WO2017110926A1

WO2017110926A1 - Antifouling coating material

Info

Publication number: WO2017110926A1
Application number: PCT/JP2016/088213
Authority: WO
Inventors: 智亮中西; 瑞菜豊田; 志郎江畑; 俊齋藤; 亮平小口
Original assignee: 旭硝子株式会社
Priority date: 2015-12-25
Filing date: 2016-12-21
Publication date: 2017-06-29

Abstract

Provided is a coating material having excellent corrosion resistance and durability to which proteins do not tend to adsorb. An antifouling coating material including a fluorine-containing polymer having units having a biocompatible group, units based on a fluoroolefin, and units based on one or more selected from the group consisting of vinyl ethers, vinyl esters, and allyl ethers; in which the biocompatible group is at least one selected from the group consisting of groups represented by formula (1), groups represented by formula (2), and groups represented by formula (3).

Description

Antifouling coating material

The present invention relates to an antifouling coating material.

The ocean structures, ship bottoms, and household waters are painted in various ways to prevent corrosion. This painting is devised to prevent protein adsorption or biological adhesion (see Patent Documents 1 to 3).

Japanese Unexamined Patent Publication No. 2007-169628 Japanese Patent Laid-Open No. 2002-069378 International Publication No. 2013/073580

However, none of the conventional coating materials sufficiently satisfy high corrosion resistance and non-adsorbability such as protein at a high level at the same time, and a coating material has been desired.
The present invention is excellent in anticorrosion durability and has a property that protein is difficult to adsorb, and is suitable for ships (particularly ship bottom), marine structures, water tanks, outer walls, roofs, building rooftops, cell culture vessels, and microchannels. An object of the present invention is to provide a coating material useful in fields such as the surface.

The present invention provides the following inventions [1] to [9].
[1] A fluoropolymer having a unit having a biocompatible group, a unit based on a fluoroolefin, and a unit based on one or more selected from the group consisting of vinyl ether, vinyl ester, and allyl ether, The affinity group is at least one selected from the group consisting of a group represented by the following formula (1), a group represented by the following formula (2), and a group represented by the following formula (3). Dirty coating material.

(In the above formula, n is an integer of 1 to 10, and m is 2 to 100 when the group represented by the formula (1) is contained in the side chain in the fluoropolymer, And R ¹ to R ³ each independently represents an alkyl group having 1 to 5 carbon atoms, a is an integer of 1 to 5, and b is an integer of 1 to 5. , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 5 carbon atoms, and X ⁻ is a group represented by the following formula (3-1) or a group represented by the following formula (3-2): And c is an integer of 1 to 20, and d is an integer of 1 to 5.)

[2] The antifouling coating material according to [1], wherein the fluoroolefin is one or more selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, and vinylidene fluoride.
[3] The antifouling coating material according to [1] or [2], wherein the unit having a biocompatible group is a unit based on a monomer represented by the following formula (m1).
CH ₂ = C (R ¹¹ ) -Q ^1- (C _n H _2n O) _m -R ¹² (m1)
(Wherein R ¹¹ is a hydrogen atom, a chlorine atom or a methyl group; Q ¹ is a single bond, an etheric oxygen atom or a divalent organic group having 1 to 20 carbon atoms; R ¹² is a hydrogen atom or — (CH ₂ ) _i —R ¹³ (wherein R ¹³ is a hydrogen atom, a fluorine atom, a trifluoromethyl group or a cyano group, i is an integer of 1 to 25), and n is 1 to 10 And m is 1 to 100.)
[4] The antifouling coating material according to any one of [1] to [3], wherein the fluoropolymer has units based on a monomer having a crosslinkable group.
[5] The antifouling coating material according to [4], wherein the crosslinkable group is a hydroxyl group.
[6] The fluoropolymer has 0.1 to 40 mol% of a unit having a biocompatible group and 20 to 80 mol of a unit based on a fluoroolefin when the entire polymer is 100 mol%. The antifouling coating according to any one of [1] to [5], wherein the antifouling coating has 10 to 75 mol% of units based on one or more selected from the group consisting of vinyl ether, vinyl ester, and allyl ether Wood.
[7] The antifouling coating material according to any one of [1] to [6], which is a marine organism adhesion prevention paint [8] Any of [1] to [6], which is an antifungal / algae paint The antifouling coating material according to item 1.
[9] The antifouling coating material according to [8], which contains an antifungal agent or an antialgal agent.

According to the present invention, a high level of anti-corrosion durability and non-adsorbability such as protein are sufficiently satisfied at a high level at the same time, in particular, ship (especially ship bottom), marine structure, water tank, outer wall, roof, building. Coating materials useful in fields such as rooftops, cell culture vessels, microchannel surfaces, and the like.

In the present specification, the following terms are defined and expressed as follows.
The “unit” means a part derived from a monomer that exists in the polymer and constitutes the polymer. The unit derived from the monomer resulting from addition polymerization of a monomer having a carbon-carbon unsaturated double bond is a divalent unit generated by cleavage of the unsaturated double bond. Moreover, what unitally converted the structure of a unit after polymer formation is also called a unit. Hereinafter, in some cases, a unit derived from an individual monomer is referred to as a name obtained by adding “unit” to the monomer name.

“Bioaffinity group” means a group having the property of inhibiting protein from adsorbing to a polymer and preventing cells from adhering to the polymer and becoming immobile.
A group represented by the formula (1) is referred to as a group (1). In addition, groups and monomers represented by other formulas will be described in the same manner.
The antifouling coating material includes a polymer having a unit having a biocompatible group and a unit based on a fluoroolefin.

[Polymer]
The polymer according to the present invention (hereinafter also referred to as a specific polymer) is one type selected from the group consisting of a unit having a biocompatible group, a unit based on fluoroolefin, and vinyl ether, vinyl ester, and allyl ether. Has units based on the above.
The specific polymer has a unit having a biocompatible group. The bioaffinity group is at least one group selected from the group consisting of the group (1), the group (2), and the group (3). Adsorption of protein is suppressed because a polymer has these bioaffinity groups. As the bioaffinity group, the group (1) is preferable because it has a high protein adsorption inhibitory effect.
The group (1) may be contained in the main chain of the polymer and may be contained in the side chain, but is preferably contained in the side chain. In the group (1), n is 1 to 10, preferably 1 to 4, and particularly preferably 2 to 3. The divalent group (oxyalkylene chain) represented by the formula (1) is preferably an oxymethylene chain, an oxyethylene chain, an oxypropylene chain, an oxytrimethylene chain, an oxybutylene chain, or an oxytetramethylene chain. A chain or an oxypropylene chain is more preferable, and an oxyethylene chain is particularly preferable.

M in the group (1) is 2 to 100, preferably 2 to 50, and particularly preferably 3 to 30 when the group represented by the formula (1) is contained in the side chain in the fluoropolymer. When m is within this range, the protein adsorption suppressing effect is high. m is preferably from 5 to 300, particularly preferably from 10 to 200, from the viewpoint of excellent water resistance when the group (1) is contained in the main chain of the fluoropolymer (A). Here, m means an average value in the monomer used. When m is 2 or more, (C _n H _2n O) of the group (1) may be one kind or two or more kinds. In the case of two or more types, the arrangement may be random, block, or alternating. The group (1) possessed by the polymer may be one type or two or more types.

In the group (2), R ¹ to R ³ are each independently an alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint of easy availability of raw materials, and a methyl group is Particularly preferred. a is an integer of 1 to 5, preferably 2 to 5, and particularly preferably 2 from the viewpoint of availability of raw materials. b is an integer of 1 to 5, preferably 1 to 4 and particularly preferably 2 from the viewpoint that protein is difficult to adsorb. The group (2) possessed by the polymer may be one type or two or more types.

In the group (3), R ⁴ and R ⁵ are each independently an alkyl group having 1 to 5 carbon atoms, and an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is preferable. Particularly preferred. c is an integer of 1 to 20, preferably 1 to 15, more preferably 1 to 10, and particularly preferably 2, from the viewpoint that the polymer is excellent in flexibility. d is an integer of 1 to 5, preferably 1 to 4 and particularly preferably 1 from the viewpoint that protein is difficult to adsorb. The group (3) possessed by the polymer may be one type or two or more types. In addition, when the polymer has a group (3), the polymer has a group (3) in which X ⁻ is a group (3-1) or X ⁻ has a group ( It is preferably any of those having the group (3) which is 3-2).

The specific polymer has units based on fluoroolefin (m10). A fluoroolefin is an olefin in which one or more fluorine atoms are bonded to carbon atoms constituting a carbon-carbon double bond. Examples of the fluoroolefin include tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, and hexafluoropropylene. Of these, one or more fluoroolefins selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, and vinylidene fluoride are preferred because the durability of the polymer tends to increase. And / or chlorotrifluoroethylene is more preferred. Only one type of fluoroolefin may be used, or two or more types may be used. Only one type is preferred because the reactivity is easy to control.

The unit having the group (1) is preferably a unit based on the monomer represented by the following formula (m1).
CH ₂ = C (R ¹¹ ) -Q ^1- (C _n H _2n O) _m -R ¹² (m1)
In formula (m1), R ¹¹ represents a hydrogen atom, a chlorine atom or a methyl group, preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
Q ¹ is a single bond, an etheric oxygen atom or a divalent organic group having 1 to 20 carbon atoms, preferably a divalent organic group having 1 to 20 carbon atoms. The divalent organic group for Q ¹ is preferably — (CH ₂ ) _e —OR ¹⁴ — (O) _f — or —COO (CH ₂ ) _g — (O) _h —. e, f, and h are each independently 0 or 1, and g is an integer of 0-4. However, when g is 0 (zero), h is 0 (zero). e is preferably 0 (zero). f is preferably 1. g is preferably 0 (zero) or 2. When g is not 0, h is preferably 1. R ¹⁴ is preferably a single bond or a divalent hydrocarbon group having 1 to 19 carbon atoms. However, when R ¹⁴ is a single bond, h is 0 (zero).
That is, as Q ¹ , —O—, —CH ₂ —O—CH ₂ — (cHex) —CH ₂ —O—, —O—CH ₂ — (cHex) —CH ₂ —O—, or —COO— Is preferred. However, cHex means a cyclohexylene group. As the cyclohexylene group, a 1,4-cyclohexylene group is preferable.
Further, in —Q ¹ — (C _n H _2n O) _m —, the oxyalkylene chain is considered as one lump and m is considered to be maximum.
As the monomer (m1), vinyl ethers having a group (1), vinyl esters having a group (1), or allyl ethers having a group (1) are preferable, and vinyl ethers having a group (1) are More preferred.

R ¹² is a hydrogen atom or — (CH ₂ ) _i —R ¹³ , and preferably a hydrogen atom. When R ¹² is a hydrogen atom, the terminal of the oxyalkylene chain is preferably a hydroxyl group, which is a crosslinkable group described later in the specific polymer. R ¹³ is a hydrogen atom, a fluorine atom, a trifluoromethyl group or a cyano group, i is an integer of 1 to 25.
Specific examples of the monomer (m1) include the following compounds.
CH ₂ ═CH—COO— (C ₂ H ₄ O) _m —H,
CH ₂ ═CH—O—CH ₂ — (cHex) —CH ₂ —O (CH ₂ CH ₂ O) _m —H

The unit having the group (2) is preferably a unit based on a monomer represented by the following formula (m2).
CH ₂ = C (R ²¹ ) -Q ^2- (CH ₂ ) _a- (PO ₄ ^- )-(CH ₂ ) _b- (N ⁺ R ¹ R ² R ³ ) (m2)

In the formula (m2), R ²¹ represents a hydrogen atom, a chlorine atom or a methyl group, preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
Q ² is a single bond, an etheric oxygen atom or a divalent organic group having 1 to 20 carbon atoms, preferably a divalent organic group having 1 to 20 carbon atoms. The divalent organic group in Q ² is the same as the divalent organic group in Q ¹ . As the monomer (m2), vinyl ethers having group (2), vinyl esters having group (2), allyl ethers having group (2), or (meth) acrylic acid having group (2) Esters are preferred, vinyl ethers having group (2), vinyl esters having group (2), or allyl ethers having group (2) are more preferred, and vinyl ethers having group (2) are more preferred.
Specific examples of the monomer (m2) include 2-methacryloyloxyethyl phosphorylcholine, 2-acryloyloxyethyl phosphorylcholine and the like.

The unit having the group (3) is preferably a unit based on a monomer represented by the following formula (m3).
_{^{CH 2 = C (R 31)}} -Q 3 - (CH 2) c - (N + R 4 R 5) - (CH 2) d -X - (m3)
In the formula (m3), R ³¹ is a hydrogen atom, a chlorine atom or a methyl group, preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom.
Q ³ is a single bond, an etheric oxygen atom or a divalent organic group having 1 to 20 carbon atoms, preferably a divalent organic group having 1 to 20 carbon atoms. The divalent organic group in Q ³ is the same as the divalent organic group in Q ¹ . As the monomer (m3), vinyl ethers having a group (3), vinyl esters having a group (3), allyl ethers having a group (3), or (meth) acrylic acid having a group (3) Esters are preferred, vinyl ethers having group (3), vinyl esters having group (3), or allyl ethers having group (3) are more preferred, and vinyl ethers having group (3) are more preferred.

Specific examples of the monomer (m3) include the following compounds.
N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, N-acryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-propylsulfoxybetaine, N-methacryloylaminopropyl-N, N-dimethylammonium-α-N-propylsulfoxybetaine, and the like.

The specific polymer is selected from the group consisting of a unit based on the monomer (m1), a unit based on the monomer (m2), and a unit based on the monomer (m3) as the unit having a biocompatible group. It is preferable to have at least one unit. In particular, the specific polymer preferably has a unit based on the monomer (m1) because of its high protein adsorption inhibiting effect.

The specific polymer further has a unit based on one or more selected from the group consisting of vinyl ether, vinyl ester, and allyl ether. However, they do not have a biocompatible group. These are excellent in alternating copolymerization with fluoroolefin, and are expected to improve the durability, weather resistance, scratch resistance and impact resistance of the coating layer to be formed. The unit is a unit based on one or more monomers (m20) selected from the group consisting of vinyl ethers, vinyl esters, and allyl ethers. As a monomer (m20), the monomer (m21) which has a crosslinkable group, or the monomer (m22) which does not have a crosslinkable group is mentioned. Examples of the crosslinkable group include a hydroxyl group, a carboxyl group, an amino group, and an epoxy group, and a hydroxyl group is more preferable.

Examples of the monomer having a hydroxyl group as a crosslinkable group include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy -2-Hydroxyalkyl vinyl ethers such as 2-methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, cyclohexanedimethanol monovinyl ether; 2-hydroxyethyl allyl ether, 3-hydroxypropyl allyl ether, 4-hydroxybutyl allyl Hydroxyalkyl allyl ethers such as ether and glycerol monoallyl ether; 2-hydroxypropanoic acid vinyl ester , Hydroxyalkyl carboxylic acid vinyl esters such as 4-hydroxy-pentanoic acid vinyl ester and the like.
Examples of a method for introducing a unit based on a monomer having a hydroxyl group into the polymer include a method of forming a unit containing a hydroxyl group after the polymerization when the polymer is synthesized. Examples of the method for forming a unit having a hydroxyl group after polymerization include a method in which a hydrolyzable vinyl ester or the like is copolymerized and then hydrolyzed to form a hydroxyl group.

Examples of monomers having a carboxyl group as a crosslinkable group include vinyloxyvaleric acid, 3-vinyloxypropionic acid, 3- (2-vinyloxybutoxycarbonyl) propionic acid, and 3- (2-vinyloxyethoxycarbonyl) propionic acid. Saturated carboxylic acid vinyl ethers such as allyloxyvaleric acid, 3-allyloxypropionic acid, 3- (2-allyloxybutoxycarbonyl) propionic acid, and 3- (2-allyloxyethoxycarbonyl) propionic acid. Allyl ethers; saturated polycarboxylic acid monovinyl esters such as monovinyl adipate, monovinyl succinate, vinyl phthalate, and vinyl pyromellitic acid.

Further, as a method for introducing a unit based on a monomer having a carboxyl group, there is a method in which a carboxyl group is formed by reacting a dibasic acid anhydride after polymerizing a polymer having a hydroxyl group.

Monomers having an amino group as a crosslinkable group include aminoalkyl vinyl ethers represented by CH ₂ ═CH—O— (CH ₂ ) _x —NH ₂ (x = 1 to 10); CH ₂ ═CH—O Examples thereof include aminoalkylcarboxylic acid vinyl esters represented by —CO (CH ₂ ) _x —NH ₂ (x = 1 to 10).
Examples of the monomer having an epoxy group as a crosslinkable group include epoxy group-containing alkyl vinyl ethers such as glycidyl vinyl ether; epoxy group-containing alkyl allyl ethers such as glycidyl allyl ether.
When the polymer in the present invention has a unit based on a monomer having a crosslinkable group, it can be crosslinked when a coating material containing the polymer is used as a coating film, and a highly durable coating film is obtained. It is done.

Examples of the monomer (m22) having no crosslinkable group include vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether; vinyl esters such as vinyl butanoate and vinyl octoate; Examples include allyl ethers such as allyl ether; acryloyl compounds such as butyl acrylate; and acrylic esters such as methacryloyl compounds such as ethyl methacrylate.
When the specific polymer has a unit based on a monomer having no crosslinkable group, when the coating material containing the polymer is used as a coating film, flexibility or the like can be imparted to the coating film.

The specific polymer further optionally has a unit having the above-mentioned bioaffinity group, a unit based on a fluoroolefin, and a unit based on another monomer (m30) other than a unit based on the monomer (m20). It may be. As a monomer (m30), the monomer (m31) which has a crosslinkable group, or the monomer (m32) which does not have a crosslinkable group is mentioned. Examples of the crosslinkable group include a hydroxyl group, a carboxyl group, an amino group, and an epoxy group, and a hydroxyl group is more preferable.
Examples of the monomer having a hydroxyl group as a crosslinkable group include hydroxyalkyl carboxylic acid allyl esters such as 2-hydroxypropanoic acid allyl ester and 4-hydroxypentanoic acid allyl ester; 2-hydroxyethyl (meth) acrylate and the like (meta ) Hydroxyalkyl esters of acrylic acid and the like.
Examples of monomers having a carboxyl group as a crosslinkable group include 3-butenoic acid, 4-pentenoic acid, 2-hexenoic acid, 3-hexenoic acid, 5-hexenoic acid, 2-heptenoic acid, 3-heptenoic acid, 6 -Heptenoic acid, 3-octenoic acid, 7-octenoic acid, 2-nonenoic acid, 3-nonenoic acid, 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid Unsaturated carboxylic acids such as cinnamic acid; unsaturated dicarboxylic acids such as itaconic acid, maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, or intramolecular acid anhydrides thereof; itaconic acid monomethyl ester, monomethyl maleate Examples thereof include unsaturated dicarboxylic acid monoalkyl esters such as ester and fumaric acid monomethyl ester.
Examples of the monomer having an amino group as a crosslinkable group include aminomethylstyrene, vinylamine, acrylamide, vinylacetamide, and vinylformamide.
Examples of the monomer having an epoxy group as a crosslinkable group include epoxy group-containing alkyl acrylates or methacrylates such as glycidyl acrylate and glycidyl methacrylate.
Examples of the monomer (m32) having no crosslinkable group include olefins such as ethylene and propylene; aromatic vinyl compounds such as styrene and vinyltoluene.

The composition of the specific polymer is preferably 0.1 to 40 mol%, more preferably 0.5 to 30 mol% of a unit having a biocompatible group when the entire polymer is 100 mol%. More preferably, it is contained in an amount of 1.0 to 10 mol%. Further, when the entire polymer is taken as 100 mol%, it is preferable to contain 20 to 80 mol%, more preferably 30 to 70 mol%, based on fluoroolefin. Further, when the whole polymer is taken as 100 mol%, the unit based on the monomer (m20) is preferably contained in an amount of 10 to 75 mol%, more preferably 30 to 70 mol%.
When the monomer (m21) having a crosslinkable group and the monomer (m22) having no crosslinkable group are used in combination, the unit based on the monomer (m21) and the unit based on the monomer (m22) The ratio is preferably 10:90 to 90:10 in molar ratio. The specific polymer may be used alone or in combination of two or more.
The specific polymer is obtained by polymerization by a known method. That is, a polymer can be produced by polymerization using a monomer having a biocompatible group, a fluoroolefin, and a monomer (m20). Examples of the polymerization method include solution polymerization and emulsion polymerization.

The antifouling coating material of the present invention may contain other components in addition to the specific polymer. Examples of other components include a solvent, a surfactant, a pigment, and a curing agent.
A hardening | curing agent plays the role which hardens the coating layer which apply | coated the coating composition by reacting with the crosslinkable group of a specific polymer, and forming a crosslinked structure. As the curing agent, a compound having two or more functional groups having reactivity with the crosslinkable group is appropriately selected according to the kind of the crosslinkable group possessed by the specific polymer.
As the curing agent, an isocyanate curing agent, a blocked isocyanate curing agent, an amino resin, or the like is preferable.

When the specific polymer has a hydroxyl group, the curing agent is preferably an isocyanate curing agent, a blocked isocyanate curing agent, or an amino resin. When the polymer has a carboxyl group, examples of the curing agent include amine-based curing agents and epoxy-based curing agents. When the polymer has an amino group, examples of the curing agent include a carboxyl group-containing curing agent, an epoxy curing agent, and an acid anhydride curing agent. When the polymer has an epoxy group, examples of the curing agent include a carboxyl group-containing curing agent, an acid anhydride curing agent, and an amine curing agent.
Examples of the isocyanate curing agent include non-yellowing polyisocyanate and non-yellowing polyisocyanate modified.
Examples of the non-yellowing polyisocyanate include alicyclic polyisocyanates such as isophorone diisocyanate (IPDI) and dicyclohexylmethane diisocyanate (HMDI); and aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI).

Examples of the non-yellowing polyisocyanate-modified product include the following modified products. An isocyanurate of an aliphatic diisocyanate or an alicyclic diisocyanate; a modified product having a structure represented by —X—C (═O) —NH— obtained by modifying an aliphatic diisocyanate or an alicyclic diisocyanate with a polyol or a polyamine; A modified product having a structure represented by —XC (═O) —NH—, wherein a part of the isocyanate group of an isocyanurate of an aliphatic diisocyanate or an alicyclic diisocyanate is modified with a polyol. However, X in —X—C (═O) —NH— is an organic group derived from a compound having a hydroxyl group or a compound having an amino group. The number of functional groups possessed by the compound having a hydroxyl group or the compound having an amino group is preferably 2 to 3.

The blocked isocyanate curing agent is a curing agent in which an isocyanate group is blocked. The isocyanate group can be blocked with epsilon caprolactam (E-CAP), methyl ethyl ketone oxime (MEK-OX), methyl isobutyl ketone oxime (MIBK-OX), pyraridine, triazine (TA) and the like.
Examples of the amino resin include melamine resin, guanamine resin, sulfoamide resin, urea resin, aniline resin, and the like. Among these, a melamine resin is preferable because it has a high curing rate. Specific examples of the melamine resin include alkyl etherified melamine resins that are alkyl etherified. Among these, a melamine resin substituted with a methoxy group and / or a butoxy group can be used more preferably.

The coating material of the present invention preferably contains a pigment for the purpose of rust prevention, coloring, reinforcement and the like of the cured coating film layer. The pigment is preferably at least one pigment selected from the group consisting of rust preventive pigments, colored pigments and extender pigments.
The rust preventive pigment is a pigment for preventing corrosion and alteration of the metal substrate. Lead-free rust-proof pigments with low environmental impact are preferred. Examples of lead-free rust preventive pigments include cyanamide zinc, zinc oxide, zinc phosphate, calcium magnesium phosphate, zinc molybdate, barium borate, and calcium cyanamide zinc.
The color pigment is a pigment for coloring the coating film. Examples of the color pigment include titanium oxide, carbon black, and iron oxide.
The extender pigment is a pigment for improving the hardness of the coating film and increasing the thickness of the coating film. Examples of extender pigments include talc, barium sulfate, mica, and calcium carbonate.

The coating material of the present invention may contain a curing catalyst for the purpose of accelerating the curing reaction and imparting good chemical performance and physical performance to the cured coating film layer that is a cured product. In particular, when curing at a low temperature in a short time, it is preferable to contain a curing catalyst. Examples of the curing catalyst include the following (1) to (3).
Curing catalyst (1): a curing catalyst used for a crosslinking reaction between a fluorine-containing polymer containing a hydroxyl group and an isocyanate curing agent or a blocked isocyanate curing agent;
Curing catalyst (2): a curing catalyst used for a crosslinking reaction between a fluoropolymer containing at least one of an alkoxysilyl group and a hydroxyl group and a metal alkoxide;
Curing catalyst (3): a curing catalyst used for a crosslinking reaction between a fluoropolymer containing a hydroxyl group and an amino resin.

As the curing catalyst (1), tin catalysts such as tin octylate, tributyltin dilaurate, and dibutyltin dilaurate are preferable.
As the curing catalyst (2), acidic phosphoric acid esters such as phosphoric acid monoester and phosphoric acid diester; acidic boric acid esters such as boric acid monoester and boric acid diester; addition reaction of acidic phosphoric acid ester and amine Products, amine adducts such as addition reaction products of carboxylic acid compounds and amines; metal esters such as tin octylate and dibutyltin dilaurate; metals such as tris (acetylacetonate) aluminum and tetrakis (acetylacetonate) zirconium Chelates; metal alkoxides such as aluminum isopropoxide and titanium butoxide. Among these, acidic phosphates are preferable from the viewpoint of curability and the smoothness of the formed cured coating layer, and carbon is preferable from the viewpoints of curability, smoothness of the formed cured coating layer, water resistance, and the like. A monoalkyl phosphate having 1 to 8 carbon atoms, a dialkyl phosphate having 1 to 8 carbon atoms, or a mixture thereof is more preferable.
As the curing catalyst (3), a blocked acid catalyst is preferred. Examples of the blocked acid catalyst include various amine salts such as carboxylic acid, sulfonic acid, and phosphoric acid. In particular, higher alkyl substituted sulfonic acid amine salts such as diethanolamine salt and triethylamine salt of p-toluenesulfonic acid and dodecylbenzenesulfonic acid are preferable. A curing catalyst may be used individually by 1 type, and may use 2 or more types together.

The antifouling coating material of the present invention is used for ships (particularly ship bottoms), marine structures, water tanks, outer walls, roofs, rooftops of buildings, cell culture vessels, microchannel surfaces, and the like.
The thickness of the coating layer is preferably 1 nm to 1 mm, particularly preferably 5 nm to 800 μm. If the thickness is equal to or greater than the lower limit, protein is difficult to adsorb. If the thickness is not more than the above upper limit value, the coating layer tends to adhere to the surface.
The method for forming the coating layer on the surface is not particularly limited, and a method of applying an antifouling coating material by a wet coating method or a method of applying and drying the coating solution of the present invention by a known wet coating method is adopted. it can.

The antifouling coating material of the present invention can be used particularly as a paint applied to the surface of a ship, offshore structure or underwater structure in order to prevent marine organisms from adhering. The antifouling coating material of the present invention has an effect that it is difficult for biopolymers such as proteins and cells to adsorb or adhere to each other. (Algae) has an effect of being difficult to adhere.
The attachment of marine organisms is considered to occur when the marine organism considers the attachment object as a solid and determines that it is a suitable habitat environment. In a coating film (hereinafter also referred to as a specific coating film) formed from the antifouling coating material of the present invention, for example, the polyoxyalkylene chain is oriented on the coating film surface, and the hydrophilic polyoxyalkylene chain, water, It is considered that at least a part of the surface of the coating film is hydrated or swollen due to the interaction. Therefore, it is considered that marine organisms regard the specific coating film as water instead of solid and do not adhere to the specific coating film. That is, the specific coating film expresses a marine organism adhesion prevention mechanism.

Moreover, the antifouling coating material of the present invention can form a coating film excellent in salt water resistance and weather resistance. That is, the specific coating film has excellent marine organism adhesion prevention properties over a long period of time, and also has excellent salt water resistance and weather resistance that can withstand environmental changes (such as atmospheric exposure and temperature changes). The specific coating film is preferably applied to a ship, an offshore structure or an underwater structure.
Objects of ships, offshore structures or underwater structures are objects used in the ocean (including nearby areas), for example, bridges, fishing nets, wave-dissipating blocks, breakwaters, submarine cables, tanks, pipelines, submarine Excavation facilities, marine floats, seawater intake and discharge ports at seaside power plants, seawater piping (cooling water piping) at seaside power plants, ship hulls (especially ship bottoms and drafting parts), ship screws, ship dredging, etc. Can be mentioned. The material of the object may be any of metal, resin, rubber, stone, glass, and concrete.

Further, the shape and state of the object (contact state with seawater) are not particularly limited. For example, even in seawater piping (cooling water piping) at seaside power plants, where the piping shape is bent and the flow rate and temperature of seawater in the piping can change greatly, a specific coating film is applied to the inner surface of the piping. By having it, a marine organism adhesion prevention function and anticorrosiveness are expressed over a long period of time.
The thickness of the specific coating film is preferably 10 to 100 μm. If thickness is more than a lower limit, the salt-water resistance of a specific coating film will be more excellent, and if it is below an upper limit, the weather resistance of a specific coating film will be more excellent.

In addition, as described above, the antifouling coating material of the present invention has an effect that biopolymers such as proteins and cells are difficult to adsorb or adhere, that is, an effect that molds or algae breeding nutrients are difficult to adhere. For this reason, the antifouling coating material of the present invention can be used as an antifungal / algae paint.
The specific coating film itself forms an unsuitable environment for the growth of mold or algae, and has a fungicide / algae control mechanism that does not depend on the fungicidal action of the fungicide (preservative) or the algae. Therefore, the specific coating film has a low environmental load and can exhibit excellent antifungal and antialgal properties over a long period of time. In addition, the specific coating film has high water resistance (low water vapor permeability) and air shielding (low oxygen permeability) that prevent water from accumulating, and forms an environment that is not suitable for the growth of mold or algae. Yes. In other words, the specific coating film not only exhibits excellent antifungal and algal resistance over a long period of time, even in an environment where mold and algae are likely to be generated and propagated, such as in a wet or wet environment. Furthermore, it has excellent water resistance and weather resistance that can withstand environmental changes (air exposure, temperature changes, etc.).
In addition, the antifouling coating material of the present invention includes other additives (for example, an antifungal agent, an algal inhibitor, a crosslinking agent, a film-forming aid, a thickener, an antifoaming agent, a light stabilizer, a design agent, a surface Adjusting agent, aqueous medium, etc.).

The antifouling coating material of the present invention may contain a fungicide or an algae from the viewpoint of further enhancing the effect.
Examples of the fungicide or algae preventive include known fungicides or algae preventives, and from the viewpoint of compatibility with the specific fluoropolymer, an agent containing a compound containing a halogen atom as an active ingredient is preferable. . When a specific fluorine-containing polymer containing a chlorine atom (for example, a specific fluorine-containing polymer in which the fluoroolefin is CF ₂ ═CFCl) is used, a compound having a chlorine atom, a bromine atom, or an iodine atom is used. An agent as an active ingredient is preferred.
The amount of the fungicide or the algae is preferably 0.01 to 5% by mass with respect to the specific fluoropolymer.
The antifouling coating material of the present invention is particularly useful for articles used in wet or wet environments. In the present invention, the wet environment means an environment where the humidity is typically 40% or more, and the wetted environment means an environment that is always in contact with water or is in contact with water occasionally.
Articles used in wet or wet environments include, for example, bathtubs, ceiling panels, wall panels, floor pans, doors, faucets, drainage units, ventilation fans, mirrors, sinks, toilets, low tanks, hand-washers, etc. Indoor structures around water, underground structures such as water pipes and sewage pipes, outdoor structures such as water storage tanks and buildings. The material of the article may be any of metal, resin, rubber, stone, glass, and concrete.

The thickness of the specific coating film is preferably 10 to 100 μm. If thickness is more than a lower limit, the water resistance of a coating film is more excellent, and if it is below an upper limit, the weather resistance of a coating film is more excellent.
The specific coating film should just be formed in the outermost surface of the articles | goods exposed to a wet environment or a wet-contact environment. That is, the antifouling paint may be applied directly to the surface of the article, or may be applied to the outermost surface via the undercoat layer.
Examples of the method for applying the antifouling paint to the object include a method using a coating apparatus such as a brush, a roller, dipping, spraying, a roll coater, a die coater, an applicator, and a spin coater.
In addition, even if the article on which the specific coating film is placed is an article in a shading environment such as the outer wall of the north and west buildings with poor sunlight, the inner surface of the water storage tank, the water pipe, and the sewage pipe, Articles having a specific coating film on the surface by the above-mentioned mold-proof / algae-proof mechanism are excellent in mold-proof / algae-proof properties over a long period of time and have a low environmental load.

The antifouling coating material of the present invention is suitably used for cell culture vessels, microchannel surfaces and the like. The specific coating film is difficult to adsorb proteins, and when applied to a cell culture container (that is, when the culture medium contact surface of the cell culture container includes the specific coating film), the cells are difficult to adhere to the specific coating film. Even if cells adhere, the cells can be removed by simple washing. On the other hand, since the specific coating film is excellent in durability, excellent durability (film persistence) can be expected even in repeated cleaning. Therefore, the antifouling coating material of the present invention is suitable for a cell culture container that is used repeatedly. That is, the present invention provides a cell culture container coated with a specific polymer. In addition, if a specific coating film does not contain a pigment, transparency will be favorable and it will not become a hindrance to cell observation.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not construed as being limited to the following examples. In addition, the symbol of the compound in the following etc. is as follows, respectively.
CTFE: chlorotrifluoroethylene (Asahi Glass Co., Ltd.).
CHVE: cyclohexyl vinyl ether (manufactured by BASF).
EVE: Ethyl vinyl ether (manufactured by BASF).
CM-15EOVE: CH ₂ ═CHOCH ₂ —cHex—CH ₂ O (CH ₂ CH ₂ O) _n1 H, n1: 15, average molecular weight 830 (hydrophilic macromonomer) (manufactured by Nippon Emulsifier Co., Ltd.).
SLS: sodium lauryl sulfate (anionic surfactant (anionic emulsifier), manufactured by Nikko Chemicals).
MPC: 2-methacryloyloxyethyl phosphorylcholine (manufactured by Tokyo Chemical Industry Co., Ltd.).

Production Example 1 Production Method of Resin A In a pressure resistant reactor with a 2.5 L stainless steel stirrer (made by pressure resistant glass industry), 259 g of CHVE, 107 g of EVE, 124 g of CM-15EOOVE, ion-exchanged water 1031 g, 2.1 g of potassium carbonate, and 2.1 g of SLS were charged, cooled with ice, pressurized with nitrogen gas to 0.7 MPa, and degassed. This pressure degassing was repeated twice, and after degassing to 0.01 MPa to remove dissolved air, CTFE (434 g) was charged and a polymerization reaction was performed at 60 ° C. for 24 hours. After the polymerization reaction, the pressure reactor was cooled from 60 ° C. to 20 ° C. to obtain an aqueous dispersion containing resin A having a solid content concentration of 49.7% by mass. CTFE / CHVE / EVE / CM-15EOOVE (mol%) was 50/28/20/2.
The water vapor transmission rate per 1 μm film thickness and the oxygen transmission rate per 1 μm film thickness of the separately prepared resin A sheet were 1.0 g / m ² · day and 0.01 mol / m ² · s · Pa, respectively. It was.

Production Example 2 Production Method of Resin B In a 2.5 L stainless steel pressure-resistant reactor with a stirrer, 590 g of xylene, 170 g of ethanol, 70 g of EVE, 385 g of CHVE, 122 g of hydroxybutyl vinyl ether (HBVE), carbonic acid 11 g of potassium and 3.5 g of perbutyl pivalde (PBPV) were charged, and dissolved oxygen in the liquid was removed by degassing with nitrogen. Next, 620 g of CTFE was introduced, the temperature was gradually raised, and the reaction was continued while maintaining the temperature at 65 ° C. After 10 hours, the reactor was cooled to stop the reaction. After the reaction solution was cooled to room temperature, unreacted monomers were purged and filtered through diatomaceous earth to remove solids. Next, xylene and ethanol were removed by distillation under reduced pressure to obtain Resin B ′. CTFE / CHVE / EVE / HBVE (mol%) was 50/30/10/10.

The obtained resin B ′ was dissolved in methyl ethyl ketone (MEK) to obtain a varnish having a solid content of 60% by mass. To 300 parts by mass of this varnish, 16.1 parts by mass of a 20% by mass acetone solution of succinic anhydride and 0.072 parts by mass of triethylamine as a catalyst were added and reacted at 70 ° C. for 6 hours for esterification. When the infrared absorption spectrum of the reaction solution was measured, the characteristic absorption of succinic anhydride (1850 cm ⁻¹ , 1780 cm ⁻¹ ) observed before the reaction disappeared after the reaction, and carboxylic acid (1710 cm ⁻¹ ) and Absorption of the ester (1735 cm ⁻¹ ) was observed. The acid value of the fluoropolymer after esterification was 10.5 mgKOH / g, and the hydroxyl value was 39.3 mgKOH / g. According to the values of the acid value and the hydroxyl value, about 2.1 mol% of 10.1 mol% of the structural unit of HBVE is esterified.
Next, 3.26 parts by mass of triethylamine is added to the reaction solution after esterification, and the mixture is stirred at room temperature (23 ° C.) for 20 minutes to neutralize a part of the carboxyl groups, and then 180 parts of ion-exchanged water is added. Gradually added. This neutralized about 2.1 mol% of about 2.1 mol% of the structural unit esterified and introduced with the carboxyl group.
Thereafter, acetone and methyl ethyl ketone were distilled off under reduced pressure. Further, about 90 parts by mass of ion-exchanged water was added to obtain an aqueous dispersion containing resin B and having a solid content concentration of 40% by mass.

Production Example 3 Production Method of Resin C Charged with a 2.5 L stainless steel pressure-resistant reactor with a stirrer was charged 503 g of xylene, 142 g of ethanol, 327 g of CHVE, 85 g of HBVE, and 12 g of potassium carbonate, and cooled and deaerated. The dissolved air was removed by repeated pressurization with nitrogen gas. 387 g of CTFE was introduced into the pressure resistant reactor and the temperature was raised. When the temperature in the pressure resistant reactor reached 65 ° C., a pressure of 1.0 kg / cm ² G was shown. Thereafter, 9 ml of a 50% xylene solution of PBPV was added to initiate the reaction. While maintaining the pressure as the pressure decreased, 273 g of CTFE, 231 g of CHVE, and 60 g of HBVE were continuously added to continue the reaction. During the reaction, 23 ml of 50% xylene solution of PBPV was continuously added. After 14 hours, the supply of each monomer was stopped and the reaction was continued to 0.5 kg / cm ² G, and then the pressure-resistant reactor was cooled with water to stop the reaction. After reaching room temperature, unreacted monomer was purged and the pressure-resistant reactor was opened. The obtained resin solution was dried under reduced pressure to obtain Resin C ′. CTFE / CHVE / HBVE (mol%) was 50/39/11.

The obtained resin C ′ was dissolved in MEK to obtain a varnish having a solid content of 60% by mass. To 300 parts by mass of this varnish, 16.1 parts by mass of a 20% by mass acetone solution of succinic anhydride and 0.072 parts by mass of triethylamine as a catalyst were added and reacted at 70 ° C. for 6 hours for esterification. Next, 3.26 parts by mass of triethylamine is added to the reaction solution after esterification, and the mixture is stirred at 23 ° C. for 20 minutes to neutralize a part of the carboxyl groups, and then 180 parts of ion-exchanged water is gradually added. It was. Thereafter, acetone and methyl ethyl ketone were distilled off under reduced pressure. Further, about 90 parts by mass of ion-exchanged water was added to obtain an aqueous dispersion containing resin C and having a solid content concentration of 40% by mass.

Production Example 4 Production Method of Resin D In a pressure resistant reactor with a 2.5 L internal volume stainless steel stirrer, 259 g of CHVE, 107 g of EVE, 56.8 g of MPC, 1031 g of ion-exchanged water, 2 of potassium carbonate 0.1 g of SLS and 2.1 g of SLS were charged, cooled with ice, pressurized with nitrogen gas to 0.7 MPa, and degassed. This pressure degassing was repeated twice, and after degassing to 0.01 MPa to remove dissolved air, CTFE (434 g) was charged and a polymerization reaction was performed at 60 ° C. for 24 hours. After the polymerization reaction, the pressure resistant reactor was cooled from 60 ° C. to 20 ° C. to obtain an aqueous dispersion containing resin D having a solid content concentration of 49.7% by mass. CTFE / CHVE / EVE / MPC (mol%) was 50/28/20/3.

Protein adsorption amount measurement (1) Preparation of color developing solution and protein solution The color developing solution is peroxidase color developing solution (3,3 ', 5,5'-tetramethylbenzidine (TMBZ), manufactured by KPL) and TMB Peroxidase Substrate (KPL). What was mixed with 50 mL was used.
As a protein solution, a protein (POD-goat anti mouse IgG, manufactured by Biorad) diluted 16,000 times with a phosphate buffer solution (D-PBS, manufactured by Sigma) was used.

(2) Protein adsorption 2 mL of the protein solution is dispensed into 3 wells in a 24-well microplate (made of polystyrene (PS)) having a coating layer formed on the surface of each well (2 mL is used for each well) at room temperature. Left for 1 hour. In the case of a glass substrate, the same procedure was performed except that 6.5 mL of the protein solution was dispensed into a 6 cmφ dish 60. As a blank, 2 μL of the protein solution was dispensed into 3 wells of a 96-well microplate (2 μL was used per well).

(3) Well washing Four times with 4 mL of a phosphate buffer solution (D-PBS, manufactured by Sigma) containing 0.05% by mass of a surfactant (Tween 20, manufactured by Wako Pure Chemical Industries) on a 24-well microplate. Washed (use 4 mL per well). In the case of the glass substrate, 13 mL of the surfactant solution was used and washed four times, and then transferred to a new dish 60.

(4) Coloring solution dispensing 2 mL of the coloring solution was dispensed onto the washed 24-well microplate (2 mL was used for each well), and a coloring reaction was performed for 7 minutes. The color reaction was stopped by adding 1 mL of 2N sulfuric acid (1 mL per well was used). The glass substrate was subjected to the same method except that the color developing solution was 6.5 mL and the sulfuric acid was 3.25 mL.
For the blank, dispense 100 μL of the coloring solution to a 96-well microplate (use 100 μL per well), perform the color reaction for 7 minutes, and add 50 μL of 2N sulfuric acid (use 50 μL per well). ) The color reaction was stopped.

(5) Preparation for absorbance measurement 150 μL of liquid was taken from each well of a 24-well microplate and transferred to a 96-well microplate. In the case of a glass substrate, 150 μL of liquid was taken from the dish 60 and transferred to a 96-well microplate.

(6) Absorbance measurement and protein adsorption rate Q
Absorbance was measured at 450 nm using MTP-810Lab (Corona Electric Co., Ltd.). Here, the average value of the absorbance (N = 3) of the blank was defined as A0. The absorbance of the liquid transferred from the 24-well microplate to the 96-well microplate was defined as A1.
The protein adsorption rate Q1 was determined by the following equation, and the protein adsorption rate Q was the average value.
Q1 = A1 / {A0 × (100 / amount of dispensed blank protein solution)} × 100
= A1 / {A0 × (100/2 μL)} × 100 [%]

[Example 1]
Water was added to the dispersion liquid of the resin A obtained in Production Example 1 so that its concentration was 0.05% by mass to prepare a coating liquid. The coating solution was dispensed in a volume of 2.2 mL onto a 24-well microplate and allowed to stand at 50 ° C. for 3 days to evaporate the solvent, thereby forming a coating layer having a thickness of about 100 nm on the well surface.
[Example 2]
The well surface of the 24-well microplate in Example 1 was used without coating the resin A dispersion.

[Example 3]
A coating solution was prepared in the same manner as in Example 1 except that the resin B dispersion was used instead of the resin A dispersion. Further, using the coating solution, a coating layer having a thickness of about 100 nm was formed on the well surface of a 24-well microplate in the same manner as in Example 1.
[Example 4]
A coating solution was prepared in the same manner as in Example 1 except that the resin C dispersion was used instead of the resin A dispersion. Further, using the coating solution, a coating layer having a thickness of about 100 nm was formed on the well surface of a 24-well microplate in the same manner as in Example 1.

[Example 5]
Water was added to the dispersion liquid of the resin A obtained in Production Example 1 so that the concentration became 5% by mass to prepare a coating liquid. Using a micro dip coater manufactured by SDI, 4 cm of a 5 cm square glass plate is dipped in the coating solution, coated at a pulling rate of 1 mm / s, then dried at 50 ° C. for one day, and about 100 nm thick on a glass substrate. A coating layer was formed. Using a glass cutter, the coated part was cut into a 3 cm square and used as a test sample.
[Example 6]
The surface of the glass substrate in Example 1 was used without coating the resin A dispersion.
[Example 7]
A coating solution was prepared in the same manner as in Example 5 except that the resin B dispersion was used instead of the resin A dispersion. Further, a coating layer having a thickness of about 100 nm was formed on the glass substrate in the same manner as in Example 5 using the coating solution.

[Example 8]
A coating solution was prepared in the same manner as in Example 5 except that the dispersion of resin C was used instead of the dispersion of resin A. Further, a coating layer having a thickness of about 100 nm was formed on the glass substrate in the same manner as in Example 5 using the coating solution.
[Example 9]
A coating solution was prepared in the same manner as in Example 1 except that the dispersion of resin D was used instead of the dispersion of resin A. Further, using the coating solution, a coating layer having a thickness of about 100 nm was formed on the well surface of a 24-well microplate in the same manner as in Example 1.

The protein adsorption amounts of Examples 1 to 9 above were measured, and the results are shown in Table 1. The protein adsorption amount is the protein adsorption rate Q. Q is preferably less than 0.1 (1.0E-01).

As shown in Table 1, protein adsorption was suppressed on the surface of the resin A coated with the biocompatible site introduced as compared with the uncoated surface and the resin-coated substrate containing no biocompatible site.

Dispersibility Using the dispersion of resin A obtained in Production Example 1, 100 parts by mass of resin A (in terms of solid content), 60 parts by mass of titanium oxide pigment CR-90 (manufactured by Ishihara Sangyo Co., Ltd.), Dispersion H-14N dispersion 2.9 parts by mass of an agent (made by Nippon Emulsifier Co., Ltd.), 0.2 parts by mass of FS Antifoam 013B antifoaming agent (made by Dow Corning), 38 parts by mass of ion-exchanged water, and 100 parts by mass of glass beads are mixed. Then, using a Glenmifle disperser, the glass beads were filtered to prepare a pigment dispersion. The pigment dispersion of the pigment dispersion was very good.

Anticorrosion The anticorrosion was evaluated according to JIS 5600-7-9. The aluminum plate with a coating is cut with a cutter so that it reaches the substrate, and this is left in a salt spray environment for 4000 hours, and then washed with ion-exchanged water and dried. The state of the crosscut wound was evaluated according to the following criteria. “◯ (good)”: The swollen width of the cross-cut portion is less than 1.0 mm. “Δ (slightly good)”: The swollen width of the cross-cut portion is 1.0 mm or more and less than 3.0 mm. “× (defect)”: The swollen width of the cross-cut portion is 3.0 mm or more. That is, a test piece having a thickness of about 50 μm was prepared on the aluminum substrate using the dispersion liquid of the resin A obtained in Production Example 1, and this test was performed. In the evaluation after the test, the swollen width of the cross-cut portion was less than 1.0 mm, and the evaluation was “good”.

As shown in Table 1, in Example 1, Example 5 and Example 9 using the coating material containing the resin A which is the scope of the present invention, the coating layer is not formed in Examples 2 and 6 regardless of the base material. Compared to the protein, it was difficult to adsorb. Further, in Examples 3 to 4 and Examples 7 to 8 using the coating material containing the resin B and the resin C having a polymer as a comparative example, protein was easily adsorbed.

<Manufacture of paints>
[Production Example 11]
The 2,2,4-trimethyl-1,3-pentadiol, a film-forming aid, was added to the dispersion containing the resin A (solid content concentration 49.7% by mass) (100.0 g) obtained in Production Example 1. Mono (2-methylpropanate) (7.5 g), Rheolate 288 (trademark) (made by Elementis Japan) (0.1 g) as a thickener was added, mixed well, and a paint containing resin A ( 1) was obtained.

[Production Example 12]
The 2,2,4-trimethyl-1,3-pentadiol, a film-forming aid, was added to the dispersion containing the resin A (solid content concentration 49.7% by mass) (100.0 g) obtained in Production Example 1. Mono (2-methylpropanate) (7.5 g), Reoleate 288 (trademark) (made by Elementis Japan) (0.1 g) as a thickener, Water-dispersed isocyanate curing agent (Sumika) as a crosslinking agent Bayer Co., Ltd. (Baihijoule 3100 (trademark)) (5.4 g) was added and mixed well to obtain a paint (2) containing Resin A.
The water vapor transmission rate per 1 μm film thickness and the oxygen transmission rate per 1 μm film thickness of the resin A sheet cross-linked with the water-dispersed isocyanate curing agent were 0.05 g / m ² · day and 0.01 mol, respectively. / M ² · s · Pa. The amount ratio of the resin A and the water-dispersed isocyanate curing agent used to produce the sheet was the same as the amount ratio used in the paint (2).

[Comparative Example 11]
The dispersion containing the resin A obtained in Production Example 1 was converted into an aqueous dispersion containing a vinylidene fluoride polymer and a (meth) acrylic polymer (product name “Kynar Aquatec FMA-12” manufactured by Arkema). A coating material (3) containing a fluoropolymer having no polyoxyalkylene chain in the side chain was obtained in the same manner as in [Production Example 11] except for the change.
The separately prepared PVDF sheet (sheet made of PVDF) has a water vapor transmission rate per 1 μm thickness and an oxygen transmission rate per 1 μm thickness of 19.6 g / m ² · day and 0.5 mol / m ² , respectively. · S · Pa.

<Anti-mold / algae test>
A test plate was prepared by the following procedure.
An epoxy resin-based paint (manufactured by Chugoku Paint Co., Ltd., product name “SEAJET 013 Main Agent” and product name “SEAJET 013 Curing Agent” mixed in a mass ratio of 4: 1) is dried on both surfaces of the aluminum base. A brush was applied so that the film thickness was about 60 μm, and the film was cured at room temperature for 1 week. Next, paint (1) is applied on one side of an aluminum base material with an applicator so that the film thickness of the dried coating film is about 30 μm, and dried at room temperature for 2 weeks, so that resin A is formed on the surface. A test plate (1) having a coating film was prepared. Test plates were similarly prepared for the paints (2) and (3), and a test plate (2) and a test plate (3) were prepared.
Each of the test plates (1) to (3) is installed on the north side of a badly exposed building exposed to a wet condition, and the adhesion state of mold and algae after 4 months is visually observed. The installation site is Ichihara City, Chiba Prefecture. The results of the mold / algae adhesion test of each test plate are shown in Table 2.

<Shell protection test>
Each of the test plates (1) to (3) is immersed in the sea (water depth: 1 m), and the adhesion state of the shellfish after 4 months is visually observed. In addition, the sea immersion place is the Seto Inland Sea, and the test plate is installed so that the coating film side faces south in the sea immersion. Table 3 shows the results of the underwater immersion test of each test plate.

<Barnacle Larvae Adhesion Test>
Nauplius larvae and adherent stage larvae (Cypris) were used. Adult adult barnacles (from Himeji City, Hyogo Prefecture) were maintained and raised by feeding Artemia in a circulating water tank (water temperature 23 ± 1 ° C.). Nauplius larvae sprouted from adults were collected, transferred into a glass beaker filled with filtered seawater, and reared with the floating diatom Cheatoceros calcitrans to obtain artificially attached larvae (Cyprus larvae). The obtained cypris larvae were preserved by cold-dark treatment. These larvae were returned to room temperature before the test, and individuals that gathered in the light while actively swimming were selected and used for the adhesion test. The sample was allowed to stand on the bottom surface of a polypropylene container (80 × 80 × 45 mm), and seawater and adhering larvae were introduced.
Natural seawater (collected from the coast of Himeji City, Hyogo Prefecture) was filtered through a mixed cellulose membrane having a pore size of 0.45 μm (manufactured by Toyo Roshi Kaisha, Ltd.). The seawater state was 29.3 PSU, 8.40 pH. The test seawater was moved by shaking at room temperature 22 ° C. ± 2 and side shaking (3 cm reciprocation 60 times / min). Larvae were introduced at about 100 individuals / test container. However, since the larvae adhere to the pipette when the larvae are put into the test container, they cannot be injected as counted, so about 20 individuals (about 120 individuals in total) are added, and the test seawater is excluded after the test is completed. Was measured. The test period was evaluated at 14 days. Each test substrate was 30 × 30 mm.

[Example 21]
The same glass test piece as in Example 5 was prepared and used. No adhesion was observed during the test period (attachment rate 0%). The appearance of searching the sample surface throughout the test period was not observed, and the appearance of searching the sample cross section to avoid the surface was observed.

[Example 22]
The same glass test piece as in Example 6 was prepared and used. Exploratory behavior was observed for the samples after the start of the test, and 5 (4.4%) young barnacles and 4 (3.5%) metamorphic individuals were observed 3 days after the start of the test. Thereafter, the number of attachments increased, and after 7 days, 74 juvenile barnacles (64.9%) were observed. Further, the adhesion test was extended, and an adhesion rate of 82 individuals (71.9%) was obtained after 14 days.

[Example 23]
The same glass test piece as in Example 8 was prepared and used. One day (0.9%) of young barnacles were observed 3 days after the start of the test, and the number of attachments did not increase thereafter, and after 7 days, the number of attachments remained in the same way. After 14 days, the adhesion to the sample increased by 1 individual, and the adhesion rate was 1.8%.

<Cell adhesion test>
IWAKI dish (24 well plate) coated with resin was sterilized with UV for 15 minutes. Next, cells (TIG3) were seeded at 20,000 cells / well, and 1 mL of medium was added. It was taken out and observed after 16 hours at 37 ° C. in an incubator. As a result, in the resin A, many spherical cells were observed and the cell density was low. On the other hand, in the resin B, it was observed that cells were adhered at a high density. This suggests that resin A has a small interaction with cells.
Further, live cells were stained with CCK8 for quantification, and the absorbance at a wavelength of 450 nm was measured. As a reference, the absorbance of the medium added with CCK8 without cells was also measured. When the value was 1, the rate of increase in absorbance of each cell culture solution was calculated. A higher absorbance increase indicates more cell attachment. Resin A had a small increase rate compared to Resin B. Together with the results of the optical microscope, it was suggested that Resin A is highly effective in suppressing cell adhesion.

The antifouling coating material of the present invention is useful in a wide range of fields such as ships (especially ship bottoms), marine structures, water tanks, outer walls, roofs, building rooftops, cell culture vessels and microchannel surfaces.

In addition, Japanese Patent Application No. 2015-254094 filed on December 25, 2015, Japanese Patent Application No. 2016-088145 filed on April 26, 2016, and Japanese Application filed on April 26, 2016. The entire contents of the specification, claims and abstract of patent application 2016-088454 are hereby incorporated herein by reference as the disclosure of the specification of the present invention.

Claims

A fluoropolymer having a unit having a bioaffinity group, a unit based on a fluoroolefin, and a unit based on one or more selected from the group consisting of vinyl ether, vinyl ester, and allyl ether, and the bioaffinity group Is at least one selected from the group consisting of a group represented by the following formula (1), a group represented by the following formula (2), and a group represented by the following formula (3): .

(In the above formula, n is an integer of 1 to 10, and m is 2 to 100 when the group represented by the formula (1) is contained in the side chain in the fluoropolymer, And R 1 to R 3 each independently represents an alkyl group having 1 to 5 carbon atoms, a is an integer of 1 to 5, and b is an integer of 1 to 5. , R 4 and R 5 are each independently an alkyl group having 1 to 5 carbon atoms, and X − is a group represented by the following formula (3-1) or a group represented by the following formula (3-2): And c is an integer of 1 to 20, and d is an integer of 1 to 5.)
The antifouling coating material according to claim 1, wherein the fluoroolefin is at least one selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, and vinylidene fluoride.
The antifouling coating material according to claim 1 or 2, wherein the unit having a biocompatible group is a unit based on a monomer represented by the following formula (m1).
CH 2 = C (R 11 ) -Q 1- (C n H 2n O) m -R 12 (m1)
(Wherein R 11 is a hydrogen atom, a chlorine atom or a methyl group, Q 1 is a single bond, an etheric oxygen atom or a divalent organic group having 1 to 20 carbon atoms, and R 12 is a hydrogen atom or — (CH 2 ) i —R 13 (wherein R 13 is a hydrogen atom, a fluorine atom, a trifluoromethyl group or a cyano group, i is an integer of 1 to 25), and n is 1 to 10 And m is 1 to 100.)
The antifouling coating material according to any one of claims 1 to 3, wherein the fluoropolymer has a unit based on a monomer having a crosslinkable group.
The antifouling coating material according to claim 4, wherein the crosslinkable group is a hydroxyl group.
The fluoropolymer has 0.1 to 40 mol% of units having bioaffinity groups and 20 to 80 mol% of units based on fluoroolefin, when the entire polymer is 100 mol%. The antifouling coating material according to any one of claims 1 to 5, further comprising 10 to 75 mol% of a unit based on one or more selected from the group consisting of vinyl ether, vinyl ester, and allyl ether.
The antifouling coating material according to any one of claims 1 to 6, which is a marine organism adhesion preventing paint.
The antifouling coating material according to any one of claims 1 to 6, which is an antifungal / algae paint.
The antifouling coating material according to claim 8, comprising an antifungal agent or an algae preventing agent.