JP6720956B2 - Substrate and its application - Google Patents

Description

The present invention relates to a substrate and its use. In particular, the present invention makes it difficult for organisms, proteins, lipids and other biomolecules to adhere to each other via a medium containing water, and to prevent organic dirt, inorganic substances, etc. floating in a medium containing water from adhering or accumulating. The present invention relates to a base material and its use.

Cells and organisms, as well as proteins, lipids and other biomolecules, contain water-containing medium (seawater
BACKGROUND ART Substrates that are difficult to adhere via fresh water, rainwater, biological water, etc., and to which organic dirt, inorganic substances, etc. floating in a medium containing water are not easily attached or deposited are used for various purposes. For example, cell culture equipment, medical bags (infusion bags, liquid medicine bags, etc.), ship bottoms and water circulation equipment (prevention of adhesion of contaminated organisms such as barnacles), food manufacturing equipment, various filters, tableware and water products, medical or health care. It is used in a wide range of applications such as micro liquid channels used in the field of care.

Conventionally, it has been proposed that a substrate having a high contact angle in water with respect to water should be used as a substrate used for these applications (Non-Patent Document 1).

Y. Tamada et al., 1 person, Polymer, 1993, 34, pp. 2208-2212

The present inventors may not be able to sufficiently suppress the adhesion of organisms and biomolecules through a medium containing water even in the case of a substrate having a surface having a high contact angle with water in air. Found. Therefore, an object of the present invention is to provide a substrate capable of sufficiently suppressing the adhesion of organisms and biomolecules through a medium containing water.

The present inventors have earnestly studied toward the solution of the above-mentioned problems, and unlike the theory that has been conventionally proposed, if the surface has a high contact angle in water with respect to water, a living organism and a medium through a medium containing water and It was found that the adhesion of biomolecules can be sufficiently suppressed.

The present invention has been completed by further trial and error based on such findings, and includes the following embodiments.
Item 1.
A substrate containing (A) a support; and (B) a surface layer,
The surface layer (B) is disposed on at least a part of the surface of the support (A) directly or via one or more other layers,
A substrate having a contact angle in water at 20° C. of the surface of the surface layer (B) of 80° or more.
Item 2.
Item 2. The substrate according to Item 1, wherein the surface layer (B) contains a fluorine-containing compound.
Item 3.
Item 3. The substrate according to Item 2, wherein the surface layer (B) is a layer surface-modified with a fluorine-containing compound.
Item 4.
Item 3. The substrate according to Item 2, wherein the surface layer (B) is a layer that has been plasma-treated using a fluorine-containing gas.
Item 5.
Item 3. The substrate according to Item 2, wherein the fluorine-containing compound is a fluorine-containing polymer.
Item 6.
The fluoropolymer is a fluoro(meth)acrylate-based polymer or fluoro(meth)
Item 6. The substrate according to Item 5, which is at least one fluoropolymer having a softening point of 0° C. or higher selected from the group consisting of an acrylamide polymer and an olefin fluoropolymer.
Item 7.
Item 7. The substrate according to any one of Items 1 to 6, wherein the surface layer (B) is bonded to a surface serving as a base via a chemical bond.
Item 8.
Item 8. The substrate according to any one of Items 1 to 7, which is an aquatic organism adhesion preventing material.
Item 9.
Item 10. A composition capable of forming the surface layer (B), which is used for producing the substrate according to any one of Items 1 to 7.
Item 10.
Item 8. The composition according to Item 7, which contains a fluorine-containing compound.
Item 11.
A surface treating agent which can make the contact angle of the treated surface in water at 20° C. 80° or more.
Item 12.
Item 12. The surface treatment agent according to Item 11, which is applied to a surface having a contact angle in water at 20°C of less than 80°.
Item 13.
Item 13. The surface treatment agent according to item 11 or 12, which contains a fluorine-containing compound.
Item 14.
Item 14. The surface treatment agent according to any one of items 11 to 13, which is an aquatic organism adhesion preventing paint.
Item 15.
Item 10. A method for treating a surface to be treated, which comprises a step of applying the composition according to Item 9 to the surface to be treated.
Item 16.
Item 7. An underwater structure having the substrate according to any one of items 1 to 7 in at least a part thereof.
Item 17.
Item 15. A method for preventing adhesion of aquatic organisms to an underwater structure, which comprises a step of applying the surface treatment agent according to any one of items 11 to 14 to the surface of the underwater structure.

According to the present invention, the adhesion of organisms and biomolecules via a medium containing water can be sufficiently suppressed on the surface of a substrate.

1. Substrate The substrate of the present invention is
A substrate containing (A) a support; and (B) a surface layer,
The surface layer (B) is disposed on at least a part of the surface of the support (A) directly or via one or more other layers,
The base material has a contact angle in water at 20° C. of the surface of the surface layer (B) of 80° or more.

At the boundary between the two layers in the present invention, the composition of the two layers may change critically or may change in a gradient.

The base material of the present invention has a surface layer having a contact angle in water at 20° C. of 80° or more, so that organisms and proteins, lipids and other biomolecules adhere to each other via a medium containing water. In addition, it is difficult for organic substances (for example, organic pollutants) and inorganic substances floating in a medium containing water to adhere or accumulate. More specifically, since the surface layer (B) has a predetermined underwater contact angle, an object is more likely to pass through a medium containing water as compared with a surface having no such underwater contact angle. It is difficult to bond. Thus, the substrate of the present invention can be used in any application where it can be advantageous to suppress the adhesion of objects through a medium containing water.

Therefore, in the above, the organism is an organism having the property of adhering to the surface of an object through a medium containing water (herein, referred to as "adhesive aquatic organism"), and is not particularly limited. For example, the following items are listed.

Barnacles, sea squirts, serpas, blue mussels, mussels, hemlock worms, sea anemones, sea lions, sea anemones, aquatic organisms such as oysters and hydro worms, various aquatic microorganisms, various seaweeds (midorige, hondawara, aosa and aonori, etc.), cyanobacteria, green algae (Amamidoro and Azalea), Euglena, Yellow-green algae, Golden-colored algae, Diatoms, Red algae, Crypto-algae, Flame-colored algae, Mosses (tea moss, etc.), Ring-shaped animals (Uzumakigokai and Shiritekai, etc.) Animals (Yuzudama sponge etc.) etc.

In the above, the organic matter (for example, organic pollutant) is not particularly limited as long as it has a property of adhering to the surface of an object through a medium containing water, and for example, floating oil (mineral oil, vegetable oil, etc.), waste Examples include foods, resins, human waste, and carcasses of living things.

In the above, the inorganic substance is not particularly limited as long as it has a property of adhering to the surface of an object through a medium containing water, and is not particularly limited, for example, debris (fine sand and mud, etc.), khaki and insoluble components of hot springs. (Yu no Hana) and so on.

The substrate of the present invention can be used for various applications including underwater structures and articles used in contact with water, and materials and members thereof (parts for assembling the structure). Although not particularly limited, examples of the underwater structures and articles include various ones including those used in or in contact with sea water or fresh water. Moreover, the base material of the present invention may be used on the surface of water. Specific applications of the substrate of the present invention include, for example, the following articles and structures, but are not limited to these.

Further, the material and the member are not particularly limited, but may have a shape such as a panel, for example.

The structure is composed of a plurality of materials and/or members and includes a building. Buildings include not only fixed structures such as piers, piers and waterways, but also mobile structures such as megafloats and ships.

<Examples of specific uses of the substrate of the present invention>
Underwater structures such as bridges, concrete blocks, wave-dissipating blocks, breakwaters and pipelines.

Port facilities such as sluice gates, offshore tanks and floating piers.

Submarine work facilities such as undersea drilling facilities and undersea communication cable facilities.

Ocean temperature difference power generation facilities using thermal power, nuclear power, tidal power, etc. (In particular, headraces, water pipes, water chambers, water intakes, water discharge ports, etc. of these facilities).
Water supply and drainage and storage facilities such as pools, water tanks, water towers, sewers and gutters.

Household equipment such as system kitchen, flush toilet, bathroom and bathtub.

Ship structures or accessories (for example, the waterfalls and bottoms of ships, as well as the exterior, screws, propellers and anchors of submarines).

Float materials such as seaplanes.

Fishing nets such as fixed nets and bottom nets, and fishing products such as long lines, buoys, cages and ropes.

Articles for ocean temperature difference power generation using thermal power, nuclear power, offshore wind power, etc. (for example, water cover and water chamber).

Undersea (underwater) laying items such as undersea (underwater) cables.

Various filters.

(A) Support The support can be appropriately selected depending on the purpose of use and the like, and is not particularly limited, but resin,
In addition to glass, ceramics, metals, etc., building materials such as slate, etc. can be mentioned.

Although not particularly limited, it is preferable that at least the surface thereof contains a material capable of forming a reaction initiation point by irradiation with radiation, and a surface layer (B) chemically bonded to the surface of the support is formed by surface graft polymerization or crosslinking reaction. can do. In this case, the support may contain a material capable of forming a reaction initiation point only on the surface thereof, or may entirely contain such a material.

The material that can form the reaction starting point is not particularly limited, and examples thereof include resin and glass. Specifically, polyimide; vinyl chloride; EVA (Ethylene-vinyl)
polystyrene; polystyrene (foam styrene etc.); polyester (polyethylene terephthalate etc.); polyolefin (low density polyethylene, medium density polyethylene, high density polyethylene and polypropylene etc.); cycloolefin; polyurethane; urethane acrylate; acrylic resin (polymethylmethacrylate) Etc.); Polyamide (Nylon (
(Registered trademark) and the like); polycarbonate; cellulose; and natural rubber having a conjugated bond, synthetic rubber having a conjugated bond, silicone rubber, and the like. The material may be a blend polymer or polymer alloy containing two or more of these.

Further, by plasma processing using carbon tetrafluoride or the like (atmospheric pressure plasma or the like), the surface layer (B) chemically bonded to the surface of the support can be formed as in the case of the radiation irradiation.
In this case, in addition to the same material as used for the radiation irradiation, it can be applied to metals such as stainless steel, aluminum and copper.

The surface shape of the support may be smooth or uneven. In addition, the support may be surface-treated or may further have another layer on the surface, as long as the effects of the present invention are not impaired.

When the substrate of the present invention is an aquatic organism adhesion-preventing material, the support (A) is not particularly limited, but examples thereof include various plastics such as polyimide, polycarbonate, polyethylene terephthalate, vinyl chloride and acrylic resin, metal, In addition, building materials such as slate can be used.

(B) Surface Layer The surface layer (B) is arranged on at least a part of the surface of the support (A) directly or via one or more other layers.

The surface layer (B) is not particularly limited, and for example, the surface layer (B) has at least 50 of the surface of the support (A).
%, directly or via one or more other layers, or at least 60% of the surface of the support (A) directly or via one or more other layers. May be.

The surface layer (B) has a surface contact angle in water at 20° C. of 80° or more. By having a surface having such properties, the substrate of the present invention can sufficiently suppress the adhesion of organisms and biomolecules through a medium containing water. In this respect, the surface layer (B) preferably has a surface contact angle in water at 20° C. of 80° or more, more preferably 90° or more. The underwater contact angle of the support (A) is usually less than 80°.

In the present invention, the contact angle in water is specifically measured as follows.
<Measurement>
The measurement sample is fixed in water and allowed to stand for 30 minutes or more on a hot plate set so that the water temperature is adjusted to 20° C. to bring it into an equilibrium state. Air bubbles (about 10
a few drops of L) on the surface of the measurement sample, and the contact angle of the bubbles is measured by DropMaster.
701 (made by Kyowa Interface Science) or its equivalent is used for the measurement. The contact angle of water measured in water, that is, the contact angle in water is
Formula: 180°-(air bubble contact angle)
Calculate from

The surface layer (B) may be a layer surface-modified with a fluorine-containing compound. In this case, the surface layer (B) means the surface-modified surface portion of the support, or the outermost surface layer of the support when other layers are present between the support and the surface layer (B). Refers to.
Examples of the fluorine-containing compound used in the surface modification include at least one fluorine-containing compound selected from the group consisting of fluorine gas, fluorine-containing gas and fluorine-containing polymer. The fluorine-containing gas is not particularly limited, but examples thereof include tetrafluoromethane, trifluoromethane, octafluorocyclobutane, hexafluoropropylene oxide and the like. Of these, fluorine-containing gas is particularly preferable because it is industrially easy to handle.
The surface modification method is not particularly limited, and can be appropriately selected depending on the fluorine-containing compound used, the type of the layer to be surface-treated, and the like. Although not particularly limited, examples thereof include plasma treatment, electron beam irradiation treatment, and gamma ray irradiation treatment. Among these, plasma treatment is particularly preferable in terms of high industrial versatility.

The surface layer (B) may be a layer containing a fluorine-containing compound, as an embodiment different from the above-mentioned surface modification. That is, in this case, the surface layer (B) is provided as a layer different from the layer below it.

The surface layer (B) only needs to have a surface contact angle in water at 20° C. of 80° or more, and the material thereof is not particularly limited. Specifically, for example, a fluorine-containing compound, an alkylsilyl group-containing Examples thereof include compounds and compounds containing a long-chain alkyl group having 16 or more carbon atoms.

The fluorine-containing compound is not particularly limited, and examples thereof include acrylic acid compounds, acrylate compounds, acrylamide compounds, olefin compounds, styrene compounds, acrylonitrile compounds, vinylpyrrolidone compounds, vinyl ether compounds and pyrrole compounds. And the like in which at least one hydrogen atom is replaced by a fluorine atom.

In the above, the acrylic acid compound is not particularly limited, but examples thereof include acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, maleic acid, fumaric acid, crotonic acid and the like.

In the above, the acrylate compound is not particularly limited, but for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-
Examples include α,β-ethylenically unsaturated carboxylic acid esters such as propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, lauryl acrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate and behenyl methacrylate.

In the above, the acrylamide compound is not particularly limited, and examples thereof include octyl acrylamide and stearyl acrylamide.

Further, as the acrylate-based compound and the acrylamide-based compound, for example, a fluoroalkyl group having an ester bond or an amide bond to a carboxyl group directly or via a divalent organic group, and having a substituent at the α-position Examples thereof include acrylic acid ester (hereinafter sometimes abbreviated as "fluoroalkyl group-containing acrylic acid ester"), acrylamide (hereinafter sometimes abbreviated as "fluoroalkyl group-containing acrylamide"), and the like.

Specific preferred examples of the fluoroalkyl group-containing acrylic acid ester or the fluoroalkyl group-containing acrylamide include:
Formula _{(1): CH 2 = C} (-X) -C (= O) -Y-Z-Rf
[In the formula, X represents a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (provided that X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.), a cyano group, and a carbon number of 1 to 2.
1 is a linear or branched fluoroalkyl group, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group;
Y is -O- or -NH-;
Z is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms or a cycloaliphatic group,
^{_{-CH 2 CH 2 N (R 1}} ) SO 2 - group (wherein, ^{R 1} is an alkyl group having 1 to 4 carbon atoms.
^{_{), - CH 2 CH (OZ}} 1) CH 2 - group (wherein, ^{Z 1} is a hydrogen atom or an acetyl group.
_{), - (CH 2) m} -SO 2 - (CH 2) n - _{group, - (CH 2) m -S-} (CH 2) n -
Group (. M is from 1 to 10, and n is 0), or _{- (CH} 2) m -COO- group (m is from 1 to 10.); And
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms, which may have a hetero atom. ]
An acrylic ester or acrylamide represented by

In the general formula (1), the fluoroalkyl group represented by Rf is an alkyl group which may have a hetero atom, in which at least one hydrogen atom is substituted with a fluorine atom,
It also includes a perfluoroalkyl group which may have a hetero atom, in which all hydrogen atoms are replaced by fluorine atoms. Further, examples of the fluoroalkyl group having a hetero atom represented by Rf include a perfluoropolyether group and the like.

In the acrylic ester or acrylamide represented by the above general formula (1), Rf
Is preferably a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, and particularly,
It is preferably a linear or branched perfluoroalkyl group having 1 to 3 carbon atoms. In recent years, the EPA (US Environmental Protection Agency) has pointed out that a compound having a fluoroalkyl group having a carbon number of 8 or more is a compound having a high environmental load which may decompose and accumulate in the environment or in the living body. However, when Rf is a linear or branched fluoroalkyl group having 1 to 6 carbon atoms in the acrylic ester or acrylamide represented by the general formula (1), such an environmental problem is pointed out. Because not.

In the above formula (1), examples of the Rf _{group, -CF 3, -CF 2 CF 3} , -CF 2 CF 2 H, -CF 2 CF 2 CF
₃ , -CF ₂ CFHCF ₃ , -CF(CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF(CF ₃ ) ₂ , -C(CF ₃ ) ₃ , -(CF ₂ ) ₄ CF
_{3, - (CF 2) 2} CF (CF 3) 2, -CF 2 C (CF 3) 3, -CF (CF 3) CF 2 CF 2 CF 3, - (CF 2) 5 CF 3, - (CF ₂ ) ₃ CF(C
F ₃ ) _{2 and the} like.

Further, as the Rf group, a fluoroalkyl group having 1 to 2 carbon atoms, a fluoroalkyl group having 2 to 3 carbon atoms in which one fluorine atom is replaced by a hydrogen atom, or two or more carbon atoms interposed by a hetero atom 1 to 3 fluoroalkyl groups are preferred. As a specific example, C ₃ F ₇ OCF(
_{CF 3) CF 2 OCF (CF} 3) -, (CF 3) 2 NC n F 2n - , and the like (n = 1~6).

Specific examples of the acrylic ester or acrylamide represented by the general formula (1) are as follows:
It is as follows.

CH ₂ =C(−H)−C(=O)−O−(CH ₂ ) ₂ −Rf
CH ₂ =C(−H)−C(=O)−O−C ₆ H ₄ −Rf
CH ₂ =C(−Cl)−C(=O)−O−(CH ₂ ) ₂ −Rf
CH ₂ =C(−H)−C(=O)−O−(CH ₂ ) ₂ N(−CH ₃ )SO ₂ −Rf
CH ₂ =C(−H)−C(=O)−O−(CH ₂ ) ₂ N(−C ₂ H ₅ )SO ₂ −Rf
CH ₂ =C(−H)−C(=O)−O−CH ₂ CH(−OH)CH ₂ −Rf
CH ₂ =C(−H)−C(=O)−O−CH ₂ CH(−OCOCH ₃ )CH ₂ −Rf
CH ₂ =C(−H)−C(=O)−O−(CH ₂ ) ₂ −S−Rf
CH ₂ =C(−H)−C(=O)−O−(CH ₂ ) ₂ −S−(CH ₂ ) ₂ −Rf
CH ₂ =C(−H)−C(=O)−O−(CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ =C(−H)−C(=O)−O−(CH ₂ ) ₂ −SO ₂ −(CH ₂ ) ₂ −Rf
CH ₂ =C(−H)−C(=O)−NH−(CH ₂ ) ₂ −Rf
CH ₂ =C(−CH ₃ )−C(=O)−O−(CH ₂ ) ₂ −Rf
CH ₂ =C(−CH ₃ )−C(=O)−O−C ₆ H ₄ −Rf
CH ₂ =C(−CH ₃ )−C(=O)−O−(CH ₂ ) ₂ N(−CH ₃ )SO ₂ −Rf
CH ₂ =C(−CH ₃ )−C(=O)−O−(CH ₂ ) ₂ N(−C ₂ H ₅ )SO ₂ −Rf
CH ₂ =C(−CH ₃ )−C(=O)−O−CH ₂ CH(−OH)CH ₂ −Rf
CH ₂ =C(−CH ₃ )−C(=O)−O−CH ₂ CH(−OCOCH ₃ )CH ₂ −Rf

CH ₂ =C(−CH ₃ )−C(=O)−O−(CH ₂ ) ₂ −S−Rf
CH ₂ =C(−CH ₃ )−C(=O)−O−(CH ₂ ) ₂ −S−(CH ₂ ) ₂ −Rf
CH ₂ =C(−CH ₃ )−C(=O)−O−(CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ =C(−CH ₃ )−C(=O)−O−(CH ₂ ) ₂ −SO ₂ −(CH ₂ ) ₂ −Rf
CH ₂ =C(−CH ₃ )−C(=O)−NH−(CH ₂ ) ₂ −Rf
CH ₂ =C(−F)−C(=O)−O−(CH ₂ ) ₂ −S−Rf
CH ₂ =C(−F)−C(=O)−O−(CH ₂ ) ₂ −S−(CH ₂ ) ₂ −Rf
CH ₂ =C(−F)−C(=O)−O−(CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ =C(−F)−C(=O)−O−(CH ₂ ) ₂ −SO ₂ −(CH ₂ ) ₂ −Rf
CH ₂ =C(−F)−C(=O)−NH−(CH ₂ ) ₂ −Rf
CH ₂ =C(−Cl)−C(=O)−O−(CH ₂ ) ₂ −S−Rf
CH ₂ =C(−Cl)−C(=O)−O−(CH ₂ ) ₂ −S−(CH ₂ ) ₂ −Rf
CH ₂ =C(−Cl)−C(=O)−O−(CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ =C(−Cl)−C(=O)−O−(CH ₂ ) ₂ −SO ₂ −(CH ₂ ) ₂ −Rf

CH ₂ =C(−Cl)−C(=O)−NH−(CH ₂ ) ₂ −Rf
CH ₂ =C(−CF ₃ )−C(=O)−O−(CH ₂ ) ₂ −S−Rf
CH ₂ =C(−CF ₃ )−C(=O)−O−(CH ₂ ) ₂ −S−(CH ₂ ) ₂ −Rf
CH ₂ =C(−CF ₃ )−C(=O)−O−(CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ =C(−CF ₃ )−C(=O)−O−(CH ₂ ) ₂ −SO ₂ −(CH ₂ ) ₂ −Rf
CH ₂ =C(−CF ₃ )−C(=O)−NH−(CH ₂ ) ₂ −Rf
CH ₂ =C(−CF ₂ H)−C(=O)−O−(CH ₂ ) ₂ −S−Rf
_{CH 2 = C (-CF 2 H} ) -C (= O) -O- (CH 2) 2 -S- (CH 2) 2 -Rf
_{CH 2 = C (-CF 2 H} ) -C (= O) -O- (CH 2) 2 -SO 2 -Rf
CH ₂ =C(−CF ₂ H)−C(=O)−O−(CH ₂ ) ₂ −SO ₂ −(CH ₂ ) ₂ −Rf
_{CH 2 = C (-CF 2 H} ) -C (= O) -NH- (CH 2) 2 -Rf

CH ₂ =C(−CN)−C(=O)−O−(CH ₂ ) ₂ −S−Rf
CH ₂ =C(−CN)−C(=O)−O−(CH ₂ ) ₂ −S−(CH ₂ ) ₂ −Rf
CH ₂ =C(−CN)−C(=O)−O−(CH ₂ ) ₂ −SO ₂ −Rf
CH ₂ =C(−CN)−C(=O)−O−(CH ₂ ) ₂ −SO ₂ −(CH ₂ ) ₂ −Rf
CH ₂ =C(−CN)−C(=O)−NH−(CH ₂ ) ₂ −Rf
CH ₂ =C(−CF ₂ CF ₃ )−C(=O)−O−(CH ₂ ) ₂ −S−Rf
_{CH 2 = C (-CF 2 CF} 3) -C (= O) -O- (CH 2) 2 -S- (CH 2) 2 -Rf
CH ₂ =C(−CF ₂ CF ₃ )−C(=O)−O−(CH ₂ ) ₂ −SO ₂ −Rf
_{CH 2 = C (-CF 2 CF} 3) -C (= O) -O- (CH 2) 2 -SO 2 - (CH 2) 2 -Rf
CH ₂ =C(−CF ₂ CF ₃ )−C(=O)−NH−(CH ₂ ) ₂ −Rf
CH ₂ =C(−F)−C(=O)−O−(CH ₂ ) ₃ −S−Rf
CH ₂ =C(−F)−C(=O)−O−(CH ₂ ) ₃ −S−(CH ₂ ) ₂ −Rf
CH ₂ =C(−F)−C(=O)−O−(CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ =C(−F)−C(=O)−O−(CH ₂ ) ₃ −SO ₂ −(CH ₂ ) ₂ −Rf
CH ₂ =C(−F)−C(=O)−NH−(CH ₂ ) ₃ −Rf

CH ₂ =C(−Cl)−C(=O)−O−(CH ₂ ) ₃ −S−Rf
CH ₂ =C(−Cl)−C(=O)−O−(CH ₂ ) ₃ −S−(CH ₂ ) ₂ −Rf
CH ₂ =C(−Cl)−C(=O)−O−(CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ =C(−Cl)−C(=O)−O−(CH ₂ ) ₃ −SO ₂ −(CH ₂ ) ₂ −Rf
CH ₂ =C(−CF ₃ )−C(=O)−O−(CH ₂ ) ₃ −S−Rf
CH ₂ =C(−CF ₃ )−C(=O)−O−(CH ₂ ) ₃ −S−(CH ₂ ) ₂ −Rf
CH ₂ =C(−CF ₃ )−C(=O)−O−(CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ =C(−CF ₃ )−C(=O)−O−(CH ₂ ) ₃ −SO ₂ −(CH ₂ ) ₂ −Rf
CH ₂ =C(−CF ₂ H)−C(=O)−O−(CH ₂ ) ₃ −S−Rf
_{CH 2 = C (-CF 2 H} ) -C (= O) -O- (CH 2) 3 -S- (CH 2) 2 -Rf
_{CH 2 = C (-CF 2 H} ) -C (= O) -O- (CH 2) 3 -SO 2 -Rf
CH ₂ =C(−CF ₂ H)−C(=O)−O−(CH ₂ ) ₃ −SO ₂ −(CH ₂ ) ₂ −Rf
CH ₂ =C(−CN)−C(=O)−O−(CH ₂ ) ₃ −S−Rf
CH ₂ =C(−CN)−C(=O)−O−(CH ₂ ) ₃ −S−(CH ₂ ) ₂ −Rf
CH ₂ =C(−CN)−C(=O)−O−(CH ₂ ) ₃ −SO ₂ −Rf
CH ₂ =C(−CN)−C(=O)−O−(CH ₂ ) ₃ −SO ₂ −(CH ₂ ) ₂ −Rf
CH ₂ =C(−CF ₂ CF ₃ )−C(=O)−O−(CH ₂ ) ₃ −S−Rf
CH ₂ =C(−CF ₂ CF ₃ )−C(=O)−O−(CH ₂ ) ₃ −S−(CH ₂ ) ₂ −Rf
CH ₂ =C(−CF ₂ CF ₃ )−C(=O)−O−(CH ₂ ) ₃ −SO ₂ −Rf
_{CH 2 = C (-CF 2 CF} 3) -C (= O) -O- (CH 2) 2 -SO 2 - (CH 2) 2 -Rf
[In the above formula, Rf is a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. ]

C ₃ F ₇ OCF(CF ₃ )CF ₂ O-CF(CF ₃ )CH ₂ -MAc
C ₃ F ₇ OCF(CF ₃ )CF ₂ O-CF(CF ₃ )CH ₂ -Ac
(CF ₃ ) ₂ CH-Ac
C ₂ F ₅ CH ₂ -MAc
C ₂ F ₅ CH ₂ -Ac
CF ₃ CH ₂ -MAc
CF ₃ CH ₂ -Ac
CF ₃ CHFCF ₂ CH ₂ -MAc
CF ₃ CHFCF ₂ CH ₂ -Ac
[In the above formula, Ac represents acrylate and MAc represents methacrylate, respectively.
]

The above-mentioned fluoroalkyl group-containing acrylic ester or acrylamide can be used alone or in combination of two or more.

In the above, the olefin compound is not particularly limited, but examples thereof include alkenes and alkyl vinyl ethers. The alkene is not particularly limited, and examples thereof include ethylene and propylene. The alkene is not particularly limited, but specific examples thereof include tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride. The alkyl vinyl ether is not particularly limited, and has, for example, 1 to 1 carbon atoms.
An alkyl vinyl ether having an alkyl group of 6, preferably having 1 to 3 carbon atoms can be mentioned. The alkyl vinyl ether may be a perfluoroalkyl vinyl ether. Specific examples of the perfluoroalkyl vinyl ether are not particularly limited, and examples thereof include perfluoropropyl vinyl ether and the like.

The above-mentioned olefin compounds can be used alone or in combination of two or more.

In the above, the styrene compound is not particularly limited, but examples thereof include styrene and alkylstyrene. The above-mentioned styrene compounds can be used alone or in combination of two or more.

In the above, the acrylonitrile compound is not particularly limited, and examples thereof include acrylonitrile. The acrylonitrile compounds described above can be used alone or in combination of two or more.

In the above, the vinylpyrrolidone compound is not particularly limited, and examples thereof include vinylpyrrolidone. The above vinylpyrrolidone compounds can be used alone or in combination of two or more.

In the above, the vinyl ether compound is not particularly limited, but examples thereof include alkyl vinyl ethers such as ethyl vinyl ether and butyl vinyl ether. The above vinyl ether compounds can be used alone or in combination of two or more.

In the above, the pyrrole compound is not particularly limited, and examples thereof include pyrrole. The above-mentioned pyrrole compounds can be used alone or in combination of two or more.

The surface layer (B) may contain the above-mentioned fluorine-containing compound as one kind alone or as a mixture of two or more kinds. Further, the surface layer (B) may contain a fluorine-containing polymer obtained by (co)polymerizing one kind of the above-mentioned fluorine-containing compound or two or more kinds.

The weight average molecular weight of the fluoropolymer is not particularly limited, but from the viewpoint of the effect of the present invention, it is preferably 1,000 or more, more preferably 5,000 to 2,000,000.
And more preferably 10,000 to 2,000,000. The weight average molecular weight can be determined by gel permeation chromatography (GPC).

The above-mentioned fluoropolymer is not particularly limited, but examples thereof include fluoro(meth)acrylate-based polymers, fluoro(meth)acrylamide-based polymers, and olefin-based fluoropolymers.

The fluoro(meth)acrylate-based polymer and the fluoro(meth)acrylamide-based polymer are polymers containing at least a structural unit based on fluoro(meth)acrylate and fluoro(meth)acrylamide, respectively. As the fluoro(meth)acrylate and the fluoro(meth)acrylamide, those mentioned above can be used.

The olefin-based fluoropolymer means a fluoropolymer that may contain a structural unit based on a polymerized olefin monomer and a structural unit based on at least one other comonomer. In the above, the olefin-based fluoropolymer preferably contains a structural unit based on a polymerized olefin monomer corresponding to a majority of the polymer based on the weight of the polymer.

In the above, the fluorine atom may be contained only in the constitutional unit based on the polymerized olefin monomer, may be contained only in the constitutional unit based on the other comonomer, or may be contained in both of them. Good. At least one of the constituent units may be one in which all hydrogen atoms are replaced by fluorine atoms, or both constituent units may be one in which all hydrogen atoms are replaced by fluorine atoms. .. In the above, in the other structural units, a part of hydrogen atoms may be replaced with a fluorine atom, or a hydrogen atom may not be replaced with a fluorine atom at all.

In the above, the polymerized olefin monomer is not particularly limited, and examples thereof include alkenes and alkyl vinyl ethers. The alkene is not particularly limited, and examples thereof include ethylene and propylene. The alkene may have at least a part of hydrogen atoms replaced with fluorine atoms and is not particularly limited, and specific examples thereof include tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride. The alkyl vinyl ether is not particularly limited, and examples thereof include an alkyl vinyl ether having an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. The alkyl vinyl ether may be a perfluoroalkyl vinyl ether. Specific examples of the perfluoroalkyl vinyl ether are not particularly limited, and examples thereof include perfluoropropyl vinyl ether and the like.

Although not particularly limited, specific examples of the olefin-containing fluoropolymer include, for example, polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer. (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), vinylidene fluoride-tetrafluoroethylene copolymer, and the like. These may be used alone or in combination.

In the above, the fluoropolymer preferably has a softening point of 0° C. or higher and a softening point of 2
It is more preferably 0° C. or higher. Although not particularly limited to the theory, when a fluoro(meth)acrylate-based polymer is used as an example, a polymer having a softening point of 0° C. or higher is R in water.
Since the reorientation of the f group (hydrophobic) and the carbonyl group (hydrophilic) is unlikely to occur, it is considered that the hydrophobicity is easily maintained. In this case, preferred specific examples include fluoro(meth)acrylate-based polymers and fluoro(meth)acrylamide-based polymers. The fluoro(meth)acrylate-based polymer is a polymer containing at least a structural unit based on fluoro(meth)acrylate. The fluoro(meth)acrylamide-based polymer is a polymer containing at least a structural unit based on fluoro(meth)acrylamide. Polymers containing constitutional units based on fluoro(meth)acrylate and fluoro(meth)acrylamide, respectively, can also be used.
More specific examples include, but are not limited to, those having a structural unit based on the fluoroalkyl group-containing acrylic acid ester and/or the fluoroalkyl group-containing acrylamide.

For example, when the softening point is less than 0° C., Rf is a perfluoropolyether group even if it has a structural unit based on the fluoroalkyl group-containing acrylic acid ester and/or the fluoroalkyl group-containing acrylamide. Therefore, a copolymer having a softening point of 0° C. or higher is preferably used.

In the present invention, the softening point is measured as follows.
<Measurement>
The softening point is the glass transition point (Tg) or melting point (Tm). These are 2 n when a polymer powder of 10 mg is measured by DSC822e [manufactured by Mettler Toledo, USA] or its equivalent under the conditions of temperature range of -50 to 150°C and temperature rising rate of 10°C/min.
From the thermogram at the d-th cycle, the extrapolated glass transition end temperature (JIS K7121-19
87) is the read value.

The alkylsilyl group-containing compound is not particularly limited, but examples thereof include silicone oil and (meth)acryl-modified polydimethylsiloxane.

The long-chain alkyl group-containing compound having 16 or more carbon atoms is not particularly limited, but, for example,
Examples include α,β-ethylenically unsaturated carboxylic acid esters such as stearyl acrylate, stearyl methacrylate, behenyl acrylate, and behenyl methacrylate.

The surface layer (B) may be arranged on the surface to be the base by physical adsorption, or may be bonded via a chemical bond. The surface layer (B) is preferably bonded to the underlying surface via a chemical bond in that the effect of suppressing the adhesion of organisms and biomolecules can be maintained for a long period of time.

Although not particularly limited, for example, by performing electron beam irradiation (EB), γ-ray irradiation, ultraviolet irradiation, plasma treatment, corona treatment, or the like, the surface layer (B) is fixed to the underlying surface through a chemical bond. May be.

From the viewpoint of the effect of the present invention, the thickness of the surface layer (B) is preferably 0.1 to 2,000 μm, more preferably 1 to 500 μm, and further preferably 5 to 100 μm. .. The film thickness is a value obtained by measurement according to the method of JIS K5600.

(C) Other Layers Other layers are not particularly limited, and examples thereof include a support reinforcing layer, a primer layer, and a radiation modification auxiliary layer.

The support reinforcing layer is a layer that mechanically or chemically reinforces the support. Specifically, it is used when the mechanical strength of the support is low, or when the support is chemically corroded by the influence of the solvent and/or the monomer used in forming the surface layer. For example, the mechanical strength can be improved by laminating a polyethylene terephthalate film having a thickness of 250 μm on a polyethylene film having a thickness of 10 μm. Further, by sticking the FEP film on the polystyrene base material, chemical corrosion of the solvent and/or the monomer can be prevented.

The primer layer is a layer for improving the adhesion between the support (A) and the surface layer (B),
Although not particularly limited, examples thereof include a double-sided tape for sticking an FEP film on the above-mentioned polystyrene substrate.

The radiation modification auxiliary layer is used when the support (A) is made of a material, such as polystyrene, in which radicals are not easily generated when irradiated with radiation. For example, by sticking a polyethylene film as a radiation modification auxiliary layer on the surface of a polystyrene device, a large amount of radicals are generated when irradiated with radiation, and it is possible to easily perform graft polymerization.

2. Manufacturing Method of Base Material Although not particularly limited, the base material can be obtained by applying to the surface of the base material a surface-treating agent capable of making the contact angle of the treated surface in water at 20° C. 80° or more.

More specifically,
(1) a step of dissolving the above-mentioned components such as a fluorine-containing compound in a solvent; and (2) applying the solution obtained in (1) above to a surface serving as a base, and further subjecting these to polymerization or crosslinking reaction. The substrate of the present invention can be obtained by a method including the step of

In the step (1), as the component such as the above-mentioned fluorine-containing compound, one kind of the above-mentioned monomers or a mixture of two or more kinds, or one kind of polymer or two or more kinds of copolymers, or A mixture of two or more of these can be used. The solvent for dissolving the above-mentioned fluorine-containing compound and the like is not particularly limited, but for example, a solvent having a boiling point of 120° C. or less under normal pressure, particularly 60 to 110° C. is preferable. As a specific example, a solvent having a fluorine atom in the molecule and having good solubility of the fluorine-containing polymer may be any of a fluorocarbon compound, an alcohol, an ether, etc., and an aliphatic or aromatic compound. It may be of any family. For example, perfluoro aliphatic hydrocarbon, polyfluoro aromatic hydrocarbon, polyfluoro aliphatic hydrocarbon,
Hydrofluorocarbon (HFC), Hydrochlorofluorocarbon (HCFC),
Examples thereof include hydrofluoroether (HFE), hydrofluoroolefin (HFO) and alkyl perfluoroalkyl ether.

The perfluoroaliphatic hydrocarbon is not particularly limited, but preferably has 5 to 12 carbon atoms. Specific examples thereof include, but are not limited to, perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, and perfluorodihydropropanol (pentafluoropropanol).

The polyfluoroaromatic hydrocarbon is not particularly limited, and examples thereof include bis(trifluoromethyl)benzene and hexafluoro-m-xylene.

The polyfluoroaliphatic hydrocarbon is not particularly limited, and examples thereof include C ₆ F ₁₃ CH.
₂ CH ₃ [for example, Asahi Klin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.]
, 1,2,2,3,3,4-heptafluorocyclopentane [for example, Zeorora (registered trademark) H manufactured by Nippon Zeon Co., Ltd.].

The hydrofluorocarbon (HFC) is not particularly limited, but for example, 1,1
, 1,3,3-pentafluorobutane (HFC-365mfc) and the like.

Hydrochlorofluorocarbon (HCFC) is not particularly limited, but preferably has 2 to 5 carbon atoms. Specific examples include, but are not limited to, HCFC-225 [dichloropentafluoropropane:asahiclin (registered trademark) AK225], HCFC141b(
Dichlorofluoroethane), CFC316 (2,2,3,3 tetrachlorohexafluorobutane) and _C 5 _H 2 _{F 10} [e.g., DuPont Vertrel (TM) XF
] Etc. are mentioned.

The hydrofluoroether (HFE) is not particularly limited, but for example, perfluoropropyl methyl ether (C ₃ F ₇ OCH ₃ ) [for example, Novec (trademark) 7000 manufactured by Sumitomo 3M Limited] and CF ₃ CH ₂ OCF ₂ CHF ₂ [for example, Asahi Klin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.] and the like can be mentioned.

The hydrofluoroolefin (HFO) is not particularly limited, but for example, 1,
2-dichloro-1,3,3,3-tetrafluoro-1-propene [eg, Bertrel (registered trademark) Scion manufactured by Mitsui DuPont Fluorochemicals] and the like can be mentioned.

In the alkyl perfluoroalkyl ether, the perfluoroalkyl group and the alkyl group may be linear or branched. Specific examples thereof include, but are not limited to, perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) [for example, Novec (trade name) 7100 manufactured by Sumitomo 3M Limited], perfluorobutyl ethyl ether (C ₄ F _9).
OC ₂ H ₅ ) [for example, Novec (trade name) 7200 manufactured by Sumitomo 3M Limited] and perfluorohexyl methyl ether (C ₂ F ₅ CF(OCH ₃ )C ₃ F ₇ ) [for example, manufactured by Sumitomo 3M Limited]. Novec (trademark) 7300] and the like.

The perfluoroaliphatic hydrocarbon is not particularly limited, but preferably has 5 to 12 carbon atoms. Specific examples thereof include, but are not limited to, perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, and perfluorodihydropropanol (pentafluoropropanol).

The polyfluoroaromatic hydrocarbon is not particularly limited, and examples thereof include bis(trifluoromethyl)benzene and hexafluoro-m-xylene.

The polyfluoroaliphatic hydrocarbon is not particularly limited, and examples thereof include C ₆ F ₁₃ CH.
₂ CH ₃ (for example, Asahi Klin (registered trademark) AC-6000 manufactured by Asahi Glass Co., Ltd.), 1
, 1,2,2,3,3,4-heptafluorocyclopentane (for example, Zeorora (registered trademark) H manufactured by Nippon Zeon Co., Ltd. and the like can be mentioned.

The hydrofluorocarbon (HFC) is not particularly limited, but for example, 1,1
, 1,3,3-pentafluorobutane (HFC-365mfc) and the like.

Hydrochlorofluorocarbon (HCFC) is not particularly limited, but preferably has 2 to 5 carbon atoms. Specific examples include, but are not limited to, HCFC-225 (dichloropentafluoropropane: ASAHIKLIN (registered trademark) AK225), HCFC141b (
Dichlorofluoroethane), CFC316 (2,2,3,3-tetrachlorohexafluorobutane) and C ₅ H ₂ F ₁₀ (for example, Vertrel (registered trademark) XF manufactured by DuPont).
Etc.

The hydrofluoroether (HFE) is not particularly limited, and examples thereof include perfluoropropyl methyl ether (C ₃ F ₇ OCH ₃ ) (for example, Novec (trademark) 7000 manufactured by Sumitomo 3M Limited) and CF ₃ CH ₂ OCF ₂ CHF ₂ (for example, Asahi Klin (registered trademark) AE-3000 manufactured by Asahi Glass Co., Ltd.) and the like can be mentioned.

The hydrofluoroolefin (HFO) is not particularly limited, but for example, 1,
Examples thereof include 2-dichloro-1,3,3,3-tetrafluoro-1-propene (for example, Bertrel (registered trademark) Scion manufactured by Mitsui DuPont Fluorochemicals).

In the alkyl perfluoroalkyl ether, the perfluoroalkyl group and the alkyl group may be linear or branched. Specific examples thereof include, but are not limited to, perfluorobutyl methyl ether (C ₄ F ₉ OCH ₃ ) (for example, Novec (trade name) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C ₄ F _9).
OC ₂ H ₅ ) (for example, Novec (trade name) 7200 manufactured by Sumitomo 3M Limited) and perfluorohexyl methyl ether (C ₂ F ₅ CF(OCH ₃ )C ₃ F ₇ ) (for example, manufactured by Sumitomo 3M Limited). Novec (trade name) 7300) and the like.

Other solvents that can be used to form the above-mentioned fluorine-containing compound as a solution include alcohol solvents such as methanol, ethanol and isopropyl alcohol; ketone solvents such as acetone and methyl isobutyl ketone; ethyl acetate and butyl acetate. An ester solvent such as and an ether solvent such as tetrahydrofuran can be used. As the solvent for dissolving the above-mentioned components such as the fluorine-containing compound, only one kind of solvent may be used, or two or more kinds of solvents may be mixed and used. If necessary, additives may be added to the solvent for use.
Although not particularly limited, examples of the additive include acids such as sulfuric acid and Mohr's salt.

In the step (2), the surface layer (B) may be previously formed by coating the surface of the underlayer with the above-mentioned component such as the fluorine-containing compound dissolved in a solvent and then performing a polymerization or crosslinking reaction. After polymerizing to form a polymer, the surface of the surface layer (B
) May be formed.

The method of polymerization or crosslinking reaction is not particularly limited, but may be, for example, radical polymerization, and more specifically, electron beam irradiation, gamma ray irradiation, ultraviolet irradiation, plasma treatment,
Examples include corona treatment, organic polymerization reaction, and organic crosslinking reaction.

The method of coating the surface of the underlayer with the polymer formed in advance is not particularly limited, and spin coating method, bar coating method, drop casting method, dip nip method, spray coating method, brush coating method, dipping method, inkjet method Printing method, electrostatic coating method, compression molding method, extrusion molding method,
A calender molding method, a transfer molding method, an injection molding method, a roto molding method, a lot lining molding method, a heat-induced phase separation method, a non-solvent-induced phase separation method and the like can be adopted.

As a method for forming a polymer on the surface by radical polymerization after coating the surface of the underlayer with the above-mentioned fluorine-containing compound dissolved in a solvent, the polymer is formed on the surface of the underlayer by surface graft polymerization. Can also In this case, both the pre-irradiation method and the simultaneous irradiation method can be adopted.

In particular, it is preferable to form the polymer on the surface of the base by radiation surface graft polymerization by the pre-irradiation method. According to this method, after the polymerization initiation point is formed on the surface of the base, the polymer can be grown there. It is preferable in that the polymer can be fixed to the surface of the base by a chemical bond.

3. Surface Treatment Agent The surface treatment agent of the present invention is used for producing the base material of the present invention, the surface layer (B).
It is a composition capable of forming.

The surface treatment agent of the present invention is a surface treatment agent which can make the contact angle of the treated surface in water at 20°C preferably 80° or more, more preferably 90° or more.

The surface treating agent of the present invention is particularly a surface treating agent which is applied to a surface having a contact angle in water at 20° C. of less than 80°. The surface treatment agent of the present invention has a contact angle in water at 20° C.
A surface treatment agent which is preferably applied to a surface of less than 80° C., more preferably 70° or less.

The surface treatment agent of the present invention is not particularly limited as an active ingredient, but includes, for example, the above-mentioned fluorine-containing compound and other ingredients.
The surface treatment agent of the present invention may contain, as an active ingredient, a monomer capable of forming the above-mentioned fluoropolymer.

The surface treating agent of the present invention contains a solvent that dissolves the active ingredient. The solvent is not particularly limited, but "the components such as the fluorine-containing compound are dissolved in "(1) the step of dissolving the components such as the fluorine-containing compound in the solvent" in "2. A "solvent" may be used.

Although not particularly limited, examples of the additive include acids such as sulfuric acid and Mohr's salt.

The surface treatment agent of the present invention can form the surface layer (B) with a desired film thickness even on a structure having a complicated shape.

As means for applying the surface treatment agent of the present invention to the surface to be treated, spin coating method, bar coating method, drop casting method, dip nip method, spray coating method, brush coating method, dipping method,
An electrostatic coating method, an inkjet printing method, etc. are mentioned. Among them, the spin coating method, the drop casting method, the brush coating method and the dipping method are preferable from the viewpoint of simplicity.

The surface treatment agent of the present invention may further contain additives, if necessary. Such additives are not particularly limited and include, for example, leveling agents, solid lubricants, pigments, glitters, fillers, pigment dispersants, surface modifiers, viscosity modifiers, ultraviolet absorbers, light stabilizers, Examples thereof include a plasticizer, a color separation preventing agent, a scratch preventing agent, a biorepellent agent, an anti-inflammatory agent, an antibacterial agent, an anticorrosive agent, an antistatic agent, a silane coupling agent, an anti-arming agent, and a matting agent.

The surface treatment agent of the present invention can be produced by mixing or dispersing the above-mentioned active ingredient and, if necessary, the above-mentioned additives and the like by a known method.

The film thickness of the coating film formed using the surface treatment agent of the present invention is 0.1 to 2 in terms of the effect of the present invention.
5,000 μm, more preferably 1 to 500 μm, and 5 to 1
More preferably, it is 00 μm. The film thickness is a value obtained by measurement according to the method of JIS K5600.

The surface treatment agent of the present invention may be an aquatic organism adhesion preventing coating material.

4. Surface Treatment Method The surface treatment method of the present invention includes a step of applying the surface treatment agent of the present invention to a surface to be treated.

As means for applying the surface treatment agent of the present invention to the surface to be treated, spin coating method, bar coating method, drop casting method, dip nip method, spray coating method, brush coating method, dipping method,
An electrostatic coating method, an inkjet printing method, etc. are mentioned. Among them, the spin coating method, the drop casting method, the brush coating method and the dipping method are preferable from the viewpoint of simplicity.

When the surface treatment agent of the present invention is an aquatic organism adhesion preventing paint, the surface treatment method of the present invention can be a method of preventing adhesion of aquatic organisms to an underwater structure. The method for preventing adhesion of aquatic organisms to the underwater structure includes a step of applying an aquatic organism adhesion preventing paint to the surface of the underwater structure.

The method for applying the aquatic organism adhesion preventing paint is not particularly limited, and it can be applied by a known method.

The method of preventing adhesion of aquatic organisms to an underwater structure of the present invention can be a method including a step of attaching the substrate of the present invention to the underwater structure.

The method of attaching the base material of the present invention to the underwater structure of the present invention is not particularly limited, and the base material of the present invention may be attached directly or indirectly (via another member or the like) to the underwater structure. Good.

The method for directly attaching the base material of the present invention to the underwater structure is not particularly limited, and an adhesive or an attachment tool such as an anchor bolt may be used as necessary.

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.

The weight average molecular weight, the softening point and the contact angle in water were measured by the following procedures.
[Weight average molecular weight]
The weight average molecular weight (Mw) was determined by mixing HCFC225 and 1,1,1,3,3,3-hexafluoro-2-propanol in a ratio of 90:10 as a solvent and using TOSOH as a column.
TSKguardcolumn HXL-L (6.0 mm ID x 4 cm), TOSO
H TSKgel G4000HXL (7.8 mm ID x 30 cm), TOSOH T
SKgel G3000HXL (7.8 mm ID x 30 cm), TOSOH TSKg
It was measured by GPC analysis at 30° C. by using a tube in which el G2000HXL (7.8 mm ID×30 cm) was connected in series. The chromatogram was calibrated using a standard PMMA (polymethylmethacrylate) sample.

[Softening point measurement]
Glass transition point (Tg) or melting point (Tm) is 10 mg of polymer powder DSC822
e [manufactured by Mettler Toledo, USA] from the thermogram at the 2nd cycle when measured in the temperature range of −50 to 150° C. and the heating rate of 10° C./min. 1987).

[Underwater contact angle measurement]
The water/oil repellency was evaluated by measuring the contact angle using Drop Master 701 manufactured by Kyowa Interface Science Co., Ltd.

That is, a 1 wt% solution of the polymer in a HCFC-225 solvent was applied onto a silicon wafer substrate (20×10 mm) by a brush coating method (10 times), and then dried at room temperature to form a film. Then, after fixing the film-formed silicon wafer substrate in water in a glass water tank (60×60×40 mm) containing 100 cc of distilled water so that the film-formed surface faces downward, the film was completely immersed in water.
The temperature was kept at 30°C for 30 minutes. Attach 10 μl of air bubbles with a syringe to the film-forming surface fixed in water,
The contact angle of the bubbles was measured. The contact angle of water measured in water, that is, the contact angle in water is "180°-
(Contact angle of bubbles)”.

Example 1
In a 300 ml autoclave, a fluorine-containing monomer CH ₂ =CHCOOC ₂ H ₄ (CF ₂
) ₈ F (hereinafter abbreviated as 17-FA) 51.8 g (100 mmol), solvent HCFC2
25 120.0 g and a radical polymerization initiator AIBN 0.164 g (1 mmol) were added and sealed, and then oxygen in the autoclave was removed by nitrogen substitution. Then, the autoclave was immersed in an oil bath, the temperature was gradually raised with stirring, and the temperature was kept at 60° C. for 12 hours to carry out a polymerization reaction. The polymerization reaction liquid cooled to room temperature was poured into a large amount of methanol to precipitate the polymer, which was collected by filtration, washed and vacuum dried to obtain a 17-FA polymer.

With respect to the obtained 17-FA polymer, the weight average molecular weight, the softening point and the contact angle in water were evaluated.

Then, the 17-FA polymer was made into a 1 wt% solution in HCFC-225 solvent, which was applied onto a polyester plate (40×40×1 mm) by a brush coating method (10 times), dried at room temperature, and tested. I made a board. To evaluate the adherence of cypris larvae (the larvae of the Tadima barnacles attached to a large amount of artificial structures in the inner bay area) to the test plate, a polystyrene container (117
The test plate, 150 ml of seawater, and 30 to 50 Cyprus larvae were placed in a (84×57 mm) area and placed in a dark place at 20±1° C. Twelve days after the introduction of the cypris larvae, the test plate was taken out from the polystyrene container, and the adhesion rate of the cypris larvae to the test plate was evaluated. The evaluation results are shown in Table 1.

Examples 2-8 and Comparative Examples 1-3
As shown in Table 1, the same operation as in Example 1 was performed except that the fluorine-containing monomer was changed. The evaluation results are shown in Table 1.

Comparative Example 4
Polyester plate (40 x 40 x 1 mm) not coated with any polymer as a support
The same operation as in Example 1 was carried out except that was used to evaluate the contact angle in water and the adhesion of cypris larvae. The evaluation results are shown in Table 1.

The base materials of Examples 1 to 8 which were surface-treated with a fluoropolymer having a softening point of 0° C. or higher developed a contact angle in water of 80° or higher, and the Cyprus larval adhesion rate was lower than that of the Comparative Example.

Example 9
In a 300 ml autoclave, a fluorine-containing monomer CH ₂ =CHCOOC ₂ H ₄ (CF ₂
) ₈ F (abbreviation: 17-FA) 51.8 g (100 mmol), solvent HCFC-225
After 120.0 g and 0.164 g (1 mmol) of radical polymerization initiator AIBN were added and sealed, oxygen in the autoclave was removed by nitrogen substitution. Then, the autoclave was immersed in an oil bath, the temperature was gradually raised with stirring, and the temperature was kept at 60° C. for 12 hours to carry out a polymerization reaction. The polymerization reaction liquid cooled to room temperature is poured into a large amount of methanol to precipitate the polymer,
After filtration, washing and vacuum drying, a 17-FA polymer was obtained.
The weight average molecular weight, softening point and contact angle in water of the obtained 17-FA polymer were evaluated.
Then, the 17-FA polymer was made into a 1 wt% solution in an HCFC-225 solvent, and this was used for a float for hydroponics by a brush coating method (5 times).
(×140×20 mm), and dried at room temperature to prepare a test plate. 3 L of the cultivation nutrient solution was placed in a PP container (internal dimensions: 300×460×150 mm), and the test plate on which the lettuce seedling (1 strain) was planted was floated. Further, air bubbling of the cultivation nutrient solution was carried out using an air pump, and hydroponic cultivation was carried out by leaving it for 3 weeks in a sunny environment, and the adhesion of green algae to the test plate was evaluated. The evaluation results are shown in Table 2.
1 point: Green algae can be easily removed by scrubbing sponge 2 points: Most green algae can be removed by scrubbing sponge 3 points remaining green algae: Almost no green algae can be removed by scrubbing sponge

Examples 10-16 and Comparative Examples 5-7
As shown in Table 2, the same operation as in Example 9 was performed except that the fluorine-containing monomer was changed. The evaluation results are shown in Table 2.

Comparative Example 8
Styrofoam plate not coated with any polymer as a support (white, 250×30
Adhesion of green algae to the test plate was evaluated by the same operation as in Example 9 except that 0×20 mm) was used. The evaluation results are shown in Table 2.
The test plates of Examples 9 to 16 which were surface-treated with a fluoropolymer having a softening point of 0° C. or higher had weak adhesion of green algae to the float in hydroponics, and the green algae could be easily removed by rubbing.

Claims (11)

A substrate containing (A) a support; and (B) a surface layer,
The surface layer (B) is disposed on at least a part of the surface of the support (A) directly or via one or more other layers,
A group in which the surface of the surface layer (B) has a contact angle in water at 20° C. of 80° or more, and the surface layer (B) is composed of a fluoro(meth)acrylate-based polymer and a fluoro(meth)acrylamide-based polymer. A layer containing at least one fluorine-containing polymer having a softening point of 0° C. or higher (provided that CH ₂ ═C(CH ₃ )COOCH ₂ CF ₃ is a homopolymer composed of structural units or has 8 or more carbon atoms. ( Excluding a layer formed by coating only poly(fluoroalkyl acrylate) having a linear fluoroalkyl group ). The base material according to claim 1, wherein the surface layer (B) is bonded to the underlying surface via a chemical bond. The substrate according to claim 1, which is an aquatic organism adhesion-preventing material. It is a composition which is used for manufacturing the base material as described in any one of Claims 1-3, and which can form the said surface layer (B), Comprising: The contact angle in water at 20 degreeC is 75 degrees. A composition capable of having a water contact angle at 20° C. of the surface of a polyester plate of 80° or more . The composition according to claim 4, which contains the fluoropolymer and/or a monomer capable of forming the fluoropolymer. Surface treatment agent containing a fluoropolymer and/or a monomer capable of forming the fluoropolymer, which can make the contact angle in water at 20° C. of the surface of the polyester plate having a contact angle in water at 20° C. of 75° to be 80° or more. And
A surface treatment agent (however, the fluoropolymer is a fluoropolymer having a softening point of 0° C. or higher, which is at least one selected from the group consisting of fluoro(meth)acrylate-based polymers and fluoro(meth)acrylamide-based polymers. CH ₂ ═C(CH ₃ )COOCH ₂ CF ₃ surface treatment agent containing only a homopolymer consisting of structural units, CH ₂ ═C(CH ₃ )COOCH ₂ CF ₃ surface treatment agent only , and carbon ( Excluding surface-treating agents containing only poly(fluoroalkyl acrylate) having a linear fluoroalkyl group of 8 or more ). The surface treatment agent according to claim 6, which is applied to a surface having a contact angle in water at 20°C of less than 80°. The surface treatment agent according to claim 6 or 7, which is an aquatic organism adhesion preventing paint. A method for treating a surface to be treated, which comprises a step of applying the composition according to claim 4 or 5 to the surface to be treated. An underwater structure having the base material according to claim 1 or 2 in at least a part thereof. A method for preventing adhesion of aquatic organisms to an underwater structure, which comprises the step of applying the surface treatment agent according to claim 6 or 7 to the surface of the underwater structure.