JPWO2018047827A1 - Anti-biofouling paint - Google Patents

Abstract

An object of the present invention is to provide an anti-biofouling paint capable of forming a coating excellent in anti-biofouling properties. Another object of the present invention is to provide a vessel or the like having a coating film formed using the above-mentioned anti-biofouling coating on the surface, and an article to be used in a wet or wet environment. The subject of the present invention is also a method of preventing the adhesion of organisms to ships etc. using the above-mentioned anti-biofouling paint, and molds etc. on the surface of articles used in a wet environment or a wet environment. There is also a method of preventing the adhesion of The anti-biofouling paint of the present invention is applied to the surface of an article to prevent bio-adhesion, and is represented by the following formula (h): polymer F, which is a fluoropolymer containing units based on fluoroolefin And Compound H, which is a compound. In the formula (h), A is an n-valent group obtained by removing a hydrogen atom of a hydroxy group from an n-valent polyhydric alcohol, n is an integer of 2 to 12, and B is a formula-(CpH2pO)-or a formula -C (= O) -CqH2qO- (a p is an integer of 2 to 4 and q is an integer of 2 to 8), m is an integer of 0 to 100 (wherein n of m R represents a hydrogen atom or an alkyl group, at least one of which is not 0).

Description

  The present invention relates to anti-biofouling paints, preferably marine anti-biofouling paints applied to the surface of ships, offshore structures or underwater structures, and anti-fungal / algal anti-reflective paints applied to the surface of articles. About.

  In order to impart water repellency to various substrates, paints containing a fluorine-containing polymer are used. As such a fluorine-containing polymer, for example, a fluorine-containing polymer including a unit based on fluoroolefin and a unit based on vinyl ether (cyclohexyl vinyl ether, alkyl vinyl ether, hydroxyalkyl vinyl ether etc.) is disclosed (patented) Reference 1).

Japanese Patent Application Laid-Open No. 57-034107

In recent years, in order to suppress coating film contamination and coating film deterioration due to biological adhesion to a coating film, development of a coating capable of preventing or suppressing biological adhesion (hereinafter, also referred to as "biological adhesion preventing coating") is advanced. There is. Specifically, examples of the anti-biofouling paint include anti-bio-fouling paint and the like for preventing or suppressing the adhesion of sessile organisms such as shellfish on the bottom of marine structures or ships in the sea or ocean. And antifungal / algal paints for preventing or suppressing the adhesion of mold and algae to members used in outdoor buildings and water around hot and humid areas.
The present inventors have found that as a result of producing a coating film on a substrate using a coating containing the fluoropolymer described in the above-mentioned Patent Document 1 as a coating for preventing bio-adhesion, biological adhesion can not be sufficiently suppressed. did.

  Then, this invention makes it a subject to provide the anti-biofouling coating which can form the coating film excellent in bio-adhesion prevention property. The present invention also provides a ship, a structure on water or a structure in water, and an article to be used in a wet or wet environment, having a coating film formed using the anti-biofouling paint as described above. It will be an issue. Further, the present invention provides a method for preventing adhesion of a sessile organism to a ship, a structure on water or a structure under water using the anti-biofouling paint, and a method for use in a wet environment or a wet environment Another object of the present invention is to provide a method for preventing mold or algae from adhering to the surface of the article.

As a result of intensive studies on the above problems, the present inventor obtains desired effects by using a fluorine-containing polymer containing a unit based on fluoroolefin and a compound represented by the formula (h) described later. It has been found that the present invention has been made.
That is, the present inventor has found that the above problem can be solved by the following configuration.

前記式（ｈ）において、Ａはｎ個のヒドロキシ基を有する多価アルコールから該ヒドロキシ基の水素原子を除いたｎ価の基、ｎは２〜１２の整数、Ｂは式−（Ｃ_ｐＨ_２ｐＯ）−または式−（ＣＯ−Ｃ_ｑＨ_２ｑＯ）−で表される２価の基、ｐは２〜４の整数、ｑは２〜８の整数、ｍは０〜１００の整数（ただし、ｎ個のｍのうち少なくとも１つのｍは０でない。）、Ｒは水素原子またはアルキル基を表す。
ただし、ｎ個の−（Ｂ）_ｍ−Ｒは互いに同一でも、異なっていてもよく、−（Ｂ）_ｍ−においてｍが２以上の場合は複数のＢは互いに同一でも、異なっていてもよい。[1] An anti-biofouling paint applied to the surface of an article to prevent bio-fouling,
Polymer F, which is a fluoropolymer containing units based on fluoroolefins;
Compound H, which is a compound represented by the following formula (h):
Anti-biofouling paint characterized by including.

In the formula (h), A is a polyvalent n-valent group from an alcohol excluding the hydrogen atoms of the hydroxy groups with n hydroxy groups, n represents an integer from 2 to 12, B is the formula - (C _p H _{2 p} O) _-or a divalent group represented by the _formula- (CO-C _q H 2 _q O)-, p is an integer of 2 to 4, q is an integer of 2 to 8, and m is an integer of 0 to 100 ( Provided that at least one of n's of m is not 0.), R represents a hydrogen atom or an alkyl group.
However, n-(B) _m -R may be the same as or different from each other, and in-(B) _m- , when m is 2 or more, plural Bs may be the same as or different from each other .

[2] the B has the formula _{- (C p H 2p O)} - is a divalent group represented by the n m is any one or more, anti-biofouling paint [1].
[3] The anti-biofouling paint of [1] or [2], wherein at least one of the n-(B) _m -is a polyoxyalkylene chain containing an oxyethylene group and an oxypropylene group.
[4] The compound H is a poly (oxyethylene-oxypropylene) polyol (however, the arrangement of the oxyethylene group and the oxypropylene group may be random or block), [1] The anti-biofouling paint according to any one of [3] to [3].
[5] The anti-biofouling paint according to any one of [1] to [4], wherein the polymer F further comprises a unit based on a monomer having a hydrophilic polyoxyalkylene chain.
[6] The anti-biofouling paint according to any one of [1] to [5], further comprising water, wherein the polymer F and the compound H are each dispersed in the form of particles.
[7] The anti-biofouling paint according to any one of [1] to [6], wherein the content of the polymer F is 50 to 99% by mass with respect to the total mass of the polymer F and the compound H. .
[8] The organism according to any one of [1] to [7], which is an anti-biofouling paint applied to the surface of a ship, a marine structure or an underwater structure in order to prevent marine organisms from adhering thereto. Adhesion prevention paint.

[9] A ship, structure on water, or structure in water having on the surface a coating film formed using the anti-biofouling paint of any of the above-mentioned [1] to [8].
[10] A coating film of the anti-biofouling paint of any one of [1] to [8] is formed on the surface of a ship, a floating structure or an underwater structure to form a biological material on the ship, a floating structure or an underwater structure. How to prevent the adhesion of
[11] Any one of [1] to [7], which is a paint applied to the surface of an article used in a wet environment or a wet environment to prevent mold or algae from adhering Anti-biofouling paint.
[12] The anti-biofouling paint of [11], further comprising a fungicide or antialgal agent.
[13] An article for use in a wet environment or a wet environment, having on the surface a coating film formed using the anti-biofouling paint of the above [11] or [12].
[14] The coating of the anti-biofouling paint of any of [1] to [7] is formed on the surface of the article used in a wet environment or a wet environment, and the mold or algae adheres to the article How to prevent

ADVANTAGE OF THE INVENTION According to this invention, the biofouling prevention coating which can form the coating film excellent in biofouling prevention property can be provided. In particular, according to the present invention, the adhesion rate of the sessile organism to the coating film is 20% or less of that of the coating film surface, and the adhesion rate of mold and algae is the coating film surface, when immersed in sea for 4 months. It is possible to provide an anti-biofouling paint that is 30% or less.
Further, according to the present invention, a ship, a structure on water or a structure in water, and an article to be used in a wet or wet environment, having a coating film formed using the above-mentioned anti-biofouling paint on the surface Can be provided. Further, according to the present invention, there is provided a method of using the above-mentioned anti-biofouling paint to prevent sticking organisms from adhering to a ship, a floating structure or a submerged structure, and a wet environment or a wet environment. A method can be provided to prevent mold or algae from adhering to the surface of the article used.

The meanings of the terms in the present invention are as follows.
The "unit" is a generic name of an atomic group derived directly from the above monomer, which is directly formed by polymerization of monomers, and an atomic group obtained by chemical conversion of part of the above atomic group. . The content (mol%) of each unit relative to the total units contained in the polymer is determined by analyzing the polymer by nuclear magnetic resonance spectroscopy.
"Number average molecular weight" and "weight average molecular weight" are values measured by gel permeation chromatography using polystyrene as a standard substance. The number average molecular weight is also referred to as "Mn", and the weight average molecular weight is also referred to as "Mw". In addition, the ratio of Mw to Mn represents a molecular weight distribution and is also referred to as "Mw / Mn".
"Average particle diameter" is a value of D50 obtained by dynamic light scattering method using ELS-8000 (manufactured by Otsuka Electronics Co., Ltd.). D50 represents a particle diameter of 50% by volume of cumulative volume calculated from the small particle side in the particle size distribution of particles measured by the dynamic light scattering method.
The “hydroxyl value” is a value measured in accordance with JIS K1557 (2007 edition).

The anti-biofouling coating of the present invention (hereinafter, also referred to as "coating of the present invention") is represented by a polymer F which is a fluoropolymer containing a unit based on fluoroolefin, and a formula (h) described later And a compound H, which is a compound. Here, the compound H has a polyoxyalkylene chain or a polyester chain as shown in the formula (h) described later (“-(B) _m- ” of the formula (h)).
The present inventors have found that the compound H has an effect that biological macromolecules such as proteins and the like do not easily adsorb or adhere, and further, an effect that organisms do not easily adhere. And, it has been found that the above-mentioned effect is remarkably exhibited by the interaction with the polymer F in the present invention.
Although the reason is not necessarily clear, it is considered as follows.

It is said that a sessile organism which adheres to a solid surface in water or a wet environment considers the adherend to be solid and adheres and adheres to the adherent when it is judged to be a suitable living environment. In the coating film formed from the coating material of the present invention (hereinafter, also referred to as "the present coating film"), it is presumed that the compound H exists stably while maintaining a certain distance with respect to the highly hydrophobic polymer F Be done. Therefore, the polyoxyalkylene chain or polyester chain possessed by the compound H is oriented on the coating film surface, and at least a part of the coating film surface is hydrated or swollen by the interaction of the oxyalkylene chain or polyester chain with water. It is thought that Therefore, it is considered that the sessile organism considers the present coating film not to be solid but water, and does not adhere to the present coating film. That is, the present coating film has an anti-biofouling mechanism independent of the anti-biofouling component other than the repellent agent for the sessile organisms and the main component (polymer) of the paint (hereinafter also referred to as the “first action mechanism”). Say). Therefore, the present coating has an excellent first action mechanism over a long period of time.
Thus, the paint of the present invention is suitably used as a biofouling paint to be applied to the surface of ships, floating structures or underwater structures in order to prevent the adhesion of sessile organisms in water or in a water-borne environment. used. In addition, examples of the sessile organisms in water or in a water-immersed environment include, for example, copepods such as barnacles, shellfish such as mussels and oysters, ascidians, bryophyte etc.

In general, the surface of a coating film formed using a coating containing a fluorine-containing polymer is easy to repel water and is excellent in physical properties such as weather resistance, but the water temporarily absorbed by the coating film is accumulated in the coating film. It tends to be easy. Also, the water on the surface of the coating tends to flow through the same path. That is, the surface of the coating film may form an atmosphere in which water or moisture is likely to be accumulated when viewed partially, and may form an environment in which fungi or algae grow.
With respect to such problems, the present inventors have found that the coating film formed from the paint of the present invention itself forms an environment unsuitable for the growth of mold or algae, and the paint of the present invention is It has been found that it has an antifungal and antialgal mechanism (hereinafter also referred to as "second action mechanism") which is not caused by the bactericidal action of an agent (antiseptic) or an antialgal agent. Therefore, the coating film formed from the paint of the present invention has a low environmental load and can exhibit an excellent second action mechanism over a long period of time.
The reason for this is that the coating film is oriented on the surface of the coating film by the interaction with the polymer F, as described above, because the biopolymer such as protein and the compound H having the effect that the cells are not easily adsorbed or adhered, It is thought to create an environment where the growth nutrient source of mold or algae is less likely to adhere. Furthermore, the coating film containing polymer F and compound H has high water resistance (low water vapor permeability) and air shielding properties (low oxygen permeability), and is not suitable for the growth of mold or algae. It is also considered to form Therefore, the present coating film exhibits a second action mechanism even under an environment in which molds and algae easily develop and propagate, such as in a wet environment or a wet environment.
Thus, the paint of the present invention is suitably used as a paint to be applied to the surface of an article to be used in a wet environment or a wet environment in order to prevent mold or algae from adhering.
In the present specification, the first action mechanism and the second action mechanism are collectively referred to simply as "the action mechanism of the present invention".

Furthermore, as described above, the polymer F and the compound H are stably present while maintaining a certain distance as described above, so that the polymer F and the compound H can perform predetermined free movement, and Strongly interact with each other. Therefore, the present coating film is excellent in flexibility, and also excellent in adhesion to an article to which the paint is applied. Therefore, the coating film is resistant to deterioration and abrasion even under severe environmental changes (air exposure, changes in ocean currents, temperature changes, etc.), and has excellent anti-biofouling properties and weatherability over a long period of time.
Thus, the synergistic action of the polymer F and the compound H contained in the paint of the present invention significantly develops the action mechanism of the present invention.

Hereinafter, the polymer F in the present invention will be described in detail.
In addition, a fluoro olefin means the olefin by which 1 or more of hydrogen atoms were substituted by the fluorine atom. In the fluoroolefin, at least one hydrogen atom not substituted by a fluorine atom may be substituted by a chlorine atom.

The polymer F includes units based on fluoroolefin (hereinafter, also referred to as “unit F1”). The polymer F may contain two or more types of units F1.
The _{fluoroolefin, CF 2 = CF 2, CF} 2 = CFCl, preferably CF 2 = CHF and _{CF 2} = CH 2, from the viewpoint of alternating copolymerization with other _monomers, CF ₂ = CF 2 and CF ₂ CFCFCl is more preferred, and CF ₂ CFCFCl is particularly preferred.
20-70 mol% is preferable with respect to the total unit which the polymer F contains, as for content of the unit F, 30-70 mol% is more preferable, and 40-60 mol% is especially preferable. When the content of the unit F1 is 20 mol% or more, the water resistance (particularly, salt water resistance) and the weather resistance of the coating film are more excellent.

The polymer F preferably further contains a unit based on a monomer having a hydrophilic polyoxyalkylene chain (hereinafter, also referred to as “unit F2”). The synergy between the polyoxyalkylene chain of the unit F2 and the compound H more effectively expresses the mechanism of action of the present invention. Further, the compatibility between the polymer F and the compound H in the paint of the present invention is improved, and the adhesion of the present coating film is improved.
The unit F2 is preferably a unit based on a monomer represented by the formula (1) (hereinafter, also referred to as "monomer F2").
Formula (1) XY-(OC _s H _2s ) _t- Z
However, X is a polymerizable group, Y is a divalent linking group, (OC _s H _{2 s} ) _t is a polyoxyalkylene chain, Z is a monovalent end group, s is an integer of 2 to 4, t is 6 or more Represents an integer.

In the polyoxyalkylene chain represented by the _formula- (OC _s H _2s ) _t- , the above-mentioned hydrophilic polyoxyalkylene chain is a polyoxyalkylene chain in which at least a part of the oxyalkylene group is an oxyethylene group. Say.
From the viewpoint that the action mechanism of the present invention is superior, t is preferably 12 or more, and more preferably 15 or more. The upper limit is preferably 40, more preferably 20.
_- (OC s H _2s) - oxyalkylene groups represented by, oxyethylene group and oxypropylene group are preferred.
_When- (OC _s H _{2 s} ) _t -has plural kinds of oxyalkylene groups different from s, the bonding order thereof is not particularly limited, and may be random or block.
The oxyalkylene group in the polyoxyalkylene chain is formed by ring-opening addition polymerization of cyclic ethers such as ethylene oxide, propylene oxide and tetrahydrofuran. Usually, a hydroxy group-containing compound such as monool or diol is used as an initiator, and ring opening addition polymerization of cyclic ether is carried out with this initiator to produce monool or diol having a polyoxyalkylene chain. The monomer F2 is produced by introducing a polymerizable group into this monool or diol. Alternatively, the monomer F2 can be produced by subjecting a monool having a polymerizable group to ring-opening polymerization of cyclic ether.
The hydrophilic polyoxyalkylene chain is a polyoxyethylene chain consisting only of an oxyethylene group or has an oxyethylene group and an oxyalkylene group having 3 or 4 carbon atoms, and the ratio of the oxyethylene group to the total of both The polyoxyalkylene chain which is 50 mol% or more is preferable. In the latter case, a polyoxyalkylene chain having an oxyethylene group and an oxypropylene group and having a ratio of the oxyethylene group to the total of both of 70 mol% or more is preferable. Particularly preferred hydrophilic polyoxyalkylene chains are polyoxyethylene chains consisting only of oxyethylene groups.

As X, a polymerizable unsaturated group forming the main chain of the polymer F is preferable. The _{X, CH 2 = CH-, CH} 2 = CHCH 2 -, CH 3 CH = CH-, CH 2 = C (CH 3) -, CH 2 = CHC (O) O-, CH 2 = C (CH _{3) C (O) O-,} CH 2 = CHO-, and _{CH 2} = CHCH 2 O- are preferable, from the viewpoint of alternating copolymerization with the _{fluoroolefin,} CH 2 = CHO- and _{CH 2} = CHCH 2 O -Is more preferred.

As Y, a C1-C20 bivalent hydrocarbon group is preferable, and a C1-C20 bivalent saturated hydrocarbon group is more preferable. The divalent linking group may be a linear group, a branched group or a group containing a cyclic structure, and the polyoxyalkylene chain is oriented to the surface in the coating film to make the mechanism of the present invention particularly From the viewpoint of effective expression, a group containing a cyclic structure is preferred.
As Z, a hydroxy group, an alkoxy group having 1 to 20 carbon atoms and a phenoxy group are preferable, a hydroxy group, a methoxy group and an ethoxy group are more preferable, and a hydroxy group is particularly preferable from the viewpoint of excellent action mechanism of the present invention.

The compound represented by the following Formula is mentioned as a specific example of monomer F2.
_{CH 2 = CHO-C a H} 2a - (OC s H 2s) t -Z
_{CH 2 = CHCH 2 OC b H} 2b - (OC s H 2s) t -Z
_{CH 2 = CHOCH 2 -cycloC 6 H} 10 -CH 2 - (OC s H 2s) t -Z
_{CH 2 = CHCH 2 OCH 2 -cycloC} 6 H 10 -CH 2 - (OC s H 2s) t -Z
In each formula, a is an integer of 1 to 10 and b is an integer of 1 to 10. The definitions of s, t and Z are as described above. In addition, -cycloC ₆ H ₁₀ -represents a cyclohexylene group, and the bonding site of (-cycloC ₆ H _10- ) includes 1,4-, 1,3- and 1,2-, usually 1 , 4-.
In addition, you may use together 2 or more types of monomers F2.

The content of the unit F2 is preferably 0.4 mol% or more with respect to all units contained in the polymer F, and from the viewpoint that the action mechanism of the present invention is more excellent, the content is preferably 1.5 mol% or more. 0 mol% or more is especially preferable. The upper limit is preferably 15 mol%, more preferably 10 mol%.
According to the study of the present inventors, the polymer F containing a unit in which the end of the hydrophilic polyoxyalkylene chain is a hydroxy group (for example, a unit based on monomer F2 in which Z is a hydroxy group) is hydrophilic Due to the interaction between the polyoxyalkylene chain and the hydroxy group of the polymer and water, the action mechanism of the present invention is excellent even if the content is small. Moreover, if the content is small, it is possible to increase the content of the unit based on the fluoroolefin mentioned above, and a weight which forms a coating film excellent in water resistance (especially, salt water resistance) and weather resistance. The united F can also be prepared.

The polymer F may contain units other than the unit F1 and the unit F2. As this unit, a unit based on a monomer having a cyclic hydrocarbon group (hereinafter, also referred to as “monomer F3”) (hereinafter, also referred to as “unit F3”), a monomer having a crosslinkable group A unit based on (hereinafter also referred to as “monomer F4”) (hereinafter also referred to as “unit F4”) can be mentioned.
In addition, the unit which has a hydrophilic polyoxyalkylene chain and a hydroxyl group corresponds to the unit F2 mentioned above, and does not correspond to "a unit based on the monomer which has a crosslinkable group." The unit F2 may react with a reactive group such as a crosslinking agent to form a crosslinked structure. A unit having a cyclic hydrocarbon group and a hydrophilic polyoxyalkylene chain corresponds to unit F2, and a unit having a cyclic hydrocarbon group and a crosslinkable group corresponds to unit F4.

The cyclic hydrocarbon group of the monomer F3 includes a hydrocarbon group having at least one cyclic structure. 4-20 are preferable and, as for carbon number of a cyclic hydrocarbon group, from a viewpoint of polymerization reactivity, 5-10 are more preferable.
Specific examples of the cyclic hydrocarbon group include monocyclic saturated hydrocarbon groups such as cyclobutyl group, cycloheptyl group and cyclohexyl group, polycyclic saturated hydrocarbon groups such as 4-cyclohexylcyclohexyl group, 1-decahydronaphthyl group And polycyclic saturated hydrocarbon groups such as 2-decahydronaphthyl group, bridged cyclic saturated hydrocarbon groups such as 1-norbornyl group and 1-adamantyl group, and spiro hydrocarbon groups such as spiro [3.4] octyl group Can be mentioned.

Specific examples of the monomer F3 include vinyl ether, allyl ether, alkyl vinyl ester, alkyl allyl ester, acrylate or methacrylate, and a monomer having a cyclic hydrocarbon group, more specifically cyclo And alkyl vinyl ethers such as cyclohexyl vinyl ether.
In addition, you may use together 2 or more types of monomers F3.

When the polymer F contains the unit F3, the water resistance of the coating film is improved.
When the polymer F contains the unit F3, the content of the unit F3 is preferably 0.1 to 45 mol% with respect to all units contained in the polymer F, from the viewpoint that the action mechanism of the present invention is more excellent. -40 mol% is more preferable, 3-35 mol% is further more preferable, and 5-30 mol% is especially preferable.

  The crosslinkable group of the monomer F4 is preferably a functional group having an active hydrogen (hydroxy group, carboxyl group, amino group or the like) or a hydrolyzable silyl group (alkoxysilyl group or the like). When the polymer F has a crosslinkable group, the coating film of the present invention can be cured by including the corresponding crosslinking agent, and the physical properties of the coating (biofouling prevention, weather resistance, water resistance Adjustment of (especially, salt water resistance), adhesion, etc. is further facilitated.

Specific examples of the monomer F4 include hydroxyalkyl vinyl ether, hydroxycycloalkyl vinyl ether, hydroxyalkyl vinyl ester, hydroxycycloalkyl vinyl ester, hydroxyalkyl allyl ether, hydroxyalkyl allyl ester, acrylic acid hydroxyalkyl ester, hydroxyalkyl methacrylate Esters, and more specifically, 2-hydroxyethyl vinyl ether, 4-hydroxymethyl cyclohexyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexane dimethanol monovinyl ether, hydroxyethyl allyl ether, hydroxyethyl acrylate, hydroxyethyl methacrylate Can be mentioned.
Two or more monomers F4 may be used in combination.

  The content of the unit F4 is preferably 0 to 20 mol%, more preferably 0 to 18 mol%, with respect to all units contained in the polymer F, from the viewpoint that the present coating film is excellent in the above-mentioned coating film properties. -15 mol% is particularly preferred.

The polymer F may further contain units other than the unit F1, the unit F2, the unit F3, and the unit F4. As the unit, a unit based on a hydrophilic polyoxyalkylene chain, a fluorine atom, a cyclic hydrocarbon group, and a monomer having no crosslinkable group (hereinafter, also referred to as "monomer F5") (hereinafter referred to as "monomer F5") , "Unit F5".
Specific examples of the monomer F5 include vinyl ethers, allyl ethers, alkyl vinyl esters, alkyl allyl esters, olefins, acrylates or methacrylates, which are hydrophilic polyoxyalkylene chains, fluorine atoms, cyclic hydrocarbon groups, and crosslinks. The monomer which does not have a sex group is mentioned. More specifically, alkyl vinyl ethers (nonyl vinyl ethers, 2-ethylhexyl vinyl ethers, hexyl vinyl ethers, ethyl vinyl ethers, n-butyl vinyl ethers, tert-butyl vinyl ethers, etc.), alkyl allyl ethers (ethyl allyl ethers, hexyl allyl ethers, etc.), carboxylic acids Vinyl esters of acetic acid (butyric acid, butyric acid, pivalic acid, benzoic acid, propionic acid etc.), allyl esters of carboxylic acids (acetic acid, butyric acid, pivalic acid, benzoic acid, propionic acid etc), ethylene, propylene, isobutylene etc. . In addition, the monomer F5 may have a polyoxyalkylene chain other than a hydrophilic polyoxyalkylene chain (for example, a polyoxyalkylene chain that does not contain an oxyethylene group as an oxyalkylene group).
Two or more types of monomers F5 may be used in combination.

  The content of the unit F5 is preferably 0 to 50 mol%, more preferably 5 to 45 mol%, and particularly preferably 15 to 40 mol% with respect to all the units contained in the polymer F.

In the polymer F, the content of the unit F1, the unit F2, the unit F3, the unit F4, and the unit F5 is 20 to 70% by mol and 0.4 to 15 mol respectively in this order with respect to all units contained in the polymer F %, 0 to 45 mol%, 0 to 20 mol%, and 0 to 50 mol% are preferable.
10-70 mass% is preferable, and, as for the fluorine content of the polymer F, 20-50 mass% is especially preferable.
3000-200000 are preferable and, as for Mn of the polymer F, 50000-180000 are more preferable.

In the paint of the present invention, the polymer F may be in the form of powder (solid) or in the form of a solution dissolved in an organic solvent, and a dispersion dispersed in water in the form of particles (aqueous dispersion It may be in the state of liquid), and from the viewpoint of the following physical properties of the coating film, the state of aqueous dispersion is preferable.
In this case, the average particle diameter of the particles of the polymer F in the aqueous dispersion is preferably 200 nm or less. In this case, the present inventors have found that the water resistance of the present coating film is more excellent. The reason is not necessarily clear, but in the coating film, the particles of the polymer F are closely packed, and generation of pinholes in the coating film is suppressed, and as a result, the water resistance of the coating film is improved. Conceivable.

  The average particle diameter of the particles of the polymer F is preferably 200 nm or less, particularly preferably 150 nm or less, from the viewpoint of water resistance of the coating film. The lower limit is usually 50 nm.

  Next, the compound H represented by the following formula (h) in the present invention will be described in detail.

In formula (h), A represents an n-valent group obtained by removing a hydrogen atom of a hydroxy group from a polyhydric alcohol having n hydroxy groups.
n is an integer of 2 to 12, preferably 2 to 10, and more preferably 3 to 5 from the viewpoint of excellent flexibility of the present coating film.
Specific examples of polyhydric alcohols include dihydric alcohols (ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-cyclohexanediol, 1,3-butanediol, 1,4-butanediol) Butanediol, 1,6-Hexanediol, 1,4-Cyclohexanediol etc., Polyhydric alcohol having 3 or more valences (glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol) Etc.).
Of the n m's, a part of m may be 0, in which case R is a hydrogen atom. That is, part of n-(B) _m -R may be a hydrogen atom constituting a hydroxy group, in which case the hydroxy group is a hydroxy group of polyhydric alcohol. In the usual preparation method of compound H, except when all _m of n-(B) _m -R is a very small numerical value, the hydroxy group of polyhydric alcohol hardly remains, and n m of All is usually one or more.

B is the formula _{- (C p H 2p O)} - or the formula _{- (CO-C q H 2q} O) - is a divalent group represented by, - _{(B) m} - is _- (C _{p H 2p} O ) _m - polyoxyalkylene chain or represented by - represents a polyester chain represented by _{- (CO-C q H 2q} O) m. However, when m is 2 or more, - _{(B) m} - is _{- (C p H 2p O)} - and _{- (CO-C q H 2q} O) - of it may be a chain having two groups .
_{Incidentally, - (C p H 2p O} ) m - bond terminal carbon atom is bound to A, bond the terminal oxygen atom is bonded to R. _{Similarly, - (CO-C q H} 2q O) m - bond of the terminal carbonyl group is attached to A, bond the terminal oxygen atom is bonded to R.
m is an integer of 0 to 100, and n pieces of m may be different from each other. As mentioned above, each m is preferably 1 or more. From the viewpoint of the action mechanism of the present invention, each m is preferably 2 to 75, and more preferably 20 to 70.

The n-(B) _m -may be the same as or different from each other. For example, - _{(B) m} - is _{- (C p H 2p O)} m - when is, each - _{(B) m} - m is not slightly different less. Also, - _{(B) m} - is 2 or more _{- (C p H 2p O)} - if the film is made of, each - _{(B) m} - in, p is different from _{- (C p H 2p O)} - percentage of It may be different.

In formula (h), R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom.
When R is an alkyl group, the number of carbon atoms is preferably 1 to 5, and more preferably 1 to 3.
The n R's may be the same as or different from each other, and preferably at least a portion is a hydrogen atom, and more preferably all are a hydrogen atom. That is, the compound H is preferably a compound having at least one hydroxy group, and more preferably a compound having n hydroxy groups.

B has the formula _{- (C p H 2p O)} - when it is a group represented by, that an oxyalkylene group, B is an oxyalkylene group having 2 to 4 carbon atoms. As the oxyalkylene group, an oxyethylene group, an oxypropylene group, an oxy-1,2-butylene group, an oxy-2,3-butylene group and an oxytetramethylene group are preferable, and an oxyethylene group and an oxypropylene group are particularly preferable.
When-(B) _m -has two or more oxyalkylene groups, the arrangement of the different oxyalkylene groups may be random or block, and both of the random part and the block part You may have.
The oxyethylene group is a hydrophilic group, and the other oxyalkylene groups are hydrophobic groups as compared to the oxyethylene group. Therefore, in order to adjust the hydrophilicity and the hydrophobicity of the polyoxyalkylene chain, it is preferable to make the polyoxyalkylene chain having an oxyethylene group and an oxyalkylene group having 3 or more carbon atoms, and to adjust the ratio of both. The oxyalkylene group having 3 or more carbon atoms is preferably an oxypropylene group.

The content of the oxyalkylene group having 3 or more carbon atoms in the compound H is preferably 5 mol% or more, more preferably 10 mol% or more, and more than 50 mol%, based on the total moles of the oxyalkylene groups contained in the compound H. Particularly preferred. Moreover, 90 mol% or less of the said content is preferable.
When the content of the oxyalkylene group having 3 or more carbon atoms is 5 mol% or more, repelling of the paint is suppressed when the paint of the present invention is applied to an article, and a smooth coating film can be obtained.
The content of the oxyalkylene group can be calculated based on the amount of the compound (for example, an alkylene oxide described later) used to introduce the oxyalkylene group.
1-90 mol% is preferable among the total moles of the oxyalkylene group which comprises the compound H, and, as for content of the oxyethylene group in the compound H, 5 mol% or more and less than 50 mol% are more preferable. Moreover, 1-50 mass% is preferable among the total mass of the compound H, and, as for content of the oxyethylene group in the compound H, 5-30 mass% is more preferable. When the content of the oxyethylene group is 50% by mass or less, when the paint of the present invention is applied to an article, repelling of the paint is suppressed, and a smooth coating film is obtained. When the content of the oxyethylene group is 1% by mass or more, the action mechanism of the present invention is more effectively expressed.

B has the formula _{- (CO-C q H 2q} O) - is a group represented by, B is a group formed from group or hydroxy carboxylic acids formed by opening of the lactone. q is an integer of 2 to 8, preferably 3 to 6.
_{- (CO-C q H 2q} O) m - represents a polyester chain, a hydrophilic / hydrophobic polyester chain can be adjusted by numeric q. It is also possible to adjust the ratio of q different two or more _{(CO-C q H 2q O} ) different adjustments and q numbers of q polyester chain comprising _{(CO-C q H 2q O} ). sequence of q different two or more _{(CO-C q H 2q O} ) may be a random form, or may be a block form.

Furthermore, - _{(B) m} - _{is, - (C p H 2p O} ) - and _{- (CO-C q H 2q} O) - and it may be a chain comprising. For example, a relatively hydrophobic _{- (CO-C q H 2q} O) - and the oxyethylene group by adjusting the proportion of both chains containing a portion of the interaction of the polymer F and the compound H Can be adjusted to adjust the hydrophilicity of the surface of the present coating.
Compound H is - with a chain having, which chain _{- - (CO-C q H} 2q O) (C p H 2p O) - preferably having the oxyethylene group, an oxypropylene group or their both It is preferable to have.
- _{(B) m} - _{is, - (C p H 2p O} ) - and - if it contains a, both sum for the _{- - (CO-C q H} 2q O) (CO-C q H 2q O) - of The proportion is preferably 5 to 95 mol%, more preferably 40 to 60 mol%.

  The compound H is preferably a compound having a hydroxy group as described above, in which case the hydroxyl value of the compound H is 5 to 150 mg KOH / g from the viewpoint of suitably controlling the hydrophilicity of the surface of the present coating film. Preferably, 5 to 120 mg KOH / g is more preferable, and 5 to 100 mg KOH / g is particularly preferable.

The method for producing the compound H is not particularly limited, and specific examples thereof include a method in which cyclic ether and lactone are subjected to ring-opening addition polymerization to a polyhydric alcohol having 2 to 12 hydroxy groups.
Specific examples of the polyhydric alcohol having 2 to 12 hydroxy groups are as described above, and thus the description thereof is omitted.
The cyclic ether capable of forming an oxyalkylene group includes alkylene oxide and tetrahydrofuran.
Specific examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide, with ethylene oxide and propylene oxide being preferred. When two or more alkylene oxides are used, the ring-opening addition polymerization may be any of random polymerization, block polymerization, or a combination of random polymerization and block polymerization.
Specific examples of lactones include β-propiolactone, δ-valerolactone, ε-caprolactone, methyl-ε-caprolactone, α-methyl-β-propiolactone, β-methyl-β-propiolactone, methoxy- ε-caprolactone and ethoxy-ε-caprolactone can be mentioned, with ε-caprolactone being preferred. When two or more lactones are used, the ring-opening addition polymerization may be any of random polymerization, block polymerization, or a combination of random polymerization and block polymerization.
Further, a chain having an oxyalkylene group and an ester-containing group is, for example, a method of ring-opening addition polymerization of alkylene oxide with polyhydric alcohol followed by ring-opening addition polymerization of lactone, ring-opening addition polymerization of lactone with polyhydric alcohol And the ring-opening addition polymerization of the alkylene oxide, and the like.

  As for Mn of the compound H, 2000-20000 are preferable, as for Mw / Mn of the compound H, 1.40 or less is preferable and 1.10 or less is especially preferable.

In the paint of the present invention, the compound H may be in the form of powder (solid) or in the form of a solution dissolved in an organic solvent, and a dispersion dispersed in water in the form of particles (aqueous dispersion Or the like, and preferably in the form of an aqueous dispersion. The method for dispersing Compound H in water in the form of particles is not particularly limited, and Compound H may be dispersed by a known dispersing method.
In this case, the average particle diameter of the particles of compound H in the aqueous dispersion is preferably 200 nm or less, more preferably 150 m or less, still more preferably 80 nm or less, particularly 70 nm or less, in that the water resistance of the coating is more excellent. preferable. The lower limit is not particularly limited, but is usually 50 nm.

  In the paint of the present invention, the content of the polymer F is preferably 50 to 99% by mass with respect to the total mass of the polymer F and the compound H. Thereby, the action mechanism of the present invention is more effectively expressed.

  The method for producing the paint of the present invention is not particularly limited, and it can be produced by mixing the polymer F and the compound H. For example, the aqueous dispersion containing the polymer F and the aqueous dispersion containing the compound H are mixed Can be manufactured.

The form of the paint of the present invention is preferably in the form of a dispersion in which the particles of the polymer F and the particles of the compound H are each dispersed in water, as described above. That is, the paint of the present invention preferably further comprises water, and the polymer F and the compound H are preferably dispersed in the form of particles, respectively. Hereinafter, the paint of the present invention in such a state is also referred to as "the water-based paint of the present invention".
30-85 mass% is preferable with respect to the total mass of the water-based paint of this invention, as for content of the water in the water-based paint of this invention, 35-75 mass% is more preferable.

As described above, the polymer F is preferably a polymer having a crosslinkable group such as a hydroxy group, and the compound H is preferably a compound in which at least a part of R is a hydrogen atom. Preferably, at least one of H has a hydroxy group. In particular, it is particularly preferable that both the polymer F and the compound H in the paint of the present invention have a hydroxy group.
When at least one of the polymer F and the compound H in the paint of the present invention has a hydroxyl group, the paint of the present invention preferably contains a crosslinking agent having two or more reactive groups that react with a hydroxyl group. As the crosslinking agent, a compound having two or more of an isocyanate group, a blocked isocyanate group, an epoxy group and the like is preferable. In particular, when the paint of the present invention is an aqueous paint, it contains a water-dispersed isocyanate curing agent (a blocked polyisocyanate having two or more blocked isocyanate groups and capable of being dispersed in water) as a crosslinking agent. Is preferred.
When the paint of the present invention contains a crosslinking agent, the content of the crosslinking agent in the paint is preferably 0.1 to 30% by mass, based on the total mass of the polymer F and the compound H in the paint, % By mass is more preferable, and 5 to 15% by mass is particularly preferable.

The paint of the present invention may contain other additives (eg, fungicides, algaecides, coalescents, thickeners, antifoaming agents, light stabilizers, design agents, surface conditioners, etc.) as required. ) May be included.
The paint of the present invention expresses the antifungal and antialgal mechanism by Compound H itself as described above, but may further contain an antifungal agent or an antialgal agent from the viewpoint of further enhancing the effect.
Antifungal agents or antialgal agents include known antifungal agents or antialgal agents, and from the viewpoint of compatibility with polymer F and compound H, an agent containing a compound containing a halogen atom as an active ingredient is employed May be Also, in the case of using a polymer F containing a chlorine atom (for example, a polymer F in which the fluoroolefin is CF ₂ CFCFCl), an agent containing a compound having a chlorine atom, a bromine atom or an iodine atom as an active ingredient May be adopted.
The content of the antifungal agent or antialgal agent in the paint is preferably 0.01 to 5% by mass with respect to the total mass of the polymer F and the compound H in the paint, respectively.

According to the present invention, there is provided a ship, a floating structure or an underwater structure having a coating film formed using the paint of the present invention on the surface. The paint of the present invention is particularly suitable as an anti-biofouling paint for applying to the surface under contact with sea water or an environment which may come into contact with sea water in ships, sea structures or subsea structures traveling on the sea There is.
No particular limitation is imposed on the application object ship, floating structure or underwater structure, as long as it is used in the ocean, lake, river, and their vicinity, etc., and it is a bridge, fishing net, wave dissipating block, Breakwaters, submarine cables, tanks, pipelines, subsea drilling equipment, floats, power plant intakes / outlets, power plant distribution pipes (cooling water piping), ship hulls (especially the bottom and draft section), ships Screws, boat traps and the like can be mentioned. Moreover, the material of the said target object is not specifically limited, either, A metal, resin, rubber | gum, a stone material, glass, and concrete may be sufficient.
Further, the shape and state (contact state with water) of the object are also not particularly limited.
For example, a seawater pipe (cooling water pipe) of a seaside power plant, which is an object having a bent shape in the pipe shape and in which the flow velocity and temperature of seawater in the pipe can be largely changed, is formed using the paint of the present invention By providing the coating film on the inner surface of the pipe, the marine organism adhesion preventing function and the corrosion resistance are exhibited over a long period of time.
The film thickness of the formed coating film is preferably 10 to 100 μm. When the film thickness of the coating film is 10 μm or more, the saltwater resistance of the coating film is more excellent, and when it is 100 μm or less, the weather resistance of the coating film is more excellent.

The present coating film may be formed on the outermost surface exposed to the aqueous atmosphere of the object. That is, the paint of the present invention may be applied directly to the surface of an object, or may be applied to the outermost surface through a subbing layer.
Moreover, as a coating method of the coating material to a target object, the method of using a coating apparatus, such as a brush, a roller, dipping, a spray, a roll coater, a die coater, an applicator, a spin coater, etc. is mentioned.
The ship, floating structure or underwater structure of the present invention has on the surface a coating formed of the polymer of the present invention and containing the polymer F as a main component. Therefore, it is not only difficult for sticking organisms to adhere over a long period of time, but is excellent in anticorrosion property, so that it can be used for a long period of time. The coating film may contain a cross-linked structure in which the polymers F are cross-linked, a cross-linked structure in which the polymers F and H are cross-linked, or a cross-linked structure in which the compounds H are cross-linked. Well, multiple types of the structure may be included.

  As described above, in the present invention, the coating film of the paint containing the polymer F and the compound H is formed on the surface of the ship, the floating structure or the underwater structure to form the ship, the floating structure or the underwater structure. It is also possible to provide a method for preventing adhesion of the sessile organism to an object.

According to the present invention, an article having a coating of the present invention on the surface and used in a wet environment or a wet environment is provided. In the present specification, the wet environment means an environment with a humidity of 40% or more, and the wet environment means an environment in which water is constantly in contact or sometimes in contact with water.
Specific examples of the articles used in a wet environment or a wet environment include a bathtub, ceiling panel, wall panel, floor pan, door, water faucet, drainage unit, ventilation fan, mirror, sink, toilet bowl, low tank, hand wash bowl Etc., and underground structures such as water pipes and drainage pipes, and outdoor structures such as water reservoirs and buildings. Specific examples of the material of the article include metal, resin, rubber, stone, glass, and concrete.
The film thickness of the coating film of the article is preferably 10 to 100 μm. If the film thickness of a coating film is 10 micrometers or more, the water resistance of a coating film will be more excellent, and if it is 100 micrometers or less, the weather resistance of a coating film will be more excellent.

The present coating film may be formed on the outermost surface of an article exposed to a wet environment or a wet environment. That is, the paint of the present invention may be applied directly to the surface of the article, or may be applied to the outermost surface through the undercoat layer.
Moreover, as a coating method of the coating material to a target object, the method of using a coating apparatus, such as a brush, a roller, dipping, a spray, a roll coater, a die coater, an applicator, a spin coater, etc. is mentioned.
It should be noted that even if the article on which the coating film is disposed is an article in a light-shielded environment such as the outer wall of a building with a bad sun contact north face or west face, the inner surface of a water tank, a water pipe, or a sewage pipe, According to the action mechanism of the paint of the invention, an article having a coating on the surface is excellent in long-term antifungal and antialgal properties, and has a feature of low environmental impact. The coating film may contain a cross-linked structure in which the polymers F are cross-linked, a cross-linked structure in which the polymers F and H are cross-linked, or a cross-linked structure in which the compounds H are cross-linked. Well, multiple types of the structure may be included.

  As described above, the present invention can also provide a method of forming a coating film of a paint containing polymer F and compound H on the surface of an article to prevent adhesion of mold or algae to the article.

  Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited to these examples. In addition, the compounding quantity of each component in the table | surface mentioned later shows a mass reference | standard.

<Production of Polymer F>
CTFE: CF ₂ = CFCl
_{CM-EOVE: CH 2 = CHOCH} 2 -cycloC 6 H 10 -CH 2 - (OCH 2 CH 2) 15 OH ( average molecular weight 830. However, -cycloC ₆ H ₁₀ - is a 1,4-cyclohexylene group. ).
CHVE: cyclohexyl vinyl ether CHMVE: 4-hydroxymethyl cyclohexyl methyl vinyl ether EVE: ethyl vinyl ether 2-EHVE: 2-ethylhexyl vinyl ether nonionic surfactant: Nippon Emulsifier Co., Ltd. Newcol-2320 (trade name)
Anionic surfactant: manufactured by Nikko Chemicals, sodium lauryl sulfate

Preparation Example 1 Method of Producing Polymer F-1 CTFE (434 g), CHVE (259 g), EVE (107 g), CM-EOVE (124 g), ion-exchanged water (1031 g), in a vacuum degassed autoclave, Potassium carbonate (2.1 g), ammonium persulfate (1.0 g) and an anionic surfactant (2.1 g) were charged, and a polymerization reaction was performed at 60 ° C. for 24 hours while stirring. After the polymerization reaction, the reaction solution was cooled to 60 ° C. to 20 ° C. to obtain an aqueous dispersion (containing 49.7% by mass of a fluoropolymer) containing a fluoropolymer. Hereinafter, the obtained fluoropolymer is referred to as "polymer F-1".
The content of the unit based on CTFE, the unit based on CM-EOVE, the unit based on CHVE, and the unit based on EVE in the polymer F-1 is 50 mol%, 2.0 mol%, 28 mol%, in this order. It was 20 mol%. In the aqueous dispersion, Polymer F-1 was dispersed in the form of particles, and the average particle size in water was 80 nm.

Preparation Example 2 Production Method of Polymer F-2 CTFE (664 g) ion-exchanged water (1280 g), EVE (185 g), CHVE (244 g), CM-EOVE (47 g), CHMVE in a vacuum degassed autoclave (194 g), potassium carbonate (2.0 g), ammonium persulfate (1.3 g), nonionic surfactant (33 g), anionic surfactant (1.4 g) are charged and stirred at 50 ° C. for 24 hours The polymerization reaction was carried out. After the polymerization reaction, the reaction solution was cooled to 50 ° C. to 20 ° C. to obtain an aqueous dispersion (50% by mass of fluoropolymer) containing a fluoropolymer. Hereinafter, the obtained fluoropolymer is referred to as "polymer F-2".
In the polymer F-2, the content of a unit based on CTFE, a unit based on CM-EOVE, a unit based on CHVE, a unit based on CHMVE, a unit based on EVE is 50 mol%, 0.5 mol%, 17 mol %, 10 mol%, 22.5 mol%. In the aqueous dispersion, the polymer F-2 was dispersed in the form of particles, and the average particle size in water was 140 nm.

Preparation Example 3 Production Method of Polymer F-3 CTFE (580 g) ion-exchanged water (1280 g), CHVE (443.4 g), 2-EHVE (230 g), potassium carbonate (3 g) in a vacuum degassed autoclave .0 g), ammonium persulfate (5.4 g), nonionic emulsifier (33 g) and anionic emulsifier (1.4 g) were charged, and a polymerization reaction was carried out under stirring at 50 ° C for 24 hours. After the polymerization reaction, the pressure resistant reactor was water-cooled to stop the reaction. After the polymerization reaction, the reaction solution was cooled to 50 ° C. to 20 ° C. to obtain an aqueous dispersion (50% by mass of fluoropolymer) containing a fluoropolymer. Hereinafter, the obtained fluoropolymer is referred to as "polymer F-2".
The unit based on CTFE, the unit based on CHVE, and the unit based on 2-EHVE in the polymer F-3 were 50 mol%, 35.25 mol% and 14.75 mol%. In the aqueous dispersion, the polymer F-3 was dispersed in the form of particles, and the average particle size in water was 240 nm.

  The compositions of the polymers F-1 to F-3 are shown in Table 1.

<Compound H>
Compound H-1: poly (ethylene oxide) obtained by ring-opening addition polymerization of propylene oxide to glycerin and then ring-opening addition polymerization of ethylene oxide; poly (Mn) 10000; polyoxyethylene content 12 mass%, hydroxyl value 16.5 mg KOH / g (Oxypropylene-oxyethylene) triol. In addition, it has about 50 oxypropylene groups and about 9 oxyethylene groups on average per molecule.
Compound H-2: obtained by ring-opening addition polymerization of propylene oxide to dipropylene glycol and then ring-opening addition polymerization of ethylene oxide, Mn 4000, content of oxyethylene group 8 mass%, hydroxyl value 27.0 mg KOH / g Poly (oxypropylene-oxyethylene) diol. In addition, it has about 31 oxypropylene group and about 4 oxyethylene group on average per molecule.
Compound H-3: ring-opening addition polymerization of propylene oxide to dipropylene glycol, followed by ring-opening addition polymerization of ethylene oxide, Mn 4000, content of oxyethylene group 24 mass%, hydroxyl value 28.0 mg KOH / g Poly (oxypropylene-oxyethylene) diol. In addition, it has an average of about 26 oxypropylene groups and about 11 oxyethylene groups per molecule.

<Production of anti-biofouling paint>
Production Example 1
The dispersion containing the polymer F-1 (solid content concentration 49.7% by mass) (100.0 g) obtained in Preparation Example 1 was added with 2,2,4-trimethyl-1,3 as a film forming aid -Pentadiol mono (2-methylpropanate) (7.5 g), Reoate 288 (trade name) as thickener (manufactured by Elemententis Japan Ltd.) (0.1 g), water-dispersed isocyanate curing as a crosslinking agent An agent (manufactured by Sumika Bayer Co., Ltd., Baihidur 3100 (trade name)) (5.4 g) and compound H-1 (4.8 g) were added and thoroughly mixed to obtain a biofouling preventive coating 1. In the paint, the polymer F-1 and the compound H-1 were both dispersed in the form of particles.
Moreover, except having used the component shown in Table 2 mentioned later, it carried out similarly to manufacture example 1, and obtained the biofouling preventing paints 2-6. In each paint, the polymer F and the compound H were all dispersed in the form of particles. The antialgal agent in Example 4 is Biocut-N 35 (trade name) manufactured by Nippon Soda Co., Ltd.

<Evaluation of anti-biofouling property A>
The test plate was produced in the following procedures.
An epoxy resin paint (made by China Paint Co., Ltd .; product name "SEAJET 013 main agent" and product name "SEAJET 013 Curing agent" mixed at a mass ratio of 4: 1) on both sides of the aluminum base, the dry film thickness Was brushed to 60 μm and dried at ambient temperature for 1 week. Next, the anti-biofouling paint 1 is coated on one surface of an aluminum base with an applicator, dried at normal temperature for 2 weeks, and the fluorine-containing polymer 1 and the polyether 1 are used as constituents on the surface of the base. The test board 1 which has a coating film (dry film thickness of 30 micrometers) was produced. Test plates 2 to 6 were prepared in the same manner as for the anti-biofouling coatings 2 to 6.
Each of the obtained test plates 1 to 6 was immersed in water (water depth 1 m), and the adhesion state of the barnacles and shellfish after 4 months was visually observed. In addition, the submersion place in the sea was Seto Inland Sea, and the test board was installed so that the coating film side turned south at the time of the submergence in the sea.
The evaluation criteria are as follows, and the results of the evaluation A of anti-biofouling properties (underwater immersion test) are shown in Table 2.
○: There was no adhesion of barnacles or shellfish on the surface of the coating.
Fair: Adhesion of barnacles and shellfish was observed in an area of 0% or more and 20% or less of the coating film surface.
X: Adhesion of barnacles and shellfish was observed in an area of more than 20% of the coating film surface.

<Evaluation B of anti-biofouling properties>
With respect to the test plates 1 to 6 prepared in the evaluation A for preventing the adhesion of organisms, generation of algae on the coating film surface was confirmed by the agar medium method according to JIS Z 2911. The types of algae used are the genus Chlorella and the genus Oscillatoria. The evaluation criteria are as follows, and the results of the evaluation B of anti-biofouling properties (algal development test) are shown in Table 2.
◎: There was no adhesion of algae to the coating film surface.
○: Adhesion of algae was observed in the area of more than 0% and 10% or less of the coating film surface.
Δ: Adhesion of algae was observed in an area of 10% or more and 30% or less of the coating film surface.
X: Adhesion of algae was observed in an area of more than 30% of the coating film surface.

<Evaluation of anti-biofouling property C>
The paint obtained in Production Example 1 was coated on the surface of a glass plate by an applicator so as to have a dry film thickness of 40 μm, and dried at 25 ° C. for 2 weeks to obtain a coated glass plate.
The coated film was peeled off from the coated glass plate and cut into 70 mm × 10 mm to obtain coated film pieces, which were subjected to the evaluation described later.
First, a point of 10 mm was fixed in the center direction from the ends of the two short sides of the coating film pieces. Subsequently, breaking elongation (%) at the time of applying tensile load to a coating piece at 50 mm / min at -20 degreeC from each point was measured. For measurement, ORIEnTEC TENSILON RTC-1310A (manufactured by Orientec Co., Ltd.) was used. The evaluation criteria are as follows, and the results of the evaluation C (the flexibility of the coating film) for preventing the biofouling are shown in Table 2.
○: Elongation at break of coating film pieces was 60% or more.
B: Elongation at break of the coated film piece was 20% or more and less than 60%.
X: Elongation at break of coating film piece was less than 20%.

  The results of the above evaluation tests are shown in Table 2. Examples 1 to 5 are Examples, and Example 6 is a Comparative Example.

As shown in the evaluation results of Table 2, it was shown that, by using a paint containing the polymer F and the compound H, it is possible to form a coating film excellent in anti-biofouling properties.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2016-173426 filed on Sep. 06, 2016 are incorporated herein by reference and incorporated as disclosure of the specification of the present invention. It is.

Claims (14)

An anti-biofouling paint applied to the surface of an article to prevent bio-fouling,
Polymer F, which is a fluoropolymer containing units based on fluoroolefins;
Compound H, which is a compound represented by the following formula (h):
Anti-biofouling paint characterized by including.

In the formula (h), A is a polyvalent n-valent group from an alcohol excluding the hydrogen atoms of the hydroxy groups with n hydroxy groups, n represents an integer from 2 to 12, B is the formula - (C _p H _{2 p} O) _-or a divalent group represented by the _formula- (CO-C _q H 2 _q O)-, p is an integer of 2 to 4, q is an integer of 2 to 8, and m is an integer of 0 to 100 ( Provided that at least one of n's of m is not 0.), R represents a hydrogen atom or an alkyl group.
However, n-(B) _m -R may be the same as or different from each other, and in-(B) _m- , when m is 2 or more, plural Bs may be the same as or different from each other . Wherein B has the formula _{- (C p H 2p O)} - is a divalent group represented by the n m is any one or more, anti-biofouling paint according to claim 1. The anti-biofouling paint according to claim 1 or 2, wherein at least one of the n-(B) _m -is a polyoxyalkylene chain containing an oxyethylene group and an oxypropylene group.   The compound H is a poly (oxyethylene-oxypropylene) polyol (however, the arrangement of the oxyethylene group and the oxypropylene group may be random or block). The anti-biofouling paint according to any one of the above.   The anti-biofouling paint according to any one of claims 1 to 4, wherein the polymer F further comprises a unit based on a monomer having a hydrophilic polyoxyalkylene chain.   The anti-biofouling paint according to any one of claims 1 to 5, further comprising water, wherein the polymer F and the compound H are each dispersed in the form of particles.   The anti-biofouling paint according to any one of claims 1 to 6, wherein the content of the polymer F is 50 to 99% by mass with respect to the total mass of the polymer F and the compound H.   The biofouling according to any one of claims 1 to 7, which is a marine anti-biofouling coating applied to the surface of a ship, a marine structure or an underwater structure in order to prevent marine organisms from adhering thereto. Prevention paint.   A ship, a floating structure or an underwater structure having a coating film formed using the anti-biofouling paint according to any one of claims 1 to 8 on its surface.   A coating of the anti-biofouling paint according to any one of claims 1 to 8 is formed on the surface of a ship, a floating structure or an underwater structure, and organisms are formed on the ship, the floating structure or the underwater structure. How to prevent it from sticking   The organism according to any one of claims 1 to 7, which is a paint applied to the surface of an article used in a wet environment or a wet environment to prevent mold or algae from adhering. Adhesion prevention paint.   The anti-biofouling paint according to claim 11, further comprising an antifungal agent or an antialgal agent.   An article for use in a wet environment or a wet environment, having a coating film formed using the anti-biofouling paint according to claim 11 or 12 on the surface.   A mold or algae adheres to an article by forming a coating of the anti-biofouling paint according to any one of claims 1 to 7 on the surface of an article used in a wet environment or a wet environment. How to prevent that.