropyl) pyridinium inner salt, 4-vinyl-1- (3-sulfobutyl) pyridinium inner salt, etc. -Vinyl-1- (3-sulfoalkyl) pyridinium inner salt, and the like.

<Monomer (A4) having a structure represented by Formula 4>
Examples of the monomer having a betaine structure represented by the general formula 4 include N- (meth) acryloyloxymethyl-N, N-dimethylamine, N- (meth) acryloyloxyethyl-N, N-dimethylamine, N -(Meth) acryloyloxypropyl-N, N-dimethylamine, N- (meth) acryloyloxybutyl-N, N-dimethylamine, N- (meth) acryloyloxymethyl-N, N-diethylamine, N- (meta N- (meth) acryloyloxy such as acryloyloxyethyl-N, N-diethylamine, N- (meth) acryloyloxypropyl-N, N-diethylamine, N- (meth) acryloyloxybutyl-N, N-diethylamine Alkyl-N, N-dialkylamines;
N- (meth) acrylamide alkyl-N, N-dialkylamines such as N- (meth) acrylamidopropyl-N, N-dimethylamine, N- (meth) acrylamidopropyl-N, N-diethylamine;
N- (meth) acryloyloxymethoxymethoxy-N, N-dimethylamine, N- (meth) acryloyloxyethoxyethoxy-N, N-dimethylamine, N- (meth) acryloyloxypropoxypropoxy-N, N-dimethylamine N- (meth) acryloyloxybutoxybutoxy-N, N-dimethylamine, N- (meth) acryloyloxyalkoxyanalkoxy-N, N-dimethylamine, and the like.

<Monomer (A5) having a structure represented by Formula 5>
Examples of the monomer having a betaine structure represented by the general formula 5 include 1-vinyl-2-alkyl-imidazole such as 1-vinylimidazole and 1-vinyl-2-methyl-imidazole.

<Monomer (A6) having a structure represented by General Formula 6>
Examples of the monomer having a betaine structure represented by the general formula 6 include vinylpyridines such as 4-vinyl-pyridine and 2-vinyl-pyridine.

  As described above, the vinyl polymer (a) of the present invention preferably has the structure represented by the general formula 1 in the side chain from the viewpoint of suppressing long-term biofilm formation. Therefore, as monomer (A), monomer (A1) or monomer (A4) having a corresponding structure can be preferably used.

<Monomer (B) having a crosslinkable group>
From the viewpoint of improving the water resistance of the polymer (a), when obtaining a vinyl polymer, in addition to the monomer (A), from the group consisting of a carboxyl group, a hydroxyl group, an epoxy group, a primary or secondary amino group and an isocyanate group. It is preferable to use a monomer (B) having at least one selected crosslinkable group. The crosslinkable group derived from the monomer (B) introduces a crosslinked structure into the polymer coating film by reacting with a crosslinking agent described later, and exhibits excellent water resistance.

  For example, a copolymer having a carboxyl group introduced therein can be crosslinked with an epoxy compound, an aziridine compound, a carbodiimide compound, or an N-hydroxyethylacrylamide compound. The copolymer introduced with a hydroxyl group can be crosslinked with an isocyanate compound or the like. A copolymer having an amino group introduced therein can be crosslinked with an epoxy compound. A copolymer having an isocyanate group introduced therein can be crosslinked with a hydroxyl group-containing compound.

  The carboxyl group-containing monomer is not particularly limited as long as it has a carboxyl group in its structure. For example, (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, or alkylene such as ethylene oxide or propylene oxide Examples include alkylene oxide addition succinic acid (meth) acrylate having a carboxyl group at the terminal where oxide is repeatedly added.

  The hydroxyl group-containing monomer is not particularly limited as long as it has a hydroxyl group in its structure. For example, 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, (meth) acrylic acid 2-hydroxypropyl, 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, glycerol monofunctional (meth) acrylate, polylactones having a hydroxyl group at the terminal by ring-opening addition of a lactone ring (meta ) Acrylic acid ester, alkylene oxide addition system (meth) acrylic acid ester having a hydroxyl group at the terminal after repeated addition of alkylene oxide such as ethylene oxide and propylene oxide, and glucose ring system (meth) acrylic acid ester.

  The epoxy group-containing monomer is not particularly limited as long as it has an epoxy group in its structure, and examples thereof include glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate. .

  The primary or secondary amino group-containing monomer is not particularly limited as long as it has an amino group in its structure. For example, monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate , (Meth) acrylic acid monomethylaminopropyl, (meth) acrylic acid monoethylaminopropyl, and the like.

  The monomer (B) having a crosslinkable group is preferably a carboxyl group-containing monomer from the viewpoint of water resistance and long-term biofilm formation inhibiting ability.

<Other monomer (C)>
In obtaining a vinyl polymer, in addition to the monomer (A) and the monomer (B), another monomer (C) having one ethylenically unsaturated group in one molecule can be used. By introducing the structure based on the monomer (C), the polarity and Tg are appropriately controlled, and excellent coating properties, water resistance, and weather resistance can be obtained.

Examples of other monomer (C) having one ethylenically unsaturated group in one molecule include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl. Alkyl (meth) acrylates such as (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate;
Α-olefin-based ethylenically unsaturated monomers such as 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene and 1-decene.

Monomers having a sulfonic acid group such as vinyl sulfonic acid and styrene sulfonic acid;
A monomer having a phosphate group, such as (2-hydroxyethyl) methacrylate acid phosphate;
(Meth) acrylamide, N-vinyl-2-pyrrolidone, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meta ) Acrylamide, N-pentoxymethyl- (meth) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N- Ethoxymethyl-N-propoxymethyl methacrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl -N- (Met Cymethyl) methacrylamide, N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) methacrylamide, N, N-dimethylaminopropylacrylamide, N, N-diethylaminopropylacrylamide, N , N-dimethylacrylamide, N, N-diethylacrylamide, diacetone (meth) acrylamide and other monomers having primary to tertiary amide groups;
(Meth) acrylic acid dimethylaminoethyl methyl chloride salt, trimethyl-3- (1- (meth) acrylamide-1,1-dimethylpropyl) ammonium chloride, trimethyl-3- (1- (meth) acrylamidopropyl) ammonium chloride, And a monomer having a quaternary amino group such as trimethyl-3- (1- (meth) acrylamide-1,1-dimethylethyl) ammonium chloride;
Polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, propoxypolyethylene glycol (meth) acrylate, n-butoxypolyethylene glycol (meth) acrylate, n-pentoxypolyethylene glycol (meth) Acrylate, phenoxypolyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, propoxypolypropylene glycol (meth) acrylate, n-butoxypolypropylene glycol (meth) acrylate N-Pentoxypolypropylene Recall (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, hexaethylene glycol (meth) acrylate, Examples thereof include monomers having a polyether chain such as methoxyhexaethylene glycol (meth) acrylate.

<Betainization>
As described above, the polymer (a) of the present invention is a reaction product of a vinyl polymer having a structure of at least any tertiary amino group represented by the general formulas 4 to 6 in the side chain and a betaine agent. Specifically, a vinyl polymer obtained by polymerizing a monomer having a structure of at least any tertiary amino group represented by the general formulas 4 to 6 and another monomer, a betaine agent, The reaction product of
Below, betaine-ization is demonstrated.

Betainization may be performed either before or after polymerization, and a betaine agent (D) is added to a solution containing a betaine structure, and 0.1 to 100 hours in the range of 20 ° C to 100 ° C, preferably A betaine polymer can be obtained by reacting for 1 to 50 hours.
In general, the amount of the betaine agent used is 0.2 to 3 times the molar equivalent of the functional group capable of betainization, that is, the tertiary amino group, and further 0.5 to 2 times. More preferably, molar equivalents are used.

<Betainizing agent (D)>
The betaine agent (D) is used for converting the nitrogen atom in formulas 4 to 6 into sulfobetaine or carbobetaine, and conventionally known ones can be used. The betaine agent (D) may be used alone or in combination of two or more.
Among them, selected from the group consisting of cyclic sulfonic acid ester (D1), ω-halogenated alkyl sulfonic acid metal salt (D2), cyclic carboxylic acid ester (D3) and ω-halogenated alkyl carboxylic acid metal salt (D4). At least one is preferred.

(Cyclic sulfonic acid ester (D1))
Examples include 1,2-ethane sultone, 1,3-propane sultone, and 1,4-butane sultone.

(Ω-halogenated alkylsulfonic acid metal salt (D2))
Examples include sodium 2-chloroethanesulfonate, sodium 2-bromoethanesulfonate, sodium 3-chloropropanesulfonate, sodium 3-bromopropanesulfonate, sodium 4-chlorobutanesulfonate, sodium 4-bromobutanesulfonate, and the like.

(Cyclic carboxylic acid ester (D3))
Examples include β-propiolactone, γ-butyrolactone, and δ-valerolactone.

(Ω-halogenated alkylcarboxylic acid metal salt (D4))
Sodium 2-chloroacetate, sodium 2-bromoacetate, sodium 3-chloropropionate, sodium 3-bromopropionate, sodium 4-chlorobutyrate, sodium 4-bromobutyrate, sodium 5-chloropentanoate, 5-bromopentanoic acid Sodium etc. are mentioned.

  The betaine agent (D) is preferably a cyclic sulfonic acid ester (D1) or a ω-halogenated alkylcarboxylic acid metal salt (D4).

<Copolymerization composition of polymer (a)>
The copolymer composition of the polymer (a) will be described.
The monomer (A) is preferably used at 1% by mass or more based on the total amount of all monomers. Preferably it is 5 mass% or more, More preferably, it is 10 mass% or more, Most preferably, it is 15 mass% or more. Moreover, it is preferable to use at 95 mass% or less. Preferably it is 90 mass% or less, More preferably, it is 60 mass% or less, Most preferably, it is 50 mass% or less. By setting it as the above range, a long-term biofilm formation inhibitory effect is exhibited.
The monomer (B) having a crosslinkable group is preferably used at 20% by mass or less based on the total amount of all monomers. Preferably it is 15 mass% or less, More preferably, it is 10 mass% or less. By setting it as the said range, when a crosslinking agent is used together, the coating film which has moderate crosslinking density can be obtained.

  The obtained polymer solution can be used as it is, but if necessary, the betaine structure-containing polymer can be isolated and used by a known method such as reprecipitation or solvent distillation. The isolated betaine structure-containing polymer can be further purified by reprecipitation, solvent washing, membrane separation, adsorption treatment, etc., if necessary.

<Betaine structure content>
In the present invention, the polymer (a) containing a betaine structure represented by the following general formulas 1 to 3 imparts biofilm formation inhibitory properties to the polymer. The betaine structure content in the polymer (a) is preferably 0.25 to 4.5 mmol / g, more preferably 0.5 to 2 mmol / g. By being 0.25-4.5 mmol / g, even if it immerses in water for a long time, the optimal biofilm formation suppression ability can be maintained.
The betaine structure content in the polymer (a) is the content of the structure represented by the general formulas 1 to 3. When the polymer having the betaine structure was polymerized to obtain the polymer (a), it was used for the polymerization. It can be determined from the amount of monomer having a betaine structure. On the other hand, when a polymer obtained after polymerizing a monomer essentially containing a tertiary amino group-containing monomer is betainized, the amine value before and after the betainization reaction is measured, and the difference between the amine values is calculated. This value corresponds to the amount of betaine (mmol / g).

<Mass average molecular weight (Mw)>
The weight average molecular weight of the polymer (a) is 2,000 to 10,000,000, preferably 5,000 to 6,000,000, more preferably 10,000 to 600,000, especially Preferably it is 50,000-100,000. When the molecular weight is 2,000 or more, a cohesive force can be imparted, peeling from the coated substrate can be suppressed, and a long-term biofilm formation suppressing effect can be exhibited. Moreover, since it becomes an appropriate viscosity by being 10,000,000 or less, coating suitability improves. Therefore, the mass average molecular weight of the polymer (a) is limited within the specific range.

As the mass average molecular weight of the polymer (a), a value measured in terms of standard polystyrene by gel permeation chromatography (GPC) is adopted. The measuring device and measurement conditions are basically based on the following condition 1 and are allowed to be set to condition 2 depending on the solubility of the sample. However, depending on the polymer type, an appropriate carrier (eluent) and a column suitable for it may be selected and used. For other matters, refer to JISK7252-1-4: 2008. In addition, it is assumed that the hardly soluble polymer compound is measured at a soluble concentration under the following conditions.
In addition, when it is difficult to measure the molecular weight of the polymer (a), the mass average molecular weight of the betaine precursor polymer can be set as the mass average molecular weight of the polymer (a). The mass average molecular weight of the betaine precursor polymer employs a value measured in terms of standard polystyrene by gel permeation chromatography (GPC), and the measurement apparatus and measurement conditions are basically based on the following condition 3.
(Condition 1)
Column: TOSOHTSKgelSuperHZM-H,
A combination of TOSHOTSKgelSuperHZ4000 and TOSHOTSKgelSuperHZ2000.
Carrier: Tetrahydrofuran Measurement temperature: 40 ° C
Carrier flow rate: 1.0 mL / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector Injection amount: 0.1 mL
(Condition 2)
Column: A column in which two TOSOHTSKgelSuperAWM-H are linked.
Carrier: 10 mM LiBr / N-methylpyrrolidone Measurement temperature: 40 ° C.
Carrier flow rate: 1.0 mL / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector Injection amount: 0.1 mL
(Condition 3)
Column: TOSOHTSKgelSuperAW4000,
A combination of TOSHOTSKgelSuperAW3000 and TOSHOTSKGgelSuperAW2500.
Carrier: N, N-dimethylformamide (1 L), triethylamine (3.04 g), mixed solution of LiBr (0.87 g) Measurement temperature: 40 ° C.
Carrier flow rate: 0.6 mL / min

<Crosslinking agent>
The biofilm formation inhibiting coating agent of the present invention can contain a crosslinking agent. By containing a crosslinking agent, when the above-mentioned polymer (a) has a crosslinkable group, the coating film can be crosslinked to improve water resistance.
The crosslinking agent that can be used in the present invention is selected from the group consisting of a carboxyl group, a hydroxyl group, an epoxy group, a primary or secondary amino group, and an isocyanate group in the monomer (B) for forming the polymer (a). Preferred are those that react with at least one crosslinkable group selected, such as those having at least one functional group selected from epoxy groups, isocyanate groups, and aziridinyl groups, metal chelate compounds, carbodiimide group-containing compounds, and the like. Can be mentioned.
These crosslinking agents can be used for the purpose of increasing the elastic modulus and resistance of the coating film, or for adjusting the adhesive force.

[Crosslinking agent having epoxy group]
The crosslinking agent having an epoxy group used in the present invention is not particularly limited as long as it has two or more epoxy groups in one molecule.
Examples of the crosslinking agent having a bifunctional epoxy group include ethylene glycol diglycidyl ether, polyethylene oxide diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, and polytetramethylene glycol diglycidyl. Ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, aliphatic epoxy compounds such as polybutadiene diglycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenol type Epoxy resin, dihydroxybenzophenone diglycidyl ether, resorcinol diglycidyl ether Ter, hydroquinone diglycidyl ether, dihydroxyanthracene type epoxy resin, bisphenol fluorenediglycidyl ether, N, N-diglycidyl aniline and other aromatic epoxy compounds, hydrogenated aromatic epoxy compounds as described above, hexahydrophthalic acid di Examples include alicyclic epoxy compounds such as glycidyl esters.
Examples of the crosslinking agent having three or more epoxy groups include triglycidyl isocyanurate, trisphenol type epoxy compound, tetrakisphenol type epoxy compound, phenol novolac type epoxy compound and the like.

[Crosslinking agent having isocyanate group]
The crosslinking agent having an isocyanate group used in the present invention is not particularly limited as long as it is a compound having two or more isocyanate groups in one molecule.
Examples of the bifunctional isocyanate compound include 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexa Examples thereof include methylene diisocyanate and isophorone diisocyanate. Examples of the trifunctional isocyanate compound include a trimethylolpropane adduct of diisocyanate described above, a burette reacted with water, and a trimer having an isocyanurate ring. Moreover, the isocyanate group in the crosslinking agent which has an isocyanate group may be blocked, and does not need to be blocked.
The blocked isocyanate crosslinking agent used in the present invention may be a blocked isocyanate compound in which the isocyanate group in the isocyanate compound is blocked with ε-caprolactam, MEK oxime, cyclohexanone oxime, pyrazole, phenol, etc., and is particularly limited. Is not to be done.

[Crosslinking agent having aziridinyl group]
The aziridine compound used in the present invention is not particularly limited as long as it is a compound having two or more aziridine groups in one molecule. Examples of the aziridine compound include 2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], 4,4-bis (ethyleneiminocarbonylamino) diphenylmethane, and the like.

[Carbodiimide group-containing compound]
As the carbodiimide group-containing compound used in the present invention, a carbodilite series manufactured by Nisshinbo Co., Ltd. can be used, and an aqueous type such as V-02, V-04, V-06, V-10, V-01, etc. , V-03, V-05, V-07, V-09, and the like.

[Β-Hydroxyalkylamide group-containing compound]
In the present invention, a β-hydroxyalkylamide group-containing compound can also be used as a crosslinking agent.
The β-hydroxyalkylamide group-containing compound is not particularly limited as long as it is a compound containing a β-hydroxyalkylamide group in the molecule. Examples of the β-hydroxyalkylamide group-containing compound include various compounds including N, N, N ′, N′-tetrakis (hydroxyethyl) adipamide (PrimidXL-552 manufactured by Ems Chemie).

In the present invention, the crosslinking agent may be used alone or in combination. From the viewpoint of water resistance and biofilm formation suppression, a carbodiimide group-containing compound is preferably used.
The amount of the crosslinking agent used may be determined in consideration of the type and mole number of the functional group contained in the polymer (a), and is not particularly limited, but is usually 100 parts by mass of the polymer (a). On the other hand, it is used in the range of 0.1 to 100 parts by mass. By blending in a range smaller than the number of moles of the functional group contained in the polymer (a), the concern that the unreacted crosslinking agent is liberated can be eliminated. If it is this range, the especially outstanding performance will be expressed by each effect of target biofilm formation suppression.

<Adjustment of biofilm formation inhibiting coating agent>
The biofilm formation-inhibiting coating agent of the present invention preferably contains 1 to 50% by mass, more preferably 5 to 30% by mass of the polymer (a) in 100% by mass of the coating agent. By setting the content of the polymer (a) to 1% by mass or more, it is possible to exert the effect of suppressing biofilm formation by the betaine structure included in the general formulas 1 to 3 of the present invention. Moreover, the biofilm formation suppression coating agent of this invention may also contain components other than a polymer (a).

<Solvent>
The biofilm formation inhibiting coating agent of the present invention may contain a solvent as a component other than the polymer (a), or may contain two or more kinds in combination. The solvent can be appropriately selected from conventionally known solvents in consideration of the solubility of the polymer (a) depending on the betaine structure content, printing conditions, and the like.
For example, when the polymer (a) has a high betaine structure content, water, alcohols such as methanol and ethanol, ketones such as acetone and ethyl methyl ketone, ethers such as tetrahydrofuran and diethyl ether, methyl acetate and ethyl acetate Such as dimethyl sulfoxide, acetonitrile, organic acids such as formic acid and acetic acid, and organic bases such as N, N-dimethylformamide. On the other hand, when the content of betaine structure in the polymer (a) is small, ketones such as acetone and ethyl methyl ketone, ethers such as tetrahydrofuran and diethyl ether, esters such as methyl acetate and ethyl acetate, dimethyl sulfoxide, acetonitrile In addition, a halogen solvent such as dichloromethane or trichloromethane can be selected.

  Furthermore, the biofilm formation suppression coating agent of the present invention may contain various additives as long as the effects of the present invention are not impaired.

<Biofilm formation suppression laminate>
The biofilm formation suppression laminated body of this invention has a coating film which consists of a biofilm formation suppression coating agent of this invention on a base material.
As a method for forming a coating film, various coating film forming methods (coating / printing / drying methods) can be selected depending on the substrate. Examples include, but are not limited to, various printing methods such as gravure and offset, ink jet methods, spray methods, immersion methods, and the like. The drying after the coating only needs to remove the solvent, and the drying temperature can be appropriately selected from the solvent and the like contained in the biofilm formation-inhibiting coating agent. Industrially, it is desirable that it is about 2 minutes at 40-180 degreeC. Furthermore, when the biofilm formation suppression coating agent of this invention contains a crosslinking agent, it is preferable to provide the process for promoting a crosslinking reaction. The crosslinking conditions are generally 40 to 150 ° C. and 6 to 24 hours, but are not limited thereto.
The thickness of the coating film composed of the biofilm formation inhibiting coating agent can be appropriately selected within the range not impairing the effects of the present invention, and a sufficient effect is exhibited even at 0.5 to 2 μm.

<Base material>
Since the biofilm formation-inhibiting coating agent of the present invention can be applied to a wide range of fields where there is a concern about the danger of biofilms, microorganisms adhere to medical devices, manufacturing facilities, water tank inner surfaces, etc., and biofilms are formed. It can be suitably used on the surface of a substance assumed to be used. Therefore, as a base material, if it is a conventionally well-known base material for the said use, it can be used without a restriction | limiting, For example, the base material which consists of materials, such as a plastics, glass, ceramics, a metal, is mentioned.

  The present invention will be specifically described with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “parts” and “%” represent “parts by mass” and “% by mass”.

<Measurement method of mass average molecular weight (Mw)>
As the mass average molecular weight of the polymer (a), a value measured by gel permeation chromatography (GPC) in terms of standard polystyrene was adopted. The measurement apparatus and measurement conditions were based on the following condition 1 and were set to condition 2 depending on the solubility of the sample. However, depending on the polymer type, an appropriate carrier (eluent) and a column suitable for the carrier were selected as appropriate. About other matters, it was based on JISK7252-1-4: 2008. In addition, about the sparingly soluble high molecular compound, it measured by the density | concentration which can be melt | dissolved under the following conditions.
Moreover, when it was difficult to measure the molecular weight of the polymer (a), the mass average molecular weight of the betaine structure precursor polymer was taken as the mass average molecular weight of the polymer (a). As the mass average molecular weight of the betaine structure precursor polymer, a value measured in terms of standard polystyrene by gel permeation chromatography (GPC) was adopted, and the measurement apparatus and measurement conditions were based on Condition 3 below.
(Condition 1)
Column: TOSOHTSKgelSuperHZM-H,
A combination of TOSHOTSKgelSuperHZ4000 and TOSHOTSKgelSuperHZ2000.
Carrier: Tetrahydrofuran Measurement temperature: 40 ° C
Carrier flow rate: 1.0 mL / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector Injection amount: 0.1 mL
(Condition 2)
Column: A column in which two TOSOHTSKgelSuperAWM-H are linked.
Carrier: 10 mM LiBr / N-methylpyrrolidone Measurement temperature: 40 ° C.
Carrier flow rate: 1.0 mL / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector Injection amount: 0.1 mL
(Condition 3)
Column: TOSOHTSKgelSuperAW4000,
A combination of TOSHOTSKgelSuperAW3000 and TOSHOTSKgelSuperAW2500.
Carrier: N, N-dimethylformamide (1 L), triethylamine (3.04 g), mixed solution of LiBr (0.87 g) Measurement temperature: 40 ° C.
Carrier flow rate: 0.6 mL / min

<Method for measuring acid value>
The acid value was measured by the following method according to JISK0070.
0.5-2 g of the sample was precisely weighed (solid content: Sg), and 10 mL of neutral ethanol was added to the precisely weighed sample and dissolved. The obtained solution was subjected to potentiometric titration with a 0.1 mol / L ethanolic potassium hydroxide solution (titer: F). The point at which the potential difference curve was maximized was taken as the end point, and the acid value was determined by (Equation 2) using the titration amount (AmL) at this time.
(Formula 2) Acid value (mmol / g) = (A × F × 0.1) / S

<Method of measuring amine value>
The amine value is mmol of potassium hydroxide in the same amount as the equivalent of hydrochloric acid required to neutralize the amino group contained in 1 g of resin. The amine value was measured by the following method.
0.5-2 g of the sample was precisely weighed (solid content: Sg), and 10 mL of neutral ethanol was added to the precisely weighed sample and dissolved. The obtained solution was subjected to potentiometric titration with a 0.1 mol / L ethanolic hydrochloric acid solution (titer: f). The point at which the potential difference curve was maximized was taken as the end point, and the titer (AmL) at this time was used to determine the amine value by (Equation 3).
(Formula 3) Amine value (mmol / g) = (A × f × 0.1) / S

<Measurement method of betaine structure content>
The betaine structure content is mmol of betaine structure contained in 1 g of resin. The betaine content was measured by one of the following methods.
(I) In the case of a vinyl polymer using the monomer (A) represented by the general formulas 1 to 3 having a betaine structure, the charged amount of the monomer represented by the general formulas 1 to 3 having a betaine structure at the time of the polymerization reaction ( mg), the molecular weight of the monomer (M), and the total amount of all monomers (Sg) were used to calculate the betaine structure content according to (Equation 4).
(Formula 4) Betaine structure content (mmol / g) = (m / M) / S × 1000

(II) A reaction product of a vinyl polymer obtained by polymerizing the monomer (A) having a structure of at least any tertiary amino group represented by the general formulas 4 to 6 with another monomer, and a betaine agent. In the case of a vinyl polymer, the amine value Am1 of the sample before betaineization and the amine value Am2 of the sample after betaineization were first determined according to the above-described amine value measurement method. Next, betaine structure content was computed by (Formula 5) using the amine titer.
(Formula 5) Betaine content (mmol / g) = Am1 (mmol / g) -Am2 (mmol / g)

<Synthesis of polymer (a)>
N-methacryloyloxyethyl-N, N-dimethylammoniumbutyl-α-sulfobetaine used for the synthesis of polymer (a) was synthesized with reference to paragraph 0262 of JP2012-187907A. Similarly, N-methacryloyloxyethyl-N, N-dimethylammoniummethyl-α-carbobetaine is described in paragraph 0045 of JP-A-11-222470 as 1-vinyl-3- (3-sulfopropyl) imidazolium inner salt. And 2-vinyl-1- (3-sulfopropyl) pyridinium inner salt were synthesized with reference to paragraph 0018 of JP-A-08-218065.

(Polymer solution (P-1))
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a refluxing vessel was charged with 100 parts of ethanol, the internal temperature was raised to 75 ° C., and the atmosphere was sufficiently replaced with nitrogen. Separately prepared, 0.3 part of 2,2′-azodiisobutyronitrile, 31 parts of N-methacryloyloxyethyl-N, N-dimethylammoniumbutyl-α-sulfobetaine as monomer (A1), monomer (B) A mixture of 4 parts of acrylic acid and 65 parts of butyl acrylate as the monomer (C) was added dropwise for 3 hours while maintaining the internal temperature at 75 ° C., and further stirred for 5 hours. After confirming that the conversion rate exceeded 98% by solid content measurement, the product was cooled and taken out. Then, after completely evaporating ethanol in an oven, ethanol was added again to obtain a 35 mass% polymer solution (P-1).
The betaine structure content of the obtained polymer solution (P-1) was 1.28 mmol / g. The obtained polymer had a mass average molecular weight of 70,000.

(Polymer solution (P-2-4, 9-14, 16-19))
In the same manner as for the polymer solution (P-1), synthesis was performed according to the composition and charged parts by mass of Table 1, and polymer solutions (P-2 to 4, 9 to 14, and 16 to 19) were obtained.

(Polymer solution (P-5))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a refluxing vessel, 100 parts of ethyl acetate was charged, the internal temperature was raised to 75 ° C., and the atmosphere was sufficiently substituted with nitrogen. Separately prepared, 0.3 part of 2,2′-azodiisobutyronitrile, 22 parts of N, N-dimethylaminoethyl methacrylate as monomer (A4), 5 parts of acrylic acid as monomer (B), A mixture of 73 parts of butyl acrylate as the monomer (C) was added dropwise for 3 hours while maintaining the internal temperature at 75 ° C., and further stirred for 5 hours. After confirming that the conversion rate exceeded 98% by solid content measurement, the solution was cooled to obtain a polymer solution having a tertiary amino group.
Next, 16 parts of 1,4-butane sultone (equal molar amount to the used N, N-dimethylaminoethyl methacrylate) was added to the resulting polymer solution having a tertiary amino group as a betaine agent at 70 ° C. By reacting for 12 hours, the amino group was betaened. After confirming that the betaine conversion rate exceeded 99%, the product was cooled and taken out. After completely evaporating the solvent in an oven, the polymer was dissolved in ethanol to obtain a 35% by mass polymer solution (P-5). .
The betaine structure content of the obtained polymer solution (P-5) was 1.31 mmol / g. Moreover, the mass average molecular weight of the obtained polymer was 71,000.

(Polymer solution (P-6-8))
In the same manner as for the polymer solution (P-5), synthesis was performed according to the composition and charged parts by mass of Table 1, and polymer solutions (P-6 to 8) were obtained.

(Polymer solution (P-15))
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a refluxing vessel was charged with 100 parts of ethanol, the internal temperature was raised to 75 ° C., and the atmosphere was sufficiently replaced with nitrogen. Separately prepared, 0.3 part of 2,2′-azodiisobutyronitrile, 17 parts of N-methacryloyloxyethyl-N, N-dimethylammoniumbutyl-α-sulfobetaine as monomer (A1), monomer A mixture of 14 parts of 2-vinyl-1- (3-sulfopropyl) pyridazolium inner salt as (A1), 4 parts of acrylic acid as monomer (B), and 65 parts of butyl acrylate as monomer (C), The dropwise addition was continued for 3 hours while maintaining the temperature at 75 ° C., and stirring was further continued for 5 hours. After confirming that the conversion rate exceeded 98% by solid content measurement, the product was cooled and taken out. Thereafter, ethanol was completely volatilized in an oven, and ethanol was added again to obtain a 35 mass% polymer solution (P-15) having a betaine structure.
The betaine structure content of the obtained polymer solution (P-15) was 1.29 mmol / g. The obtained polymer had a mass average molecular weight of 69,000.

(Polymer solution (P-20))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a refluxing vessel, 100 parts of ethyl acetate was charged, the internal temperature was raised to 75 ° C., and the atmosphere was sufficiently substituted with nitrogen. Separately prepared was a mixture of 0.3 part of 2,2′-azodiisobutyronitrile, 5 parts of acrylic acid as monomer (B), and 95 parts of butyl acrylate as monomer (C). While maintaining at 75 ° C., dropwise addition was continued for 3 hours, and stirring was further continued for 5 hours. After confirming that the conversion rate exceeded 98% by solid content measurement, the product was cooled and taken out, and diluted with ethyl acetate to obtain a 35 mass% polymer solution (P-20). Moreover, the mass average molecular weight of the obtained polymer was 56,000.

(Polymer solution (P-21))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a refluxing vessel, 100 parts of ethyl acetate was charged, the internal temperature was raised to 75 ° C., and the atmosphere was sufficiently substituted with nitrogen. Separately prepared, 0.3 part of 2,2′-azodiisobutyronitrile, 20 parts of N, N-dimethylaminoethyl methacrylate as monomer (A4), 4 parts of acrylic acid as monomer (B), A mixture of 76 parts of butyl acrylate as the monomer (C) was added dropwise for 3 hours while maintaining the internal temperature at 75 ° C., and further stirred for 5 hours. After confirming that the conversion rate exceeded 98% by solid content measurement, the product was cooled and taken out, and diluted with ethyl acetate to obtain a 35 mass% polymer solution (P-21) having a tertiary amino group. The amine number was also 54,000 for the polymer obtained.

(Polymer solution (P-22))
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a refluxing vessel was charged with 60 parts of ethyl acetate and 40 parts of ion-exchanged water, and the internal temperature was raised to 75 ° C. and sufficiently substituted with nitrogen. Separately prepared 0.3 parts of 2,2′-azodiisobutyronitrile, 4 parts of acrylic acid as monomer (B), 69 parts of butyl acrylate as monomer (C), 27 parts of methacryloylcholine chloride The mixture was added dropwise for 3 hours while maintaining the internal temperature at 75 ° C., and further stirred for 5 hours. After confirming that the conversion rate exceeded 98% by solid content measurement, the product was cooled and taken out, and diluted with ethanol to obtain a polymer solution (P-22) having 35% by mass of a quaternary amino group. The obtained polymer had a mass average molecular weight of 51,000.

  The obtained polymers are shown in Table 1.

The abbreviations in Table 1 are shown below.
DMBS: N-methacryloyloxyethyl-N, N-dimethylammoniumbutyl-α-sulfobetaine DMMC: N-methacryloyloxyethyl-N, N-dimethylammoniummethyl-α-carbobetaine VSPI: 1-vinyl-3- (3 -Sulfopropyl) imidazolium inner salt VSPP: 2-vinyl-1- (3-sulfopropyl) pyridizolinium inner salt DMAEMA: N, N-dimethylaminoethyl methacrylate VI: 2-methyl-1-vinylimidazole VP: 4-vinyl Pyridine AA: acrylic acid HEA: 2-hydroxyethyl acrylate GMA: glycidyl methacrylate BA: butyl acrylate OA: n-octyl arylate TMAEMC: methacryloylcholine chloride AIBN: 2,2′-azodiisobutyronite Le BS: 1,4-butane sultone CSC: 2-sodium chloroacetate

<Adjustment of biofilm formation inhibiting coating agent>
[Example 1]
(Biofilm formation inhibiting coating agent 1)
4.0 parts of the obtained polymer solution (P-1) and 2.0 parts of V-02 (Nisshinbo Co., Ltd .; Carbodilite V-02) as a cross-linking agent are mixed and diluted with 16.0 parts of ethanol. Then, a 10% coating solution was prepared to obtain biofilm formation inhibiting coating agent 1.

[Examples 2 to 17, 19 to 22] [Comparative Examples 1 to 4]
(Biofilm formation inhibiting coating agent 2-17, 19-26)
In the same manner as in Example 1, biofilm formation inhibiting coating agents 2 to 17 and 19 to 26 were prepared with the compositions and charged parts by mass shown in Table 2.

[Example 18]
(Biofilm formation inhibiting coating agent 18)
4.0 parts of the obtained polymer (P-14) obtained was diluted with 16 parts of ethanol to prepare a 10% coating solution, thereby obtaining a biofilm formation inhibiting coating agent 18.

The abbreviations in Table 2 are shown below.
V-02: Carbodiimide group-containing compound (Nisshinbo Co., Ltd .; Carbodilite V-02)
V-10: Carbodiimide group-containing compound (Nisshinbo Co., Ltd .; Carbodilite V-10)
V-05: Carbodiimide group-containing compound (Nisshinbo Co., Ltd .; Carbodilite V-05)
MDI: isocyanate-containing compound (2,2′-diphenylmethane diisocyanate)
40E: Epoxy group-containing compound (manufactured by Kyoeisha Chemical Co., Ltd .; Epolite 40E)
LV11: Amino group-containing compound (manufactured by Mitsubishi Chemical Corporation; epoxy resin curing agent jER cure)
EtOH: ethanol EtOAc: ethyl acetate

<Evaluation of biofilm formation inhibiting coating agent>
The following evaluation was performed about the biofilm formation suppression coating agent (coating liquid) obtained by the Example and the comparative example. The results are shown in Table 3.

[water resistant]
2.0 g of the obtained coating agent was added to a precisely weighed shallow metal container, and dried by heating at 150 ° C. for 10 minutes. After taking out from the oven and precisely weighing together with the shallow metal container, 5.0 g of ion-exchanged water was added to the shallow metal container and allowed to stand overnight. After the ion exchange water was sucked and discharged from the shallow metal container, it was again dried at 150 ° C. for 10 minutes, and the shallow metal container was precisely weighed. The solubility in water was calculated according to the following formula, and the water resistance was evaluated based on four evaluation criteria.
Solubility in water (%) = 100 − [(z−x) / (y−x)] × 100
x: Mass of shallow metal container (g)
y: Mass before processing with ion-exchanged water (g)
z: Mass (g) after treatment with ion-exchanged water
◎: Solubility in water ≦ 2%: Very good ○: 2% <Solubility in water ≦ 4%: Good Δ: 4% <Solubility in water ≦ 10%: Usable ×: 10% <Water Solubility: Unusable

<Production and evaluation of biofilm formation-suppressed laminate>
The obtained coating agent 1-26 was placed on a 75 μm-thick polyethylene terephthalate (PET) film (manufactured by Panac Corporation; Lumirror # 75, surface ozone-treated) so that the film thickness after drying was 1.0 μm. After coating with a coater and drying at 80 ° C. for 2 minutes, the laminate was heated at 80 ° C. for 24 hours to obtain a laminate 1-26. Separately, S. aureus (ATCC 25923) was pre-cultured at 37 ° C. for 24 hours and grown. The bacterial solution was added to phosphate buffered water (PBW) to prepare a 1% bacterial solution. The obtained laminate was cut into a size of 1.5 cm × 1.5 cm, and set one by one in each well of a 24-well microplate (manufactured by Falcon) so that the coated surface faced upward. 0.0 mL was added and immersed at 37 ° C. for 24 hours.
Subsequently, 1.0 mL of sterilized water was removed from the 24-well microplate, 1.0 mL of a separately prepared Staphylococcus aureus solution was added, and the cells were cultured at 25 ° C. for 24 hours or at 25 ° C. for 168 hours, respectively. After culturing for 24 hours or 168 hours, the bacterial solution is removed, the coating film is washed 3 times with 1.2 mL of sterilized water, and 0.1% crystal violet aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) is added for 20 minutes. The biofilm was stained by standing. Thereafter, the laminate was washed three times with 1.2 mL of sterilized water and air-dried to obtain a laminate in which the biofilm was dyed.
About the dyed laminate, crystal violet was extracted using 2.0 mL of 33% acetic acid solution, and the absorbance of the extract was measured using a microplate reader. The biofilm formation inhibitory property was evaluated according to the following four evaluation criteria from the absorbance.
A: Absorbance ≦ 0.10: Very good ○: 0.10 <Absorbance ≦ 0.13: Good Δ: 0.13 <Absorbance ≦ 0.20: Usable ×: 0.20 <Absorbance: Unusable

From Table 3, the biofilm formation inhibiting coating agent comprising a polymer (a) containing a betaine structure and having a mass average molecular weight of 2,000 to 10,000,000 is excellent in water resistance and long-lasting. It was confirmed that the biofilm formation suppression performance showed an excellent effect. The betaine structure content in the polymer (a) at this time was within the range of 0.25 to 4.5 mmol / g. In particular, the vinyl polymer having the structure represented by the general formula 1 in the side chain was excellent from the viewpoint of suppressing long-term biofilm formation. Further, when the vinyl polymer has a carboxyl group as a crosslinkable group and further contains a carbodiimide group-containing compound as a crosslinking agent, when the weight average molecular weight of the vinyl polymer is 10,000 to 100,000, It was excellent in terms of water resistance and long-term biofilm formation suppression.
On the other hand, Comparative Example 1 was poor in water resistance due to the small mass average molecular weight of the vinyl polymer, and further, the coating film was peeled off. Since Comparative Example 2 was a polymer having no betaine structure, the biofilm formation inhibitory property was poor. Since Comparative Example 3 is a polymer having a tertiary amino group but not having a betaine structure, the biofilm formation inhibitory property was poor. Since Comparative Example 4 is a polymer having a quaternary amino group but not having a betaine structure, the water resistance and biofilm formation inhibitory properties were poor.

Claims (6)

A biopolymer comprising a vinyl polymer (a) having at least one structure represented by the following general formulas 1 to 3 in a side chain and having a mass average molecular weight of 2,000 to 10,000,000. Film formation inhibitor coating agent.



(In general formulas 1 to 3,
R ₁ is an alkylene group having 1 to 6 carbon atoms,
R ₂ and R ₃ are each independently an alkyl group having 1 to 4 carbon atoms,
R ₄ is an alkylene group having 1 to ₄ carbon atoms,
X is an oxygen atom or NH,
Y is COO ⁻ or SO ₃ ⁻ ,
R ₅ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ₆ is an alkylene group having 1 to 6 carbon atoms or a hydroxyalkylene group having 1 to 6 carbon atoms,
4 of R _{7 to} R ₁₁ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and one of R _{7 to} R ₁₁ represents a bonding position with the main chain of the vinyl polymer,
R ₁₂ is an alkylene group having 1 to 6 carbon atoms or a hydroxyalkylene group having 1 to 6 carbon atoms,
* Represents a bonding position with the main chain of the vinyl polymer (a). )   The biofilm formation suppression coating agent of Claim 1 in which a polymer (a) contains 0.25-4.5 mmol / g of a betaine structure. The polymer (a) has at least one structure represented by the general formulas 1 to 3 (wherein the bonding position with the main chain of the vinyl polymer in the general formulas 1 to 3 represents the bonding position with the monomer). Reaction of a vinyl polymer having a side chain with at least one of the structures represented by the following general formulas 4 to 6 that is a vinyl polymer obtained by polymerizing a monomer having a monomer and other monomers The biofilm formation suppression coating agent of Claim 1 or 2 which is a product.



(In general formulas 4-6,
R ₁₃ is an alkylene group having 1 to 6 carbon atoms,
R ₁₄ and R ₁₅ are each independently an alkyl group having 1 to 4 carbon atoms,
X is an oxygen atom or NH,
R ₁₆ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
4 of R _{17 to} R ₂₁ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and one of R _{17 to} R ₂₁ is a bonding position with the main chain of the vinyl polymer (a), Represents
* Indicates the bonding position with the main chain of the vinyl polymer,
** represents a reaction site with a betaine agent. )   The biofilm formation suppression coating agent of any one of Claims 1-3 in which a polymer (a) has a crosslinkable group.   Furthermore, the biofilm formation suppression coating agent of any one of Claims 1-4 containing a crosslinking agent.   The biofilm formation suppression laminated body which has a coating film which consists of a biofilm formation suppression coating agent of any one of Claims 1-5 on a base material.