WO2020144953A1

WO2020144953A1 - Antifouling agent, antifouling coating film and base material with antifouling coating film

Info

Publication number: WO2020144953A1
Application number: PCT/JP2019/046011
Authority: WO
Inventors: 勇樹牧野; 善知中田; 直記小林; 飛鳥菅原
Original assignee: 株式会社日本触媒
Priority date: 2019-01-09
Filing date: 2019-11-25
Publication date: 2020-07-16
Also published as: JPWO2020144953A1

Abstract

An antifouling agent which contains a copolymer that has a structural unit derived from a polymerizable double bond-containing monomer that has two or more hydroxyl groups and a structural unit derived from an alkyl (meth)acrylate that has an alkyl group having 4-12 carbon atoms.

Description

Antifouling agent, antifouling coating film and substrate with antifouling coating film

The present invention relates to an antifouling agent, an antifouling coating film and a substrate with an antifouling coating film.

Dirt due to proteins, microorganisms, etc. causes problems such as impairing the aesthetics of the article and being unsanitary. However, it is usually not easy to remove stains once attached to an article. Therefore, various antifouling agents have been studied to prevent the stains from adhering or to easily remove the stains.

For example, Patent Document 1 proposes an antifouling agent containing an ether ester type nonionic surfactant or the like for the purpose of preventing dirt on a textile product. In addition, Patent Document 2 proposes an antifouling agent containing an aromatic sulfonic acid-based formalin condensate for the purpose of preventing dirt on a hard surface of a toilet bowl or the like.

Japanese Patent Laid-Open No. 2002-371466 JP, 2007-99793, A

However, as a result of studies by the present inventors, the antifouling agent described in Patent Document 1 has an insufficient antifouling effect against stains of proteins and microorganisms, and the antifouling agent described in Patent Document 2 has a problem of odor and the like. It became clear that there was a problem.

Therefore, the present invention provides an antifouling agent having an excellent antifouling effect against protein and microbial stains and having a sufficiently reduced odor, and an antifouling coating film and a substrate with an antifouling coating film using the same. With the goal.

In view of the above circumstances, the present inventors have conducted intensive studies, and as a result, completed the inventions shown in [1] to [8] below.
[1] A copolymer having a structural unit derived from a polymerizable double bond-containing monomer having two or more hydroxyl groups and an alkyl (meth)acrylate derived structural unit having an alkyl group with 4 to 12 carbon atoms Antifouling agent containing.
[2] The antifouling agent according to [1], wherein the polymerizable double bond-containing monomer having two or more hydroxyl groups contains a monomer represented by the following formula (I).

(In the formula (I), R ¹ represents a hydrogen atom or a methyl group, and X represents an oxygen atom or a —NH— group.)
[3] The antifouling agent according to [1] or [2], which is for treating fibers.
[4] The antifouling agent according to [3], wherein the fiber is at least one selected from the group consisting of polyester, nylon and urethane.
[5] The antifouling agent according to [1] or [2], which is for treating water-related products.
[6] An antifouling coating film containing the antifouling agent according to [1] or [2].
[7] A substrate with an antifouling coating film, which has the antifouling coating film according to [6] on a substrate.
[8] The base material with an antifouling coating film according to [7], wherein the base material is a ship, an underwater structure, a fishing net or fishing gear.

According to the present invention, an antifouling agent having an excellent antifouling effect against stains of proteins and microorganisms and having a sufficiently reduced odor, an antifouling coating film using the same, and a substrate with an antifouling coating film are provided. be able to.

An embodiment of the present invention will be described below in detail, but the present invention is not limited to this. In addition, in this specification, the term "(meth)acrylic acid" means acrylic acid or methacrylic acid. The same applies to similar expressions such as “(meth)acrylate”.

<Antifouling agent>
The antifouling agent of the present embodiment is a structural unit derived from a polymerizable double bond-containing monomer having two or more hydroxyl groups (hereinafter, also referred to as “monomer (A)”) and carbon of an alkyl group. A copolymer having a structural unit derived from an alkyl (meth)acrylate having a number of 4 to 12 (hereinafter, also referred to as "monomer (B)") is included. Such an antifouling agent has an excellent antifouling effect against stains of proteins and microorganisms and has a sufficiently low odor.

The antifouling agent of this embodiment will be described in detail below.

(Copolymer)
The monomer (A) is not particularly limited as long as it has a polymerizable double bond and two or more hydroxyl groups, but is preferably a compound represented by the following formula (II). As the monomer (A), one type may be used alone, or two or more types may be used in combination.

(In the formula (II), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an organic group having 2 or more hydroxyl groups.)

In formula (II), R ² is an organic group having two or more hydroxyl groups. Among them, -COOR ³ group, -OCOR ³ group, -OR ³ group, -CONHR ³ group, -CH ₂ OR ³ group, -CH ₂ OCOR ³ group, -CONHR ³ group, -CON(R ³ ) ₂ group Alternatively, it is preferably —NHCOR ³ group (R ³ represents an organic group having two or more hydroxyl groups).

R ³ is an organic group having 2 or more hydroxyl groups, preferably an organic group having 1 to 30 carbon atoms having 2 or more hydroxyl groups, and more preferably an organic group having 1 to 20 carbon atoms having 2 or more hydroxyl groups. It is a base. Examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a polyoxyalkylene group having 4 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. When two or more R ³ are contained in one molecule, each R ³ may be the same or different. Further, R ³ may contain, for example, a halogen atom such as a fluorine atom or a chlorine atom, a nitrogen atom, or a functional group other than a hydroxyl group.

As the monomer (A), for example, an ester of a polyhydric alcohol having 3 or more hydroxyl groups and (meth)acrylic acid, an ester of a saccharide and (meth)acrylic acid, a saccharide having an amino group and (meth) Examples thereof include esters with acrylic acid. These esters may be prepared not only by esterification reaction but also by transesterification reaction or ring-opening reaction of glycidyl (meth)acrylate ester.

Examples of the polyhydric alcohol having 3 or more hydroxyl groups include glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, pentaerythritol, 1,2,6-hexanetriol, 2-hydroxymethyl-2- Examples thereof include methyl-1,3-propanediol and 2-ethyl-2-hydroxymethyl-1,3-propanediol. Examples of saccharides include monosaccharides such as glucose, mannose, galactose, gulose, fructose, and D-ribose, glucosides derived from the monosaccharides, galactoside, fructoside, and dimers and trimers thereof. Can be mentioned. Examples of the saccharide having an amino group include D-glucosamine.

From the viewpoint of further improving the antifouling effect, the monomer (A) is more preferably a monomer represented by the following formula (I).

(In the formula (I), R ¹ represents a hydrogen atom or a methyl group, and X represents an oxygen atom or a —NH— group.)

Examples of the monomer represented by the formula (I) include glycerol monoacrylate (R ¹ =hydrogen atom, X=oxygen atom), glycerol monomethacrylate (R ¹ =methyl group, X=oxygen atom), glycerol monoacrylamide ( R ¹ =hydrogen atom, X=-NH-group) or glycerol monomethacrylamide (R ¹ =methyl group, X=-NH-group).

The structural unit derived from the monomer represented by the formula (I) corresponds to the structural unit represented by the following formula (I′).

(In formula (I′), R ¹ and X have the same meaning as in formula (I).)

The molecular weight of the monomer (A) is preferably 500 or less.

The monomer (A) is preferably a monomer synthesized by a method in which a monomer having a 1,3-dioxolane structure is used as a raw material or an intermediate. A copolymer obtained by polymerizing a monomer synthesized through a monomer having a 1,3-dioxolane structure as a raw material or an intermediate has a smoothness of a coating film and a texture when used as a fiber treatment agent. It is preferable as an antifouling agent because it has good

From the viewpoint of further improving the antifouling effect, the content of the structural unit derived from the monomer (A) is preferably 5 to 90 mass% with respect to the total amount of the copolymer, and 10 to 75 mass%. Is more preferable, and 15 to 60% by mass is further preferable.

The constitutional unit derived from the monomer (A) may be any constitutional unit having two or more hydroxyl groups in the copolymer. That is, it may be a constitutional unit obtained by polymerizing using a monomer (A), and after polymerizing a monomer in which two or more hydroxyl groups are protected by a protecting group, depolymerizing the protecting group such as deprotecting the protecting group. By doing so, a structure having two or more hydroxyl groups may be introduced.

Examples of the monomer (B) include n-butyl(meth)acrylate, isobutyl(meth)acrylate, tert-butyl(meth)acrylate, cyclohexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, n-octyl. Examples thereof include (meth)acrylate, isooctyl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate. Of these, n-butyl (meth)acrylate is preferred. As the monomer (B), one type may be used alone, or two or more types may be used in combination.

From the viewpoint of further improving the antifouling effect, the content of the structural unit derived from the monomer (B) is preferably 10 to 95% by mass, and 25 to 90% by mass with respect to the total amount of the copolymer. Is more preferable, and 40 to 85 mass% is even more preferable.

The copolymer of the present embodiment may include a structural unit derived from the monomer (C) which is neither the monomer (A) nor the monomer (B). Examples of the monomer (C) include (meth)acrylic acid; alkyl groups such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. (Meth)acrylic acid alkyl ester having 1 to 3 carbon atoms; vinyl esters such as vinyl acetate and vinyl propionate; vinyl chloride, vinylidene chloride; olefins such as ethylene, propylene, butene, isoprene; N-vinyl N-vinyl compounds such as formamide and N-vinylacetamide; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and propyl vinyl ether; and methylmaleimide. As the monomer (C), one type may be used alone, or two or more types may be used in combination.

The content of the structural unit derived from the monomer (C) is preferably 25% by mass or less, more preferably 20% by mass or less, and more preferably 10% by mass or less, based on the total amount of the copolymer. And more preferable.

The glass transition temperature of the above copolymer is preferably −10° C. or lower. When the temperature is -10°C or lower, the adhesion of proteins and microorganisms is particularly suppressed, and the antifouling effect is further improved. The glass transition temperature can be measured by DSC (differential scanning calorimeter) or the like.

The above copolymer can be produced by appropriately selecting the above monomers and carrying out a polymerization reaction. The preferred amount of the monomer used in the polymerization reaction is the same as the preferred content of the structural unit derived from these monomers in the copolymer.

The polymerization reaction is preferably performed in the presence of a polymerization initiator. Examples of the polymerization initiator include hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate; dimethyl 2,2′-azobis(2-methylpropionate), 2,2′-azobis. Azo compounds such as (isobutyronitrile); organic peroxides such as benzoyl peroxide, peracetic acid, and di-t-butyl peroxide are preferable. These polymerization initiators may be used alone or in the form of a mixture of two or more kinds.
The amount of the polymerization initiator used is preferably 0.01 g or more and 10 g or less, and more preferably 0.1 g or more and 5 g or less, based on 1 mol of the monomer used in the polymerization reaction.

The above polymerization reaction may be carried out without using a solvent, but it is preferable to use a solvent. Examples of the solvent include acetonitrile, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropyl alcohol and the like. These solvents may be used alone or in the form of a mixture of two or more kinds. The amount of the solvent used is preferably 40 to 250 parts by mass with respect to 100 parts by mass of the monomer used in the polymerization reaction.

The above-mentioned polymerization reaction is usually preferably carried out at 0°C or higher, and preferably at 150°C or lower. The temperature is more preferably 40° C. or higher, further preferably 60° C. or higher, and particularly preferably 80° C. or higher. Further, it is more preferably 120°C or lower, and further preferably 110°C or lower. The above-mentioned polymerization temperature does not always have to be kept substantially constant in the polymerization reaction and may be changed once or twice (heating or cooling). The polymerization reaction may be carried out under any conditions of normal pressure, increased pressure and reduced pressure.

In the above-mentioned polymerization reaction, the monomers, the polymerization initiator and the like may be added to the reactor all at once or sequentially.

The method for producing the copolymer may include steps other than the above polymerization reaction step. Examples of other steps include an aging step, a neutralization step, a deactivation step of a polymerization initiator and a chain transfer agent, a dilution step, a drying step, a concentration step, and a purification step.

The copolymer of the present embodiment may be crosslinked using a crosslinking agent or the like, but is preferably a non-crosslinked (non-crosslinked) copolymer.

The antifouling agent of the present embodiment may contain only the above-mentioned copolymer, or may be used in combination with other components other than the above-mentioned copolymer.

Further, the antifouling agent of the present embodiment is preferably used as a solution by dissolving the above-mentioned copolymer in a solvent from the viewpoint of improving handleability. As the solvent, for example, methanol, ethanol, toluene, ethyl acetate, tetrahydrofuran (THF), chloroform, acetone, isopropyl alcohol (IPA), acetonitrile, dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and the like can be used. Of these, ethanol is preferable from the viewpoint of safety and the like.

The concentration of the antifouling agent in the form of a solution can be appropriately adjusted according to the application method of the antifouling agent and the like. For example, the concentration of the above-mentioned copolymer is 0.1 to 20% by mass. It can be a solution.

<Use of antifouling agent>
The antifouling agent of the present embodiment has an excellent antifouling effect against stains of proteins and microorganisms, and has a sufficiently low odor, so it should be used for all articles in which sebum, starch, protein or microbial stains may adhere. You can Examples of protein stains include stains derived from living bodies such as sweat, saliva and blood, and stains derived from foods such as eggs and milk. Examples of microbial stains include bacteria such as Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and mutans, and stains caused by molds that easily grow around water such as black yeast-like bacteria, formers, scabs, and black molds. ..

The antifouling agent of the present embodiment is preferably used as an antifouling agent for fiber treatment or water treatment.

When the antifouling agent of the present embodiment is applied to a fiber treatment, it has an excellent antifouling effect, does not cause a problem of odor and toxicity, and does not impair the texture of the textile product.

The fiber to be treated with the antifouling agent is not particularly limited, but examples thereof include polyester such as polyethylene terephthalate, nylon, or urethane. When the fibers are treated with the antifouling agent, the single fibers may be directly treated or the cloth-like fibers may be treated.

The method of treating the fibers with the antifouling agent is not particularly limited, and examples thereof include a method of immersing the fibers in a solution of the antifouling agent and a method of spraying the solution of the antifouling agent on the fibers.

The suitable weight of the coating film (copolymer attached to the fiber) formed when the fiber is treated with the antifouling agent varies depending on the fiber used, but is preferably 0.1 to 15 mg per 1 g of the fiber. , And more preferably 0.5 to 12 mg. By setting the weight of the coating film formed when the fiber is treated with the antifouling agent within the above range, it is possible to further reduce the influence on the texture of the fiber product. Furthermore, since the antifouling agent of the present embodiment is excellent in antifouling property, even if the weight of the coating film per 1 g of the fiber is small, the antifouling effect is sufficiently exhibited.

When the antifouling agent of the present embodiment is applied to the treatment of products around water, it has an excellent antifouling effect and does not cause a problem of odor or toxicity.

Examples of water products to be treated with antifouling agents include kitchen bodies such as sinks, workshops and faucets; kitchen appliances such as draining baskets; bathroom bodies such as bathtubs, floors and walls; washbasins and bath chairs. Bath products such as; brushes such as oral toothbrushes; wash basins; toilet bowls and the like. There are no particular restrictions on the material of the water supply article, but examples thereof include resins such as polyester resin, nylon resin, urethane resin, and acrylic resin; metals such as stainless steel; and pottery.

The film thickness of the coating film formed when the water-based article is treated with an antifouling agent is not particularly limited, but is, for example, 0.01 μm to 10 μm, preferably 0.1 μm to 5 μm, more preferably 0.5 μm to It can be 3 μm.

<Anti-fouling coating>
The antifouling coating film of this embodiment contains the above-mentioned antifouling agent. By forming the antifouling coating film of the present embodiment on the substrate, the antifouling property of the substrate can be improved. The antifouling coating film of the present embodiment can be suitably applied to a substrate that may come into contact with seawater, for example, articles such as ships, underwater structures, fishing nets and fishing gear. By applying the antifouling coating film of the present embodiment to these substrates, it is possible to prevent stains derived from microorganisms contained in seawater.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<Synthesis example>
[GLMA (glycerol monoacrylate)]
A reaction vessel containing a stirrer was equipped with a gas inlet tube, a thermometer, a cooling tube, and a V-shaped tube connected to a distillate receiver, and 230 g of methyl acrylate, 2,2-dimethyl-1,3 -70 g of dioxolane-4-methanol (DOM) was charged, the reaction solution was stirred while blowing an oxygen/nitrogen mixed gas (oxygen concentration 7 vol%) through a gas introduction tube, and heating was started in an oil bath (bath temperature 110°C). .. After water did not come out to the distillate, 4.5 g of titanium tetraisopropoxide was added to the reaction vessel to start the transesterification reaction. The area ratio of iPGLMA (isopropylidene glyceryl acrylate)/DOM was traced by gas chromatography (GC) analysis while azeotropically distilling off the produced methanol with methyl acrylate. After 7 hours from the start of the reaction, it was confirmed by GC analysis that the area ratio of iPGLMA/DOM exceeded 9/1, the reaction was terminated, and the temperature was cooled to room temperature. In this manner, iPGLMA, which is a monomer having a 1,3-dioxolane structure, was obtained as an intermediate for GLMA synthesis. To the reaction solution, 150 g of purified water and 300 g of ethyl acetate as an extraction solvent were added, and the mixture was stirred for 10 minutes. The titanium oxide precipitate generated by the hydrolysis of titanium tetraisopropoxide was removed by suction filtration, and the filtrate was transferred to a separatory funnel to separate an organic layer and an aqueous layer. The organic layer was washed twice with purified water and then transferred to a rotary evaporator to distill off residual methyl acrylate and light-boiling components to obtain 96 g of iPGLMA.
A gas introduction tube was provided in a round-bottomed flask containing a stirrer, 160 ml of purified water and 80 g of iPGLMA were added and dissolved therein, and then 35 g of solid acid catalyst Amberlyst 15Jwet (manufactured by Organo) which had been previously air-dried in water was added. The reaction solution was stirred while blowing an oxygen/nitrogen mixed gas (oxygen concentration 7 vol%) through the gas introduction tube, and the deprotection reaction was started at room temperature. The area ratio of GLMA/iPGLMA was traced by GC analysis, and it was confirmed that the area ratio exceeded 99/1, and the reaction was completed in 4 hours. The filtrate obtained by filtering off the solid acid catalyst was washed with n-hexane to remove unreacted iPGLMA. The aqueous layer was concentrated under reduced pressure to obtain 53 g of the target GLMA.

[Copolymer GB37]
A reaction vessel containing a stirrer was equipped with a gas introduction tube, a thermometer, and a cooling tube, and glycerol monoacrylate (GLMA) 12 g as a monomer, butyl acrylate (BA) 28 g, and 1,4-dioxane 60 g as a solvent were charged. Then, stirring and temperature rising were started while flowing nitrogen gas. At an inner temperature of 80° C., 0.004 g of an azo radical polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-601) was added to initiate polymerization, and a reaction was carried out for 6 hours. The obtained reaction solution was diluted with acetone and poured into a large amount of hexane with stirring for purification. The precipitate was dried under reduced pressure at 80° C. for 4 hours under reduced pressure using a vacuum dryer to obtain a solid copolymer GB37. The weight average molecular weight of the obtained copolymer was 131,000. The glass transition temperature measured by DSC according to JIS K7127 was -38.5°C.

[Copolymer GB46]
A solid copolymer GB46 was obtained in the same manner as in Example 1 except that 16 g of glycerol monoacrylate (GLMA) and 24 g of butyl acrylate (BA) were used as monomers and 60 g of methyl ethyl ketone was used as a solvent. The weight average molecular weight of the obtained copolymer was 141,000. The glass transition temperature measured by DSC according to JIS K7127 was -32.8°C.

[Copolymer GB55]
A solid copolymer GB55 was obtained in the same manner as in Example 1 except that 20 g of glycerol monoacrylate (GLMA) and 20 g of butyl acrylate (BA) were used as monomers and 60 g of ethanol was used as a solvent. The weight average molecular weight of the obtained copolymer was 57,000. The glass transition temperature measured by DSC according to JIS K7127 was −26.8° C.

[Copolymer DB46]
A reaction vessel containing a stirrer was equipped with a gas introduction tube, a thermometer, and a cooling tube, and 4 g of 2,3-dihydroxypropylmethacrylamide (hereinafter also referred to as “DHPMA”) as a monomer and butyl acrylate (hereinafter 6 g, methanol as a solvent 40 g, and azo radical polymerization initiator 0.02 g (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-65) are charged, and stirring and rising are performed while flowing nitrogen gas. Warm started. Polymerization was started at an internal temperature of 65°C, and a reaction was performed for 6 hours.
The obtained reaction solution was diluted with acetone and poured into a large amount of n-hexane with stirring to reprecipitate. The precipitate was dried under reduced pressure at 40° C. for 12 hours using a vacuum dryer to obtain a solid copolymer DB46. The weight average molecular weight of the obtained copolymer was 51,000. The glass transition temperature measured by DSC according to JIS K7127 was −27.2° C.

<Evaluation method>
[Protein adhesion evaluation]
30 sheets of double-sided polymer coat film (0.75×1 cm ² ) are dipped in 3.6 mL of D-PBS(−) (Fuji Film Wako Pure Chemical Industries, Ltd., distributor code 045-29795), and priming treatment is performed at 37° C. for 1 hour. did. Subsequently, the film was immersed in 3.6 mL of each protein solution (1 mg/mL) shown below at 37° C. for 1 hour. Thereafter, the film was washed with PBS(-) in a reservoir 10 times by pipetting, and this was repeated 5 times. Subsequently, 10 films each were placed in a 1.5 mL tube (WATSON: low adhesion of prokeep protein, product number: PK15C-500), and each 1% SDS aqueous solution (Fuji Film Wako Pure Chemical Industries, Ltd., vendor code 191). -07145) 1.2 mL was added, and the protein was washed out by stirring at 37° C. for 1 hour. Then, the contaminants were removed and the protein was concentrated by the chloroform/methanol method. After resuspending with 50 μL of PBS(−) and 50 μL of 2× sample buffer (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., distributor code 193-11032) and reducing at 98° C. for 5 minutes, SDS-PAGE electrophoresis (Laemmli method) ) (E-PAGEL manufactured by ATTO, model ER 520L). SYPRO Ruby staining (Thermo fisher scientific, product number S12000) was performed, and densitometry quantitative evaluation based on the molecular weight was performed by an imaging device (Bio Rad, ChemiDoc ^™ Touch) to measure the amount of attached protein. When the PS coated film produced in Comparative Example 1 was used, the protein adhesion amount was set to 100% for comparative evaluation.
(Various protein solutions)
Albumin, human, plant expressed recombinant:
Fuji Film Wako Pure Chemical Industries, Ltd., distributor code 018-21541
Fibrinogen, derived from human plasma:
Aldrich, product number F3879-250MG
Fibronectin, derived from human plasma:
Aldrich, product number F2006-1MG
γ-globulin, derived from human plasma:
Fuji Film Wako Pure Chemical Industries, Ltd., distributor code 075-06691
Lysozyme, human, recombinant (plant expression):
Fuji Film Wako Pure Chemical Industries, Ltd., distributor code 189-02064
Myoglobin salt-free, from horse:
Product made from Nakarai Tesque, product code 23550-74
Trypsin inhibitor from soybean:
Fuji Film Wako Pure Chemical Industries, Ltd., distributor code 202-20123

[Microbial adhesion evaluation]
The strains shown below were used. After inoculating 5 mL of the culture medium into a culture test tube from a cryopreserved strain and performing regenerative culture while stirring at a predetermined temperature and 300 rpm (shaking culture machine: Takasaki Kagaku Kikai Co., Ltd., TXY-16R-3F). , Subculture (20 mL) was carried out for 18 hours. Then, the cells were collected by centrifugation at 5000×g for 5 minutes, and the supernatant was removed, followed by washing with 15 mL of PBS(−) or 0.85% NaCl aqueous solution. This cleaning work was performed twice in total. The washed bacterial solution was adjusted to 1×10 ⁹ cells/mL in a 6-well microplate (IWAKI product code 3810-006), and 3 mL was added to each well. Subsequently, a 2×2 cm ² square polymer-coated film, which had been separately immersed in sterilized water, was placed in the well and allowed to stand at a predetermined temperature for 1 hour. Then, the bacterial solution was removed from the wells using Pipetman, and 4 mL of PBS(-) or 0.85% NaCl aqueous solution was added to perform weak pipetting to perform rinsing. This was repeated twice. Transfer the film to a 6-well microplate prepared separately, and add 3 mL of 2.5% glutaraldehyde aqueous solution (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., vendor code 072-02262, diluted with PBS(-) or 0.85% NaCl aqueous solution). Was added and the mixture was allowed to stand at room temperature for 2.5 hours for immobilization. Subsequently, PBS (−) or 5 mL of 0.85% NaCl aqueous solution was added to the wells, pipetting was performed 10 times, and then the liquid was removed. Similarly, washing was performed twice with 5 mL of distilled water. Then, freeze-drying was performed and dehydration was performed. After the central part of the film was cut into 0.75×0.75 cm ² squares, placed on an SEM stand and subjected to gold vapor deposition (Smart Coat manufactured by JEOL), after observing the entire film with SEM (JSM7600F manufactured by JEOL Ltd.) An average of 5 locations was photographed. The surface coverage of the bacteria was calculated from the obtained SEM photograph using ImageJ software to determine the amount of adhered microorganisms. When the PS coated film produced in Comparative Example 1 was used, the amount of adhered microorganisms was set to 100% for comparative evaluation.
(Strain/medium/culture temperature)
Pseudomonas sputida ATCC700801 strain/Trypticase Soy medium/30° C.
Streptococcus mutans NBRC13955 strain/BHI medium/37°C
Staphylococcus aureus NBRC12732 strain/BHI medium/37° C.
Pseudomonas aeruginosa NBRC13275 strain/LB medium/37° C.

[Texture evaluation]
As the cloths used for evaluation, two kinds of cloth were used: PET (Cloth 1) by Shikiso Co., Ltd. and attached white cloth PET (Cloth 2) for testing by the Japanese Standards Association. The cloth 1 and the cloth 2 each having a weight of 5×5 cm ² which had been measured in advance were dipped in a test solution having a solid content of 1% and then squeezed with a mangle (manufactured by Daiei Kagaku Seiki Seisakusho). The amount of the test liquid remaining on the cloth was calculated from the weight change before and after the impregnation, and the impregnated polymer (copolymer) weight was calculated from the polymer concentration of the test liquid. Further, the cloth after the impregnation was sufficiently dried, and then sensory evaluation was performed by 10 panelists based on the following criteria, and the average score was shown.
<Score>
5 points: A soft texture is imparted compared to the target cloth 4 points: A slightly soft texture is imparted compared to the target cloth 3 points: A texture equivalent to that of the target cloth 2 points: A slight texture compared to the target cloth Is harder 1 point: Remarkably harder than the target cloth

[Odor evaluation]
The evaluation film produced by coating the evaluation sample on both sides was cut into A4 size, placed in a tea envelope and left for one day and night, and then the tea envelope was opened to evaluate the odor contained therein. The odor was evaluated by 5 expert panelists by the 6-level odor intensity display method shown in Table 1, and the obtained intensities were shown by the average value (rounded off) of the 5 panelists.
<Odor intensity>
5 points: No odor.
4 points: Smells enough to be detected.
3 points: It is a weak odor that allows you to know what odor it is.
2 points: The odor is easily perceivable.
1 point: It has a strong odor.
0 point: It has a very strong odor.

[Evaluation of antifouling coating film]
200 ml of seawater collected from Koshienhama, Nishinomiya-shi, Hyogo prefecture was circulated and passed for 2 months in a glass tube with an inner diameter of 5 mm and a length of 100 mm with a coating film on the inner surface, and then dried at room temperature for 1 day. Then, the stain state of the inner surface was visually evaluated.
[Score]
5 points: The transparency is equivalent to that in the initial state.
4 points: The transparency is slightly lower than that in the initial state, but there is no stain like stains.
3 points: Compared with the initial state, the transparency is slightly lowered, and there are stains in places.
2 points: Compared with the initial state, the transparency is slightly lowered and there are many stain-like stains.
1 point: Compared with the initial state, it is clouded white and the transparency is lowered.

<Examples 1 to 4>
Using a spin coater (MIKASA CO. LTD., SPIN COATER 1H-D7), the easy-adhesion PET film (Toray, Lumirror T60) was diluted with ethanol to dilute each of the copolymers GB37, GB46, GB55, and DB46. The prepared 1 (w/w)% solution was added dropwise and air dried. This was performed on both sides to produce a double-sided polymer coat film. Protein adsorption was evaluated using the produced film. The results are shown in Table 1.

<Comparative Example 1>
Using a spin coater (MIKASA CO. LTD., SPIN COATER 1H-D7), 1 (polystyrene (PS; manufactured by Aldrich, product number 441147-1KG)) of 1 ( The w/w)% solution was added dropwise and air dried. This was performed on both sides to prepare a double-sided polymer coat film (PS coat film). Protein adsorption was evaluated using the produced film. The results are shown in Table 1.

From the above examples, it is clear that the antifouling agent of the present invention has an excellent protein adhesion suppressing effect.

<Examples 5 to 8>
Using the double-sided polymer-coated films prepared in Examples 1 to 4, microbial adhesion evaluation was carried out. The results are shown in Table 2.

<Comparative example 2>
Using the PS coated film produced in Comparative Example 1, microbial adhesion evaluation was carried out. The results are shown in Table 2.

From the above examples, it is clear that the antifouling agent of the present invention has an excellent effect of inhibiting bacterial adhesion.

<Examples 9 to 12>
Copolymers GB37, GB46, GB55 and DB46 were each diluted with ethanol to prepare a 1 (w/w)% ethanol solution. Each of the obtained ethanol solution is dipped with PET (Cloth 1) from Shikiso Co., Ltd. and PET (Cloth 2) attached to the Japanese Standards Association for testing, and the solution is drained with a mangle (manufactured by Daiei Kagaku Seiki Seisakusho), and then air-dried. did. After that, texture evaluation was performed. The results are shown in Table 3.

<Examples 13 to 16>
Copolymers GB37, GB46, GB55, and DB46 were diluted with ethanol to prepare ethanol solutions having concentrations of 10 ppm and 10000 ppm. Table 4 shows the results of the odor evaluation performed using the double-sided coated film produced using each ethanol solution as an evaluation film.

<Comparative Examples 3 to 5>
Aromatic sulfonate formalin condensates, naphthalene sulfonate formalin condensates (Labelin FP: manufactured by Dai-ichi Kogyo Seiyaku), melamine sulfonate formalin condensates (Labelin FP: manufactured by Dai-ichi Kogyo Seiyaku), and fluorine compounds. The perfluoroalkylethylene oxide adduct (Unidyne DS-401: manufactured by Daikin Industries, Ltd.) was diluted with ethanol to prepare ethanol solutions having concentrations of 10 ppm and 10000 ppm. Table 4 shows the results of the odor evaluation performed using the double-sided coated film produced using each ethanol solution as an evaluation film.

<Examples 17 to 20>
Copolymers GB37, GB46, GB55 and DB46 were each diluted with ethanol to prepare a 1 (w/w)% ethanol solution. A glass tube having a solution inner diameter of 5 mm and a length of 100 mm was filled with the obtained ethanol solution, and then the solution was discharged and dried at room temperature for 60 minutes. The same operation was repeated once again to coat the inner surface of the glass tube with the polymer. The glass tube was connected to a circulation pump and a container containing 200 ml of seawater with a silicon rubber tube, and the seawater was passed through the glass tube for 2 months and circulated to evaluate the antifouling coating film. The results are shown in Table 5.

<Comparative example 6>
The inner surface of the glass tube was coated with polystyrene and the antifouling coating film was evaluated in the same manner as in Examples 17 to 20 except that the polymer solution to be filled in the glass tube was a 1(w/w)% acetone solution of polystyrene. .. The results are shown in Table 5.

<Comparative Example 7>
The inner surface of the glass tube was coated with polyvinyl alcohol in the same manner as in Examples 17 to 20 except that the polymer solution filled in the glass tube was a 1 (w/w)% aqueous solution of polyvinyl alcohol, and the antifouling coating film was evaluated. It was The results are shown in Table 5.

From the above examples, it is clear that the antifouling agent of the present invention exhibits excellent antifouling property against stains derived from microorganisms contained in seawater.

Claims

A protective film containing a copolymer having a structural unit derived from a polymerizable double bond-containing monomer having two or more hydroxyl groups and an alkyl (meth)acrylate derived structural unit having an alkyl group with 4 to 12 carbon atoms Dirt.
The antifouling agent according to claim 1, wherein the polymerizable double bond-containing monomer having two or more hydroxyl groups includes a monomer represented by the following formula (I).

(In the formula (I), R 1 represents a hydrogen atom or a methyl group, and X represents an oxygen atom or a —NH— group.)
The antifouling agent according to claim 1 or 2 for treating fibers.
The antifouling agent according to claim 3, wherein the fiber is at least one selected from the group consisting of polyester, nylon and urethane.
The antifouling agent according to claim 1 or 2 for treating water-related products.
An antifouling coating film comprising the antifouling agent according to claim 1 or 2.
A substrate with an antifouling coating film, which has the antifouling coating film according to claim 6 on a substrate.
The base material with an antifouling coating film according to claim 7, wherein the base material is a ship, an underwater structure, a fishing net or fishing gear.