WO2001060923A1 - Resin composition for preventing attachment of aquatic organism or physiological substance - Google Patents

Abstract

A resin composition for preventing the attachment of an aquatic organism or a physiological substance which comprises a hydrolyzable organic metal compound capable of imparting hydrophilic property to a surface and a resin as a binder; and a composition, a structure and a medical member prepared by using the resin composition, which are capable of preventing the attachment of an aquatic organism, a physiological substance and a hydrophobic stain and also are easy to remove stains therefrom.

Description

 Akira Itoda Aquatic organisms or resin compositions for preventing adhesion of physiological substances

 The present invention does not use chemicals that can be dissolved or released into the water, and can be used to aquatic or water-based products or structures. The present invention relates to a technique for preventing the attachment of organisms, or preventing the attachment of cells or physiological substances to medical components, and easily removing even if attached. Background art

 Objects and structures used over or under water for extended periods of time will have aquatic organisms attached and grow, which will not only make them unfavorable in appearance but also impair their function. Various methods have been adopted to prevent the attachment of these aquatic organisms and to kill them.

 For example,

(1) A method of killing aquatic organisms by applying or impregnating a water-soluble metal poison such as copper, zinc, organic tin, or organic zinc.

(JP-A-54-78733, JP-A-57-43176, JP-A-7-90200, JP-A-9-176577, etc.) (2) Silicon oil By applying or impregnating and releasing silicone oil from the surface, the smoothness of the surface is enhanced, and water currents (ocean currents, waves, ship movements, etc.) To prevent the attachment of aquatic organisms (Japanese Patent Publication Nos. Hei 5-53878, Hei 4-1370173, Hei Hei 5-78617, Hei 8-193173, Hei 8-193173, Japanese Patent Publication No. 8-23] 898 (3) If a water-swellable resin film such as polyvinyl alcohol or vinyl acetate resin is provided, the coating film will be reduced (the film thickness will be reduced). Accordingly, methods for preventing the attachment of aquatic organisms (Japanese Patent Publication No. 7-90200, Japanese Patent Publication No. 9-227821, Japanese Patent Publication No. 11-29725, etc.),

 (4) A hydrophobic fluororesin coating, such as polytetrafluoroethylene (PTFE), is applied to the bottom of a ship, and the surface lubricity of the surface is used for aquatic organisms. A method for preventing the adhesion of water (Japanese Patent Publication No. 58-221795),

 (5) A method in which a metal oxide powder such as titanium oxide having photocatalytic activity is contained in a coating film, and the oxidizing power is used to prevent the attachment and growth of aquatic organisms ( Japanese Patent Publication No. 10-204335) is known.

 In the method (1), the dissolution of the metal poison is inevitable, which is not preferable because of the influence on the environment.

 In the above method (2), a relatively low toxicity silicone foil is used, but basically, the action of releasing from the surface is used. In addition, there is a concern about the impact on the environment.

 In addition, the method (3) also uses the reduction of the film thickness of the water-swellable resin, so it is necessary to consider the effect on the environment. Insufficient durability and stability.

 In the methods using the dissolution and release of the anti-adhesion components as described in (1) to (3), the anti-adhesion effect for a long time is expected because these components are consumed. Can not .

The method (4) utilizes the characteristics of fluororesin, which is hydrophobic and has good surface lubricity, to reduce the resistance of a ship during traveling. However, it is possible to prevent aquatic organisms from adhering by the generated water flow. Processing such as painting and baking is not easy, and at the time of berthing, adhesion of various kinds of dirt cannot be prevented, the surface activity decreases, and the attachment and growth of aquatic organisms over time. It cannot be suppressed.

 Furthermore, in the method (5), it is difficult to uniformly form a durable coating film, and the film-forming resin itself is deteriorated by a catalytic action. The durability cannot be obtained.

 As described above, the conventional methods for preventing aquatic organisms from adhering have problems to be solved.

 However, in the conventional method for preventing aquatic organisms from adhering, except for the method (3), a resin whose surface is mainly hydrophobic (a contact angle with water of 70 ° or more) (epoxy resin) is mainly used. , Urethane resin, silicone resin, fluorine resin, curable acrylic resin, thermoplastic acrylic resin, polyester resin, alkyl resin, pheno resin Resin, melamine resin, urine resin, chlorinated rubber, etc.) are used as film-forming components.

 It has been found that hydrophobic dirt is easy to adhere to such a coating film whose surface is hydrophobic, and that if it adheres, it is difficult to remove.

In addition, recent studies on the mechanism of the attachment of aquatic organisms and the attachment of dirt of biological origin have shown that organic substances (proteins, Substances that change to hydrophobic or water-insoluble in water, such as peptides and polysaccharides, adhere to the surface of structures, and that these organic substances contribute to the attachment of organisms. (Keiji Yamashita, “Electrochemistry and Industrial Physical Chemistry,” Vol. 58, No. 1, pp. 3–11 (1990). Fouling caused by organic substances released from the surface is also reported to occur when the surface has a hydrophobic structure (M. Fletcher, GI Loeb, Applied A Applied & Enviromental Microbio) (1979); R.H. Brewer "Noological Bulletin (Applied & Enviromental Microbio)" Biol. Bull.) ", Vol. 166, NO. 11 (1984).

 The purpose of the present invention is to provide a resin composition which does not release harmful components and prevents the attachment of aquatic substances or biological substances. .

 Another purpose of the present invention is to prevent the release of harmful components into water, prevent aquatic organisms from adhering, and allow easy removal even if attached. To provide such structures.

 Yet another object of the present invention is to provide a medical device to which cells and biological materials are not easily adhered and which can be easily removed even if adhered. It is in . Disclosure of the invention

 That is, the present invention relates to an aquatic organism or a biological substance containing a hydrolyzable organic metal compound (a) for surface hydrophilicity and a resin (b) for a binder. The present invention relates to a resin composition for preventing adhesion of a substance.

 In addition, the present invention relates to a product or structure used on a water surface having a surface on which a coating layer obtained from the resin composition is present or on the surface of water. About structures.

 Further, the present invention provides a method for manufacturing a semiconductor device, comprising: a surface having a coating layer obtained from the resin composition; or a resin layer obtained from the resin composition. It relates to medical materials formed into shapes such as films, sheets or tubes.

Further, the present invention provides a resin film having a coating layer obtained from the above resin composition on one surface of one of the resin films, and the other surface of the resin film. A film that has an adhesive layer on the surface, The present invention also relates to a marking film for use in an article or a structure or a medical member used in water or in water.

 The present invention also provides a method of applying the resin composition to a surface of a product or a structure used on the surface of water or in water to form a coating film. How to prevent aquatic organisms from attaching to goods or structures, or

By applying the resin composition to the surface of a medical member that comes into contact with a cell or a physiological substance released from a living body to form a coating film, the cells to the medical member are formed. The present invention also relates to a method for preventing the attachment of physiological substances. Not only the best form for carrying out the invention, but also the aquatic organisms and physiological substances covered by the invention that are intended for use on the surface or in the water Structures and medical components that come into contact with physiological substances released from cells or living organisms are described.

 There are various types of goods or structures used on the surface of the water or in the water, regardless of whether they are seawater or freshwater. For example, the following goods and structures can be exemplified, but not limited to these. In addition, structures include not only fixed structures such as piers and waterways, but also structures that mainly move such as ships.

Structures used on or below the water

Fixed type:

 Underwater structures such as piers, concrete blocks, wave-dissipating blocks, breakwaters, etc .;

Port facilities such as sluice gates, marine tanks and floating piers; Subsea operations such as undersea digging facilities and undersea communication cable facilities Facility;

 Thermal power, atomic power, ocean thermal power generation facilities such as headraces, flood pipes, water chambers, etc .;

 Water supply and drainage and storage facilities for pools, water tanks, water towers, sewers, rain, etc .;

 Domestic equipment such as system kitchen, flush toilet, bathroom, bathtub, etc .;

Mobile type:

 Draft or bottom of the vessel, submarine exterior, skull propeller, anchor, etc., and other vessel structures or accessories

Goods used on or below the water

Fixed type:

 Fishery goods such as fishnets such as fixed nets, buoys, fish cages and ropes;

 Thermal power such as water covers, water chambers, nuclear power, ocean thermal energy conversion materials;

 Undersea (underwater) cable and other seabed (waterbed) laying goods;

 Fishing products such as trawls and fly traps;

 Objects or structures used on the surface of the water or in the water will be contaminated with aquatic organisms and organic dirt, such as spikes, which will reduce their appearance and function. .

Aquatic organism

Fusippos, mussels, mussels, squirrels, sea squirts, worms, bryozoans, various aquatic organisms, various seaweeds Diatoms, horned straws, vasas, vasculatures, etc. Various diatoms, annelids (such as zebras, squirrels, etc.), and sponges (as swords) Etc.), and others The adherent organisms

Organic stains:

 Floating oil (mineral oil, vegetable oil, etc.), waste foods, resins, human waste, dead creatures of living things, etc.

 In addition, as medical members that come into contact with physiological substances released from cells or living bodies, for example, sponge materials are required, but these are limited to these. It is not something.

 Medical components used directly on living bodies such as catheters, artificial blood vessels, artificial tissues, artificial bones, dialysis equipment, and various tubes;

 Equipment that comes in contact with physiological substances such as antithrombotic materials, test tubes, and chare;

 Medical-related research and analysis equipment such as tissue, cell, and bacterial culture equipment, and physiological substance analysis equipment;

 As the cells and physiological substances adhering to these medical members, for example, the most prominent ones can be obtained. Cells also include unicellular organisms such as viruses and bacteria.

Cells:

 Blood cells, various viruses, bacteria, etc.

Physiological substances:

 Various proteins, various enzymes, various peptides, various amino acids, various polysaccharides, various nucleic acids, cholesterol, fats, etc.

 The resin composition of the present invention, which can prevent the adhesion of these various organisms and substances, comprises a hydrolyzable organometallic compound (a) for surface hydrophilicity and a resin (b) for a binder. Including.

The hydrolyzable organometallic compound (a) is present on the surface of a matrix (film or molded body) formed by the resin (b), and the hydrolyzable group is hydrolyzed. Makes the surface hydrophilic And acts to prevent the adhesion of the above-mentioned various organisms, physiological substances, and hydrophobic dirt. Therefore, such a hydrolyzable organometallic compound may be hereinafter referred to as a “hydrophilizing agent”.

 Suitable hydrolyzable organometallic compounds (a) for the present invention include, for example, those of formula (I):

X _b M (OR ¹ ) _a R ² _c (I)

[Where a is 0 or an integer from 1 to 6, b is 0 or an integer from 1 to 5, c is 0 or; An integer from 6 to 6 (where a + b + c ≥ 3 and a and c are not simultaneously 0), and X is the same or different O-, N-, F- and Z- or chlorine-containing monovalent organic groups having 1 to 5,000 carbon atoms or hydrogen atoms, and M is small In particular, a metal atom having a valence of trivalent, R ¹ is the same or different and each represents an oxygen atom, a nitrogen atom, a fluorine atom and / or a chlorine atom. A monovalent organic group having 1 to 1000 carbon atoms, a siloxane residue or a hydrogen atom which may be contained, and R ² is the same or different, and each is an oxygen atom or a nitrogen atom Atom represents an organic group having 1 to 20 carbon atoms capable of chelation, which may contain a fluorine atom or a chlorine atom. Hydrolyzable organometallic compound Re that, its O Li sesame over or of two or more or al Ru Nobi Li sesame one there down et been ing the organometallic compound. The compounds that can be used are described in detail in WO 97 11130 Novel fret.

In this organometallic compound, in the formula (I), a is an integer of 0 or 1 to 6 from the viewpoint of surface concentrating property, hydrolyzing property, and desorbing property; It is preferably an integer from 2 to 4. b is an integer of 0 or 1 to 5 from the viewpoint of surface enrichment and hydrophilicity And preferably an integer of 0 to 1, and c is an integer of 0 or 1 to 6 from the viewpoint of surface concentrating, hydrolyzing and desorbing properties. It is preferably an integer from 0 to 3.

Also, molar ratio of 0.2 or less against the Ri + R ² of X (b / (a + c ) ≤ 0. 2) Oh Ru's is not to good or at.

The total amount of a, b and c is determined by the valency of the metal atom M, but in the formula (I), either OR ¹ or R ² is used. One of them is necessary for its anti-bioadhesive properties, anti-fouling adhesive properties, surface condensing properties, and hydrolyzability (hydrophilizing ability), so that a and c do not become 0 at the same time. The total amount of a, b and c is at least 3.

 In particular, when a is 4 and b and c are zero, or when a is 3 and b is 1 and c is zero, they are excellent in hydrolyzability and surface hydrophilicity. It is good.

 X is a hydrogen atom, or an oxygen atom, a nitrogen atom, a fluorine atom, or a chlorine atom, as in (i) to (iii) above. Is a monovalent organic group having 1 to 5,000 carbon atoms.

(i) The organic group X is, for example, H (CH ₂ ) _p , (CH ₃ ) ₂ CH, H (CH ₂ ) _p C = 0, F (CF ₂ ) _q (CH ₂ ) _p , ( CF ₃ ) ₂ CH, H (CF ₂ ) _q (CH ₂ ) _p (where p is 0 or an integer from 1 to 6, q is an integer from! To 10) Some of the fluorine atoms are May be substituted with a chlorine atom), and these organic groups may be linear or branched.

Examples of these are, for example, CH ₃ , CH ₃ CH ₂ , CH ₃ CH ₂ CH ₂ , (CH ₃ ) ₂ CH, CF ₃ CH ₂ , CF ₃ CF ₂ CH ₂ , (CF ₃ ) ₂ CH, F (CF ₂ ) ₄ CH ₂ CH ₂ , F (CF ₂ ) ₈ CH ₂ CH ₂ , H (CF ₂ ) ₄ CH ₂ etc., but surface concentrating and hydrolyzing In terms of detachability CF ₃ CF ₂ CH ₂ (CF ₃ ) ₂ CH is preferred.

(ii) or the organic group X, was example, if NH _2, secondary A Mi amino group, tertiary § Mi amino group, OH NCO C_〇 ₂ HC_〇 _{2 Na C0 2 K SO 3 H} SO ₂ Na S0 ₃ K, et Po key sheet group, O key Shechi les down group (CH ₂ CH ₂ 0), etc. functional groups organic group of Dogaa up al is Ru that Yusuke.

Examples of these are, for example, H ₂ N (CH ₂ ) ₃ OCN (CH ₂ ) 3 CH ₃₀ (CH ₂ CH ₂₀ ) (CH ₂ ) ₃ CH ₃₀ (CH ₂ CH ₂₀ ) ₅ (CH ₂ ) ₃ , CHgO CCHsCHzOi ^ iCHs); ^ CH ₂ CHCH ₂₀ (CH ₂ ) ₃

, O,

Although OCN (CH ₂ ) ₃ CH ₃₀ (CH ₂ CH ₂₀ ) ₅ (CH ₂ ) ₃ is preferred in terms of hydrophilicity, compatibility, and adhesion.

 (iii) The organic group X is a polymerizable organic group which may contain, for example, an oxygen atom, a nitrogen atom, a fluorine atom, a chlorine atom, a silicon atom, and the like. The group is removed.

Examples of this are found that was example, if _{CH 2 = C (CH 3)} C0 2 (CH.) 3,

CH ₉ = CH CH, = CHCH _? CH ₉ = CHO (CH _? 2) 3 CH ₂ = CH

OCO (CH ₂ 2) 3 CH _H = CHC ₆ H ₄ , CH _?. = CHC 0 ₂ (CH ₂ ) ₃ etc., but polymerizable and easily available CH ₂ C (CH ₃ ) CO ₂ (CH ₂ ) ₃ CH ₂ = CHO (CH ₂ ) ₃ is preferred.

 In the present invention, the molecular weight obtained by polymerizing or copolymerizing the compound represented by the formula (I) having such a polymerizable organic group is 200,200,000. Also, preferably 5000 to 20000 polymers or copolymers are included in the present invention.

R ¹ may contain the same or different oxygen, nitrogen, fluorine, and / or chlorine atoms, and may be bioadherent. Monovalent with 11000 carbons in terms of prevention, surface concentration, hydrolyzability (hydrophilicity), and desorption It is an organic group or a hydrogen atom, and the number of carbon atoms is preferably from 1 to 100, and more preferably from 1 to 16. No. However, at least one of R ¹ is CF ₃ CH FCF ₂ CH ₂ , CF ₃ CHFCF ₂ CHCH ₃ or CF ₃ CHFCF ₂ C (CH

₃ ) It is 2.

These monovalent organic groups of R ¹ other than CF ₃ CHFCF ₂ CH ₂ , CF ₃ CHFCF ₂ CHCH ₃ and CF ₃ CHFCF ₂ C (CH ₃ ) ₂ are as follows. For example, H (CH ₂ ) _m , (CH ₃ ) ₂ CH, H (CH ₂ ) _m C = 〇, F (CF ₂ ) _n (CH ₂ ) _m , (CF ₃ ) ₂ CH, H (CF ₂ ) _n (CH ₂ ) _m , F (CF ₂ ) _n (CH ₂ ) _m C = 0, H (CF ₂ ) _n (CH ₂ ) _m C = 0, (F (CF ₂ ) _n (CH ₂ ) _m ) ₂ N. ((CF ₃ ) ₂ CH) ₂ N, (H (CF ₂ ) _n (CH ₂ ) _m ) ₂ N, F (CF ₂ ) _n O (CF (CF ₃ ) CF ₂₀ ) _m CF ( CF ₃ ) C = O, (F (CF ₂ ) _n (CH ₂ ) _m ) ₂ C = N, ((CF ₃ ) ₂ CH) ₂ C = N, (H (CF ₂ ) _n (CH ₂ ) _m ) ₂ C = N, F (CF ₂ ) _n (CH

₂ ) _m C = ONR ³ , H (CF ₂ ) _n (CH ₂ ) _m C = ONR ³ , F (CF ₂ ) _n (CH ₂ ) _m C = CH ₂ , H (CF ₂ ) _n (CH ₂ ) _m C = CH ₂ , F (CF ₂ ) _n (CH ₂ ) _m C = CF ₂ , H (CF ₂ ) _n (CH ₂ ) _m C = CF ₂ (where m is 0 or 1 to 6 N is an integer of 1 to: 10, R ³ is a carbon number:! To 6 and represents an alkyl group, and the alkyl group may be a straight chain or a branched chain. ) Are preferred.

Specific examples of these organic groups are, for example, CF ₃ CH ₂ , CF ₃ CF ₂ CH ₂ , CF ₃ (CF ₂ ) ₂ CH ₂ , CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ , (CF

₃ ) ₂ CH, CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ , H (CF ₂ ) ₂ CH ₂ , H (CF ₂ ) ₃ CH ₂ , H (CF ₂ ) ₄ CH ₂ , CF ₃ C = 0, CF ₃ CF ₂ C = O, CF ₃ (CF ₂ ) ₆ C = 0> CF ₃ (CF ₂ ) ₇ C = O, etc., but the surface condensability, water decomposability, desorption CF ₃ CH ₂ , CF ₃ CF ₂ CH ₂ , CF ₃ (CF ₂ ) ₂ CH ₂ , CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ , CF ₃ C = O, CF ₃ CF ₂ C = 0 is preferable, CF ₃ CH ₂ and CF ₃ CF ₂ CH ₂ are more preferable, and even if R ¹ is an organic high molecular chain up to 1000 carbon atoms. Yo I

R ² may be the same or different, and has excellent chelating ability even if it contains a fluorine atom or a chlorine atom. It has a carbon number of 1 to 20 in terms of bioadhesion prevention, surface thickening, hydrolyzability (hydrophilicity), and desorption properties. A value of ~ 10 is a preferred organic group.

 In the present invention, a water-decomposable organic metal compound to which an organic base having such a capability of binding is combined is used. As a result, excellent storage stability, anti-bioadhesive properties, reactivity, solubility, and compatibility can be obtained.

Compounds that can be such organic compounds that have the ability to chelate include, for example, 2,41 pentanes, 2,4 pentanes, 4 _ Heptanedione, etc.] 3-Ketostears such as diketons, methyl acetate acetate, ethyl acetate acetate, butylacet acetate, etc. , Lactic acid, methyl lactate, methyl lactate, ammonium lactate, salicylic acid, methyl salicylate, methyl ethyl salicylate, linoleic acid Hydroxycarboxylic acids such as formic acid, ethyl linoleate, tartaric acid, and ethyl tartrate, or their esters, salts, and 4-hydroxy acids 4—Methyl 1—2—pentanone, 4—Hydroxy — 2—Pen 2—Non, 4-Hydroxy 1—2—Heptanone, 4—Hydro Roxie I 4 _Me Chil_2—Cetolic alcohols such as heptanones, monoethanolamines, diethanolamines, and triethanolamines Amin, N-methylmonoamine, N-methylamine, N_methylmonoethanol, Amin, ,, Ν-methylethanol Amino alcohols such as min, Ν, Ν-ethyl ethanolamine, dimethyl alcohol malonate, methylol melamin And enol-active hydrogenated compounds such as methylol urine and methyl acrylamide. In addition, compounds in which all or part of these hydrogen atoms are substituted with a fluorine atom or a chlorine atom are not suitable in terms of surface enrichment. Is preferred.

 The metal atom M is, for example, B, Al, Ga, In, Tl, Sc, Y, La, Ac, Si, Ge, Sn, Pb, Ti, Zr, Hf, As, Sb, Bi, V , Nb, Ta, Te, Po, Cr, Mo, W, At, Mn, Tc, Re, Fe, Co, Ni, Ru, Rh, Pd> Os, Ir, Pt, etc. From the viewpoint of synthesis and availability, Al, Ti, B, Zr or Si, particularly Si is preferred.

 As the organometallic compound represented by the formula (I), for example, an organometallic compound as described above, or a polyolgomer or a coli obtained therefrom can be used. Sesame sesame etc. are excreted.

 When b is 0 in equation (I):

B (OCH ₃ ) ₃ , B (OC ₂ H ₅ ) ₃ ,

B (OCH ₂ CF ₂ CF ₃ ) ₃ , B (OCH (CF ₃ ) ₂ ) ₃ , B (OCH ₂ C ₃ F ₆ H) ₃ ,

B (OCH ₂ CH ₂ C ₈ F ₁₇ ) ₃ ,

B (OCH ₂ CF ₂ CF ₃ ) ₂ (OCH ₃ ),

B (OCH ₂ C ₃ F ₆ H) ₂ (OCH ₃ ),

B (OCH (CF ₃ ) ₂ ) ₂ (OCH ₃ ),

B (OCH ₂ CH ₂ C ₈ F ₁₇ ) ₂ (〇 CH ₃ ),

B (OCH ₂ CF ₂ CF ₃ ) ₂ (OH), B (OCH (CF ₃ ) ₂ ) ₂ (OH),

B (OCH ₂ CH ₂ C ₈ F ₁₇ ) 2 (OH),

B (OCOCF3) 3, B (OCOC ₂ F ₅ ) ₃ ,

B (OCOC ₈ F ₁₇ ) 3,

B (OCOCF ₃ ) ₂ (OCH ₃ ), B (OCOC ₂ F ₅ ) ₂ (OCH ₃ ),

B (OCOC ₈ F ₁₇ ) ₂ (OCH3),

Al (〇CH ₂ CF ₂ CF ₃ ) ₃ , Al (OCH (CF ₃ ) ₂ ) ₃ , A 1 (OCH ₂ C ₃ F ₆ ) ₃ , Al (OCH ₂ CH ₂ C ₈ F ₁₇ ) ₃ , A OCH ₂ CF ₂ CF ₃ ) ₂ (O CH ₃ ),

A OCH ₂ C ₃ F ₆ H) ₂ (OCHg),

A OCH (CF ₃ ) ₂ ) ₂ (OCH ₃ ),

A OCH ₂ CH ₂ C ₈ F ₁₇ ) ₂ (OCH ₃ ),

A OCH ₂ CF ₂ CF ₃ ) ₂ (OH),

A OCH (CF ₃ ) ₂ ) ₂ (OH),

A OCOCF ₃ ) ₃ , Al (OCOC ₂ F ₅ ) ₃ ,

A OCOC ₈ F ₁₇ ) ₃ ,

A OCOCF ₃ ) ₂ (OCH ₃ ), Al (OCOC ₂ F ₅ ) ₂ (OCH ₃ ) A OCOC ₈ F ₁₇ ) ₂ (OCH ₃ ),

A CF3COCHCOCF3) ₃

A CF ₃ COCHCOCF ₃ ) ₂ (CH ₃ COCHCOCH ₃ ), A CF ₃ COCHCOOC ₂ H ₅ ) ₃ ,

A CF ₃ COCHCOOC ₂ H ₅ ) ₂ (CH ₃ COCHCOCH ₃ )> A CF ₃ COCHCOCF ₃ ) ₂ (OH),

A CF ₃ COCHCOOC ₂ H ₅ ) ₂ (OH),

T OCH ₂ CF ₂ CF ₃ ) ₄ , Ti (OCH (CF ₃ ) ₂ ) ₄ ,

T OCH ₂ C ₃ F ₆ H) ₄ ,

₇) ₄、 T

₇ ) ₄ ,

T OCH ₂ CF ₂ CF ₃ ) ₂ (OCH ₃ ) ₂ ,

T OCH (CF ₃ ) ₂ ) ₂ (OCH 3) ₂ ,

T OCH ₂ C ₃ F ₆ H) ₂ (OCHg),

T OCH ₂ CH ₂ C ₈ F ₁₇ ) ₂ (OCH ₃ ) ₂ ,

T OCH ₂ CF ₂ CF ₃ ) ₂ (OCH (CH ₃ ) ₂ ) ₂ ,

T OCH (CF ₃ ) ₂ ) ₂ (OCH (CH ₃ ) ₂ ) ₂ ,

T OCH ₂ CH ₂ C ₈ F ₁₇ ) ₂ (OCH (CH ₃ ) ₂ ) ₂ ,

T OCH ₂ CF ₂ CF ₃ ) ₂ (〇H) ₂ , i (OCH (CF ₃ ) ₂ ) ₂ (OH) ₂ ,

i (〇CH ₂ CH ₂ C ₈ F ₁₇ ) ₂ (OH) ₂ ,

i (OCOCF3) ₄ Ti (OCOC ₂ F ₅ ) ₄ ,

i (OCOC ₈ F ₁₇ ) ₄ ,

i (OCOCF3) ₂ (OCH3) ₂ ,

i (OCOC ₂ F ₅ ) ₂ (OCH ₃ ) ₂ ,

i (OCOC ₈ F ₁₇ ) ₂ (OCH3) ₂ ,

i (CF ₃ COCHCOCF ₃ ) ₂ (OCH (CH ₃ ) ₂ ) ₂ >

i (CF ₃ COCHCOOC ₂ H ₅ ) ₂ (OCH (CH ₃ ) ₂ ) ₂ ,

i (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , S i (OCH ₂ CF ₂ CF ₃ ) ₄ , i (OCH ₂ CF ₂ CF ₃ ) ₃ (OCH ₃ ), Si (OCH ₂ C ₃ F _{6 H) 4, i (OCH} 2 C 3 F 6 H) 3 (OCH3),

i (OCHCH ₃ CF ₂ CHFCF ₃ ) ₄ ,

i (OCHCH ₃ CF ₂ CHFCF ₃ ) ₄ ,

i (OCHCH ₃ CF ₂ CHFCF ₃ ) ₃ (OCH ₃ ),

i (OC (CH ₃ ) ₂ CF ₂ CHFCF ₃ ) ₄ ,

i (OC (CH ₃ ) ₂ CF ₂ CHFCF ₃ ) ₃ (OCH ₃ ),

i (OCH ₂ CH ₂ C ₈ F ₁₇ ) ₄ ,

i (OCH ₂ CH ₂ C ₈ F ₁₇ ) ₃ (OCH ₃ ),

i (OCOCF3) ₄ ,

i (OCOC ₈ F ₁₇ ) ₄

 What.

 When b is 1 in the formula (I):

Si (OCH ₂ CF ₃ ) ₃ , HSi (OCH ₂ CF ₂ CF ₃ ) ₃ ,

Si (OCH (CF ₃ ) ₂ ) ₃ , HSi (〇CH ₂ CH ₂ C ₈ F ₁₇ ) ₃ , Si (OCH ₂ CF ₂ CF ₃ ) ₂ (OCH ₃ ),

Si (〇CH (CF ₃ ) ₂ ) ₂ (OCH ₃ ),

Si (〇CH ₂ CH ₂ C ₈ F ₁₇ ) ₂ (OCH ₃ ), HSi (OCH ₂ CF ₂ CF ₃ ) ₂ (OH),

HSi (OCH (CF ₃ ) ₂ ) ₂ (OH),

HSi (OCH ₂ CH ₂ C ₈ F ₁₇ ) ₂ (OH),

HSi (OCOCF ₃ ) ₃ , HSi (OCOC ₂ F ₅ ) ₃ ,

HSi (〇COC ₈ F ₁₇ ) ₃ ,

HSi (OCOCF ₃ ) ₂ (OCH ₃ ),

HSi (OCOC ₂ F ₅ ) ₂ (OCH ₃ ),

HSi (OCOC ₈ F ₁₇ ) ₂ (OCH ₃ ),

CH ₃ Si (OCH ₃ ) ₃ ,

₇)CH ₃ Si (OCH ₂ CF ₃ ) ₃ CH ₃ Si (OCH ₂ CF ₂ CF ₃ ) ₃ , CH ₃ Si (OCH (CF ₃ ) ₂ ) ₃ , CH ₃ Si

₇ )

CH ₃ S i (OCH ₂ CF ₂ CF ₃ ) ₂ (OCH ₃ ),

CH ₃ S i (OCH (CF ₃ ) ₂ ) ₂ (OCH3),

CH3S i (OCH ₂ CH ₂ C ₈ F ₁₇ ) ₂ (OCH ₃ ),

CH ₃ S i (OCHCF ₂ CF ₃ ) ₂ (OH)

CH ₃ S i (OCH (CF ₃ ) ₂ ) ₂ (OH),

CH ₃ S i (OCH ₂ CH ₂ C ₈ F ₁₇ ) ₂ (OH),

CH ₃ S i (OCOCF3) ₃ , CH ₃ Si (OCOC ₂ F ₅ ) ₃ ,

CH, S i (OCOC ₈ F ₁₇ ) ₃ ,

CH ₃ S i (OCOCF3) ₂ (OCHg),

CH ₃ S i (OCOC ₂ F ₅ ) ₂ (OCH ₃ ),

CH, S i (OCOC ₈ F ₁₇ ) ₂ (OCH3),

H ₂ N (CH ₂ ) ₃ Si (OCH ₂ CF ₃ ) ₃ ,

H ₂ N (CH ₂ ) ₃ Si (OCH ₂ CF ₂ CF ₃ ) ₃ ,

H ₂ N (CH ₂ ) ₃ Si (〇CH (CF ₃ ) ₂ ) ₃ ,

H ₂ N (CH ₂ ) ₃ Si (OCH ₂ CH ₂ C ₈ F ₁₇ ) ₃ ,

H ₂ N (CH ₂ ) ₃ Si (OCH ₂ CF ₂ CF ₃ ) ₂ (〇CH ₃ ),

H ₂ N (CH ₂ ) ₃ Si (〇CH (CF ₃ ) ₂ ) ₂ (OCH ₃ ), X

CH ₃ 0 (CH ₂ CH ₂ 0) g (CH _{2 3} s OCH ₂ CH ₂ C ₈ F ₁₇ ) ₂ (OCH ₃ )

CH, O (CH ₂ CH ₂ 0) g (CH _{2 3} s OCH ₂ CF ₂ CF ₃ ) ₂ (OH),

CH3O (CH ₂ CH ₂ 0) g (CH _{2 3} s OCH (CF ₃ ) ₂ ) ₂ (OH),

CHqO (CH ₂ CH ₂ 0) g (CH _{2 3} s 〇CH ₂ CH ₂ C ₈ F ₁₇ ) ₂ (OH),

CH ₃ 0 (CH ₂ CH ₂ 0) g (CH _{2 3} s OCOCF3) ₃ ,

CH, O (CH ₂ CH ₂ 0) g (CH _{2 3} s OCOC ₂ F ₅ ) ₃ ,

CH3O (CH ₂ CH ₂ 0) g (CH _{2 3} s OCOC ₈ F ₁₇ ) ₃ ,

CH.O (CH ₂ CH _z O) g (CH _{2 3} s OCOCF3) ₂ (OCH ₃ ),

CH3O (CH ₂ CH ₂ 0) g (CH _{2 3} s OCOC ₂ F ₅ ) ₂ (OCH3),

CH3O (CH ₂ CH ₂ 0) g (CH _{2 3} s OCOC ₈ F ₁₇ ) ₂ (OCH3)

 (Where g is an integer of 00

CH ₂ C (CH ₃ ) co ₂ (CH ₂ ) ₃ Si (OCH ₂ CF ₃ ) ₃ ,

CH ₂ C (CH ₃ ) co ₂ (CH ₂ ) ₃ Si (OCH ₂ CF ₂ CF ₃ ) ₃ ,

CH ₂ C (CH ₃ co ₂ (CH ₂ ) ₃ Si (OCH (CF ₃ ) ₂ ) ₃ ,

CH ₂ C (CH ₃ ) co ₂ (CH _{2 3} Si (OCH ₂ CH ₂ C ₈ F ₁₇ ) 3,

CH ₂ c (CH ₃ ) CO ₂ (CH ₂ ) ₃ Si (OCH ₂ CF ₂ CF ₃ ) ₂ (OCH ₃ ),

_{CH 2 C (CH 3) co} 2 (CH 2) 3 Si (OCH (CF 3) 2) 2 (OCH3),

CH ₂ C (CH ₃ ) co ₂ (CH ₂ ) ₃ Si (OCH ₂ CH ₂ C ₈ F ₁₇ ) ₂ (OCH ₃ ),

CH ₂ c (CH ₃ ) co ₂ (CH ₂ ) ₃ Si (OCH ₂ CF ₂ CF ₃ ) ₂ (OH),

CH ₂ C (CH ₃ ) co ₂ CH ₂ ) ₃ Si (OCH (CF ₃ ) ₂ ) ₂ (OH),

CH ₂ C (CH ₃ ) co ₂ (CH ₂ ) ₃ Si (OCH ₂ CH ₂ C ₈ F ₁₇ ) ₂ (OH),

CH ₂ C (CH ₃ ) co ₂ (CH ₂ ) ₃ Si (OCOCF3) ₃ ,

CH ₂ C (CH ₃ ) co ₂ (CH ₂ ) ₃ Si (OCOC ₂ F ₅ ) ₃ ,

CH ₂ C (CH ₃ ) co ₂ (CH ₂ ) ₃ Si (〇COC ₈ F ₁₇ ) ₃ ,

CH ₂ c (CH ₃ ) co ₂ CH ₂ ) ₃ Si (OCOCF3) ₂ (OCH3),

CH ₂ C CH ₃ ) co ₂ (CPi ₂ ) ₃ Si (〇C〇C ₂ F ₅ ) ₂ (〇CH ₃ ),

CH ₂ C CH ₃ ) co ₂ CH ₂ ) ₃ Si (〇COC ₈ F ₁₇ ) ₂ (OCH3) In addition, as the oligomers or oligomers, the oligomers or linear oligomers such as linear, branched, cyclic, and three-dimensional are exemplified. can give . The degree of polymerization of the oligomer or the oligomer is preferably from 2 to: 1000, and more preferably from 4 to: 100. As the degree of polymerization decreases, the boiling point of the oligomers or oligomers tends to be low, and the oligomers or oligomers tend to volatilize during coating and are incorporated into the coating film It becomes difficult. If the degree of polymerization exceeds 1000, it becomes difficult to control the degree of polymerization during synthesis, and the viscosity of the oligomer or oligomers tends to increase, resulting in poor workability. There is an inferior tendency. The polymerization degree of the oligomer and the oligomer can be controlled by the molar ratio of the water to be reacted and, for example, the organometallic compound represented by the formula (I). For example, when [H ₂ O] / [organometallic compound represented by the formula (I)] is reacted at a mole ratio in the range of 0.4 to 0.95, polymerization occurs. Oligomers or kooligomers having a degree of about 2 to 20 can be obtained. In addition, by setting the mole ratio in the range of 0.94 to 2.0, an oligomer or a polymer having a degree of polymerization exceeding 20 can be obtained. It is. The composition ratio (mol) of a unit constituting a coco ligomer obtained by using two kinds of organometallic compounds represented by the formula (I) as the coco ligoma The ratio is preferably 1 Z 9 to 9/1.

The GPC molecular weight (value converted into polystyrene using tetrahydrofuran as an eluent) of an oligomer or a cooler is 500-500 by weight average molecular weight. A value of 10,000 is preferred, and a value of 1,000 to 5,000 is even more preferred. As the molecular weight decreases, the effect of hydrophilization decreases, and when the molecular weight exceeds 10,000, gelation tends to occur during synthesis and during storage. The organometallic compound represented by the above formula (I) can highly hydrophilize the surface of a coating film by the action of its hydrolyzable group, and has anti-bioadhesive and anti-fouling properties. It is possible to provide a coating composition having excellent adhesion, low chargeability and anti-fog property.

In the organic metal compound represented by the formula (I), at least ^{one of} R ¹ and R ² is CF ₃ CHFCF ₂ CH ₂ , CF ₃ CHF CF ₂ CHCH ₃ or CF ₃ CHFCF ₂ C (CH ₃ ) ₂ , for example, has excellent surface enrichment, reproducibility of surface hydrophilicity, and blocking resistance. The effect is obtained.

 In addition, the content of fluorine atoms in the organometallic compound represented by the formula (I) is at least 5% by weight, preferably 15 to 60% by weight. As a result, for example, effects such as excellent surface concentrating property and reproducibility of surface hydrophilization can be obtained.

 This is also true because in formula (I), a is 4, b and c are 0, and M is Si and an organometallic compound having a fluorine atom. In this case, excellent effects such as excellent appearance of the coating film, resistance to dulling, and resistance to alkaline can be obtained.

 Another component of the present invention, a resin for a binder (b), is basically a film-forming agent or a film-forming agent for retaining a hydrolyzable organic metal compound (a). Works as a matrix for molded products.

As such a resin (b), a solvent-soluble resin is preferable because it is easy to form and form a coating film. Solvent-soluble resins include, for example, fluororesin, thermoplastic acrylic resin, acrylpolyol resin, acrylsilicon resin, and fluorosilicone resin. Examples include non-fluorinated solvent-soluble resins such as silicone resin and inorganic materials. Among the non-fluorine-based solvent-soluble resins, thermoplastic acrylic resin, acrylic polyol resin, and inorganic materials have been used from the viewpoint of their use results. I like it.

 Although the solvent-soluble fluororesin used in the present invention has been known in the art, it is known that the ethylene-tetrafluoroethylene copolymer (ETFE) Highly hydrophobic, similar to heat-meltable fluororesins insoluble in solvents such as tetrafluoroethylene copolymers and other solvents such as hexafluoropropylene copolymer (FEP) However, there is a similar problem in terms of the ability to prevent adhesion to living bodies and contamination.

 When using a fluorine resin that is soluble in an organic solvent, not only can low-temperature processing in a solution state be possible, but also because of the presence of an organic solvent, a hydrolyzable group can be used. This is preferable because the organometallic compound containing sulphate is collected on the surface during film formation, and the action of hydrophilizing the surface is strengthened.

 Solvent-soluble fluororesins that can be particularly preferably used in the present invention include, among conventionally known organic solvent-soluble fluororesins,

 (1) a force having a fluorine content of 60% by weight or more, preferably 63% by weight or more, particularly 65 to 75% by weight;

 (2) Is the refractive index less than 1.40, preferably 1.39 ~: 1.25?

(3) The crystal melting point is 100-180t, preferably 100-: 150t:

 (4) A force that is amorphous and has a glass transition point of 70 to 250, preferably 70 to 180.

(5) Equation (11), Equation (III) or Equation (IV;), ie, Equation ( ¹¹⁾ : _f FF,

 4- c− cX- 〇 o

C

CF ₃ CF ₃ Expression (in)

 CF

CF o-CF CF

 O-CF, or formula (IV)

で示 さ れる 環状構造 を 有 し て い る か 、 ま た は CF ₃ CF ₃

Has a cyclic structure represented by

(6) Tetrafluoroethylene (TFE) 10 to 50 mol%, Hexafluoropropylene (HFP) 0 to 50 mol%, and vinylidenefluoro Ride (VdF) 90 ~: 10 mol%, preferably TFEZ HFP No. VdF is 10 ~ 30 no. 3 ~ 40/77 ~ 40 force.

 Particularly preferred are those that have more than one of these properties.

 Specifically, the following fluororesins are required, but not limited thereto.

 (A) Fluororesins having a ring structure of the above formula (II) (USP 3,865,845, USP 3,978,030, USP 4,533,741, etc.) .

As other monomers, fluorine-based, hydrocarbon-based, and other monomers having radical polymerizability can be used, and in particular, TFE , Perfluorovinyl ether, vinylidene fluoride, bifluoride, black mouth trifluoroethylene, etc. . This solvent-soluble fluororesin has a fluorine content of 60% by weight or more, a refractive index of 1.39 to 1.27, is amorphous, and has a glass transition. point Is 70-250t: Commercially available products include Teflon AF series (manufactured by Dupont).

 (A) Fluororesins having a ring structure of the formula (III) (for example, JP-A-63-238111, JP-A-63-238115).

 As other monomers, fluorine-based, hydrocarbon-based, and other monomers having radical polymerizability can be used. For example, TFE, perfluorovinyl ether, VdF, vinyl fluoride, and tri-fluoroethylene in the mouth can be used. This solvent-soluble fluororesin has a fluorine content of 60% by weight or more, a refractive index of 1.39 to: I.27, and is amorphous and glassy. The transition point is 70-250. Examples of commercially available products include a site manufactured by Asahi Glass Co., Ltd.

 (Ii) A fluorine resin having a ring structure represented by the formula (IV) (eg, Japanese Patent Application Laid-Open No. 63-238115).

 As other monomers, fluoropolymers, hydrocarbons, and other monomers that have a radical polymerizability can be used. Specifically, for example, TFE , Perfluorovinyl ether, vinylidene fluoride, vinyl fluoride, tri-fluoroethylene, etc. This solvent-soluble fluorine resin has a fluorine content of 60% by weight or more, a refractive index of 1.39 to: 1.27, and is amorphous and glass. The transition point is 70-250. As a commercially available product, there is a site manufactured by Asahi Glass Co., Ltd.

 (D) TFEZ HFP / VdF copolymer (Japanese Patent Publication No. Sho 60-190353, Japanese Patent Publication No. 61-123646, Japanese Patent Publication No. Sho 62-104877, Japanese Patent Publication No. 1-225653, Japanese Patent Publication No. 1-223151 bulletin etc.).

As described above, the composition ratio of the monomer is TFE 10 to 50 %, HFP 0 ~ 50mol% and VdF 90 ~: 10mol%, preferably TFE / HFPZ VdF 10 ~ 30Z 3 ~ 40/77 ~ 40 force It is a thing. This copolymer may be modified with an isocyanate compound or the like. This solvent-soluble fluororesin has a fluorine content of 60% by weight or more, a refractive index of 1.39 to: 1.27, and a crystal melting point of 100 to: I80. belongs to . Examples of commercially available products include THV series (manufactured by Sumitomo SLIM Co., Ltd.).

 In addition, as a solvent-soluble fluororesin that can be used, for example, a fluorosol having a hydroxyl group or a carboxyl group which is soluble in a solvent is used. Thinner copolymers are required. Specific examples include, for example, Japanese Patent Publication No. 60-21686, Japanese Patent Publication No. 3-121107, Japanese Patent Publication No. 4-279612, Japanese Patent Publication No. 4-28707, Japanese Patent Publication No. 2-232221. Such publications as described in each gazette are given. The number average molecular weight (according to GPC) of the copolymer is from 1,000 to 100,000, preferably from 1500 to 30,000. If the molecular weight is less than 1,000, the curability and weather resistance tend to be insufficient, and if it exceeds 100000, there is a tendency for problems in workability and coatability.

 The hydroxyl value of the copolymer is from 0 to 200 (mgKOH / g), and preferably from 0 to: ISO mgKOHZg. When the amount of the hydroxyl group is reduced, curing tends to be poor, and when it exceeds 200 (mgKOHZg), a problem tends to occur in the flexibility of the coating film.

The acid value of the copolymer is from 0 to 200 (mgKOH / g), and from 0 to; OO (mgKOHZg) is even more preferred. If the acid value is low, curing tends to be poor, and if the acid value exceeds SOOimgKOHZg), the coating film will be flexible. There is a tendency for problems with gender.

 As one of the copolymers, a fluororefin-based copolymer is used from the viewpoints of bioadhesion-preventing property, anti-contamination-adhesion property, decontamination-removing property, and anti-pollution property. You can do whatever you want.

 Examples of the copolymer include Zefful manufactured by Daikin Industries, Ltd., Lumifuron manufactured by Asahi Glass Co., Ltd., and Cefra manufactured by Central Glass Co., Ltd. Commercial products such as LeCoat, Fluoronet manufactured by Dainippon Ink and Chemicals Inc., and Zaflon manufactured by Toa Gosei Co., Ltd. are available.

 In addition, as the non-fluorine-based solvent-soluble resin, for example, a special resin is used.

 First, thermoplastic acrylic resins include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methyl acrylate. Methacrylic acid esters such as acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and butyl acrylate Homopolymers of acrylates such as latex, copolymers of these, or copolymers of these with a copolymerizable monomer. It is. Examples of the copolymerizable monomer include aromatic biel compounds such as styrene, acrylonitrile, various vinyl ethers, aryl ethers, and the like. Various vinyl compounds such as vinyl esters, unsaturated monomers having a functional group such as a carboxyl group, an amino group, an epoxy group, and the like are required. .

 Examples of the thermosetting acrylic resin include acrylpolyol resin and acrylsilicon resin.

Examples of the acrylic polyol resin include (a) a hydroxyl group-containing (meth) acrylic acid ester and hydroxyvinyl. Hydroxyl-containing ethylenically unsaturated monomers such as ether and aryl alcohol, and (b) hydroxyl-free olefins; Vinyl ether, aryl ether, vinyl ester, pulp vinyl ester, (meta) acrylic acid ester, vinyl Aromatic compounds, (meta) acrylonitrile, unsaturated monomers containing carboxyl groups, unsaturated monomers containing epoxy groups, and amino groups A polymer with a hydroxyl-free unsaturated monomer such as an unsaturated monomer is used.

 As described above, the acrylic polyol resin may have a hydroxyl group, a carboxyl group, an epoxy group, or an amino group.

 The hydroxyl value of the acrylic polyol resin is from 0 to 200 (mgKOH / g), and preferably from 0 to 100 (mgKOHZg). If the hydroxyl value is too low, curing tends to be poor, and if it exceeds SOOimgKOHZg), there is a problem in the flexibility of the coating film. There is a direction.

 The acid value of the acrylic polyol resin is 0 to 200 (mgKOH / g), and more preferably 0 to 100 (mgKOH / g). It is better. If the acid value is too low, curing tends to be poor, and if it exceeds 200 (mgKOH / g), there is a problem in the flexibility of the coating film. Tend .

 Acrylic polyol resins include, for example, Dianal made by Mitsubishi Rayon Co., Ltd., and Dainippon Ink Chemicals Co., Ltd. This product uses marketed products such as Acrylic, Hitachi, Ltd., Hitaroid Co., Ltd. and Mitsui Toatsu Kagaku Co., Ltd. And are confused.

The aforementioned acrylic silicone resin has, for example, at least one silane group and one radically polymerizable unsaturated group in one molecule. Replace the existing acrylic monomer with the hydroxyl It may be one which has been polymerized with the group-containing ethylenically unsaturated monomer (a) and Z or its hydroxyl-free unsaturated monomer (b). .

 The acrylic silicone resin may have a hydrolyzable silyl group, a hydroxyl group, or an epoxy group.

 Acrylic silicone resins include commercially available products such as Zemrack manufactured by Kanegafuchi Kagaku Kogyo Co., Ltd. and Krymar Co., Ltd. manufactured by Sanyo Kasei Kogyo Co., Ltd. Can be used.

 In the present invention, the non-hydrogen-containing non-hydrolyzable group-containing metal (such as Si, Ti, A1, etc.) is used as the coating resin. Inorganic materials such as non-hydrolysable group-containing organopolysiloxanes, non-fluorine-containing metals (such as Si, Ti, and A1) and alcohols can also be used. .

 The inorganic materials include, for example, Toray Industries, SH, SR and DC series manufactured by Silicone Corporation, and Shin-Etsu Chemical Co., Ltd. In addition to silicone resins such as KR series (KR_255, KR-300, KR-500, KR-212) and X-22-8904, manufactured by Gunze Sangyo Co., Ltd. Launched Ecotone, Nihon Synthetic Rubber Co., Ltd. glass power, Tobe Co., Ltd. porcelain, Nihon Yushi Yushi Co., Ltd. Belclean, Belher Do, Ajinomoto Co., Inc.'s plan, Nihon Soda Co., Ltd.'s organic titanium, Kawaken Fine Chemical Co., Ltd.'s Aluminum Arylate and aluminum chelate compounds, Gilco Alcoxide manufactured by Hokuko Chemical Industry Co., Ltd., manufactured by Nihon Nikka Co., Ltd. Duplicate Commercially available products such as inconsistent silicone oil and MMCA can be used.

Examples of the fluorine-containing silicone resin include, for example, those described in JP-A-4-1279612. .

 Epoxy resins include, for example, Epikote Series manufactured by Yuka Shell Co., Ltd.

 Polyester resins and alkyd resins include, for example, Bekkozol series and super-products manufactured by Ink Chemicals Co., Ltd. of Japan. -Becco Rose Series, Stille Resole, Becco Light Series, Sino, etc. Ichigo Kakko Kogyo Co., Ltd.'s full-kid series and Esper series, such as the Becco Light Series and the Burnock Series. The throat is destroyed.

 Further, as the amino resin, for example, Pekka Min Series and Super Beck Min Series manufactured by Dainippon Ink and Chemicals, Inc. And other products, such as Melanseries, manufactured by Hitachi Chemical Co., Ltd .; Cymer Series, manufactured by Mitsui CyAnamid Inc .; and Mitsui Toatsu Chemicals, Inc. Such as the New Series made by Sanwa Chemical Co., Ltd. and the Nikki Rack Series made by Sanwa Chemical Co., Ltd.

 These may be used alone or in combination.

 The resin composition of the present invention contains a hydrolysis accelerator (c) in order to promote hydrolysis and promote hydrophilicity, and to quickly and effectively exert a bioadhesion preventing ability. You may.

 Metal chelates such as aluminum chelates, titanium chelates, and zirconium chelates are examples of hydrolysis promoters. In addition to compounds, organic tin compounds, organic acid phosphate esters, organic titanate compounds, reaction products of acid phosphate esters with amines, saturated or unsaturated compounds Examples include polyvalent carboxylic acids, their anhydrides, and organic sulfonic acids.

The amount of the hydrolysis accelerator (c) to be added is about 0.01 to 20 parts with respect to 100 parts of the resin (b), and 0.01 to 10 when the pot life is long. Department The degree is preferred.

 In the present invention, more importantly, the action of preventing the attachment of aquatic organisms or physiological substances, particularly diatoms, without releasing harmful substances such as heavy metals. A known compound having the formula (I) may be used in an amount of 50 parts or less, preferably 0.05 to 50 parts, per 100 parts of the solid component of the resin (b). Examples of commercially available diatom adhesion preventive agents include, for example, Net King 300 manufactured by Keiai Densei Co., Ltd., Net King 400, and Tobe Co., Ltd. Clean fish 5000 etc. are required.

 In addition, a known repellent that prevents the access of aquatic organisms without releasing harmful substances such as heavy metals and the like is used. Preferably, 0.05 to 50 parts may be added. Such biorepellents have the formula:

R ⁵

(Wherein, R ⁵ is the same or different, and each is an alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, or all or a part of halo. A nitrogen-containing amide-type repellent represented by an alkyl group or a hydrogen atom substituted by a gen atom, formula:

 (Wherein X is H or a halogen atom, preferably C1 F or F), a nitrogen-containing amide-type repellent represented by the formula:

(式 中 、 R⁵お よ び X は前記 と 同 じ ） で示 さ れ る フ ラ ノ ン 型忌避剤があ げ ら れ、 市販 の忌避剤 と し て は、 た と え ば ケィ ア イ イ匕成 （株）製 の ノ ィ オ ダ ン G 、 バ イ オ ダ ン GPA、 バイ オ ク リ ン P 、 K S— 339な ど が あ げ ら れ る 。 R ⁵ X

(Wherein, R ⁵ and X are the same as described above), and flavonoid-type repellents represented by the formula (1) are exemplified. Examples include BioDan G, BioDan GPA, BioClin P, and KS-339 manufactured by Idanari Co., Ltd.

 The combined use and addition of these diatom adhesion inhibitors and biological repellents can further extend the effects of the present invention.

 When the resin (b) is a curable resin in the present invention, a curing agent is added. Such a curing agent may be appropriately selected from known curing agents depending on the crosslinking reactive group of the curable resin. For example, in the case of a fluorine-based polyacryl polyol resin, isocyanates are preferred as low-temperature curing agents, and commercial products are preferred. Examples include the Colony Series manufactured by Japan Polyurethane Industry Co., Ltd., and the LTI manufactured by Kyowa Hakko Co., Ltd.

 The compounding amount is preferably about 0.1 to 30 parts with respect to 100 parts of the curable resin (b).

 In the present invention, as the resin (b), a resin that is soluble in an organic solvent is preferred. In such a case, an organic solvent is added to the composition. The organic solvent may be fluorine-based or non-fluorine-based, but as the resin (b), a fluorine-containing resin, particularly a fluorine-containing resin having a fluorine content of 60% or more is used. When used, fluorine-based organic solvents are preferred in terms of the solubility of the fluororesin, the transparency of the obtained film, and the like.

Examples of the fluorine-based organic solvents include CF ₃ CH ₂ OH, F (CF ₂ ) ₂ CH ₂ （H, (CF ₃ ) ₂ CHOH, F (CF ₂ ) ₃ CH ₂ OH, F Fluorine alloys such as (CF ₂ ) ₄ C ₂ H ₅ OH, H (CF ₂ ) ₂ CH ₂ 〇H, H (CF ₂ ) ₃ CH ₂ OH, H (CF ₂ ) ₄ CH ₂ 〇H Cooling solvent; Emissions zero emissions, meta key sheet les down to key support full o la I de, etc. containing full Tsu-containing aromatic _{solvents; CF 4 (HFC- 14),} CHC1F 2 (HCFC- 2 2), CHF 3 _{(HFC - 23), CH 2} CF 2 (HFC- 32), CF 3 CF 3 (PFC- 116), CF 2 C1CFC1 2 (CFC- 113), C 3 HC1F 5 (HCFC- 225), CH 2 FCF 3 (H FC _ 134a), CH 3 CF 3 (HFC- 143a), CH 3 CHF 2 (HFC - 152a), CH 3 CC1 2 F (HCFC- 141b), CH 3 CC1F 2 (HCFC- 142b), C 4 F ₈ (PFC-C318), etc. full O filtration one port emissions-based solvents, etc. nitrous up et al are of, was one or the ∎ you can by used by mixing on two or more kinds.

Non-fluorine-based organic solvents include, for example, hydrocarbons such as xylene, toluene, solbeso 100, solirebeso 150, and hexane. Solvents: methyl acetate, ethyl acetate, ethyl acetate, ethyl glycol acetate monomethyl ether, ethyl acetate glycol monoethyl acetate Chill ether, ethyl acetate alcohol monobutyrate ether, diethyl acetate alcohol monomethyl ether, ethyl acetate Long glycol monoethyl ether, diethyl alcohol monobutyrate ether, ethyl alcohol methyl alcohol, acetic acid Ester-based solvents such as ethylene glycol; dimethyl ether, dimethyl ether Relay, dibutyl ether, ethyl glycol monomethyl ether, ethyl glycol monoethyl ether, ethyl Render color monobutyl ether, ethyl alcohol dimethyl ether, ethyl alcohol dimethyl ether , Ethylene glycol, butyril-tele, ethylene glycol, monomethyl ether, polyethylene glycol Nozzle ethers, polyethylene glycol monobutyrates, polyethylene glycols, methyl ethers, jewelry Calendar Call Jewelry Ether solvents such as toluene, diethyl glycol, dibutyl ether, tetrahydrofuran, etc .; methyl ethyl ketone , Methylisobutyl ketone, acetone, and other ketone-based solvents; N, N-dimethyl acetate amide, N-methyl acetate amide, For example, set amide, N, N-dimethylformamide, N, N-methylformamide, N-methylformamide, etc. Amide-based solvents; sulphonic acid ester-based solvents such as dimethyl sulfoxide; methanol, ethanol, and isoprono Knoll, rubber, ethylene glycol, ethylene glycol, polyethylene glycol (weight: 3 to 100) What's a Koh was Lumpur-based Solvent, etc. one or two mixed-solvent on more kinds is Ru been Oh up, et al.

 A mixture of a fluorine-based solvent and a non-fluorine-based solvent may be used.

 Of these, the above-mentioned various fluorine-based solvents, ketone-based solvents, and ester-based solvents are preferred in view of solubility, coating appearance, and storage stability. In particular, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cellosolve acetate, butyric acetate, ethyl acetate , Perfluorobenzene, metahexylene fluoride, HCFC_225, CFC-113, HFC-134a, HFC-143a, HFC-142b are preferred. (B) As for the combination ratio of the organic metal compound, the organic metal compound is 0.1 to 50 parts per 100 parts of the resin (b), and 1 to 50 parts. Preferably it is 30 copies. If the amount is less than 0.1 part, the water-repellent effect on the surface (anti-bioadhesive property) will be reduced. descend .

When an organic solvent is used, the mixing ratio is 1 to 2000 parts with respect to 100 parts of the solvent-soluble resin (b). It is more preferable that the amount be 100 to 150 parts in view of shape, film forming property, curability, and appearance of the coating film. In addition, an alcohol-based solvent is used as an organic solvent, and the above-mentioned curing agent has a high reactivity with alcohol, such as a room-temperature-curable isosilicate. In such a case, it is preferable that the alcohol-based solvent is 1 to 15 parts, and the type of the alcohol-based solvent is 2 or 3 grade. Le Colle is preferred.

 The resin composition of the present invention may be used to form a coating film on the surface of a product or structure by painting, or it may be a casting method or an extrusion method. It may be molded as a single molded product such as a film, sheet, or tube.

 Therefore, depending on the method of application and the purpose, it may be used as a coating film or as a molded product, but according to the respective application, a known additive may be blended as appropriate. It is also good. Hereinafter, such optional additives will be described, but such components are described in WO97 / 11130 brochure. Anything can be used.

 Additives include, for example, surface conditioners, pigments, pigment dispersants, thickeners, leveling agents, defoamers, film-forming aids, ultraviolet absorbers, HALS, and anti-glare. Inhibitors, fillers, colloidal silicas, antifungal agents, silane coupling agents, anti-skinning agents, antioxidants, flame retardants, anti-sagging agents, antistatic Agents, protective agents, and water-soluble resins (polyvinyl alcohol, polyethylene oxide, etc.).

The surface conditioner not only prevents unevenness after painting and improves leveling properties, but also contributes to preventing the color from being separated in the color paint and preventing color floating. The addition is optional, and if necessary, a known one may be used. In addition, when an appropriate antifoaming agent is added, the defoaming property is improved without significantly impairing the surface hydrophilicity. Suitable antifoaming agents include, for example, long-chain fluoroalkyl-modified siloxanes of Zeffle GH-200 (manufactured by Daikin Industries, Ltd.). Fluorosilicone-based defoamers such as siloxane-based defoamers such as FA-600 and FS-126265 (both manufactured by Shin-Etsu Chemical Co., Ltd.) And silicone compound-based antifoaming agents, silicone-based antifoaming agents, and acrylic-based antifoaming agents.

 As described above, the resin composition of the present invention may be used for forming a coating film as a coating composition, or may be used as a molding material for a film, a sheet, or a tube. It may be molded into any shape. Various painting methods can be used, such as spraying, brushing, rollers, curtains, rolls, and dips. Further, as the coating composition, various forms such as clear, solid, and compounding of filler (filament) can be adopted. Examples of the molding method include a casting method, an extrusion method, an injection method, and a blow method.

 After being applied or formed by these methods, they are dried at a temperature from room temperature to 250, preferably at a temperature from room temperature to 180. Thus, a molded article such as a coating film or a film having a surface having a hydrophilicity can be obtained.

The thickness of the coating film may be determined as appropriate according to the application and use environment. It can be selected from the range of ~ 2 mm. In addition, depending on the application and environment, the surface of the base material (resin (b)) may be subjected to blast treatment, corona discharge treatment, ozone treatment, etc. Alternatively, a middle coating layer may be provided. Especially for marine applications, durability can be improved by performing such treatments as desired. The surface of the coating film or molded article formed by the composition of the present invention is easily and highly hydrophilized, and does not allow aquatic organisms and physiological substances to adhere and grow. As a result, it is possible to obtain anti-fouling properties, not to adhere lipophilic dirt, and to achieve anti-fouling properties. In addition, when fluorocarbon resin is used, it has a high degree of weather resistance, chemical resistance, optical properties (such as transparency), mechanical properties (strength and elongation), It has excellent adhesiveness, heat resistance, and heat yellowing resistance.

 The resin composition of the present invention provides a highly hydrophilic coating layer or film having a surface contact angle with water of less than 70 degrees and even 55 degrees or less. You can do it.

 As described above, the resin composition of the present invention can be applied to various water surfaces or objects or structures used in water regardless of seawater or freshwater.

 In particular, when used in a marine environment with a flow rate exceeding 100 mm / s and a flow rate of 300 mm / second or more, excellent aquatic organism adhesion prevention ability is exhibited. At this flow velocity, aquatic organisms such as Fujipo are difficult to maintain their life in less than 100 mmZ seconds, and in power plants and ships, etc., they are used at speeds exceeding that flow velocity. It is a stipulated criterion because it often occurs, and it is required that the attachment of aquatic organisms in this environment can be effectively prevented.

According to the present invention, the adhesion rate of the Fujibo is less than 15%, preferably less than 5%, especially less than 5% in the following zippo adhesion test. Can provide goods or structures that are zero percent. Fujipo adhesion test Water tank: 150mm X 100mm X 200mm (inside dimensions)

Seawater: 3 liters

Test organism: Buchius fondapo (Balanus kondakovi)

 Population 600

Test temperature: 22 ~ 24:

Examination period: 60 days

 Furthermore, the resin composition of the present invention not only can prevent the aquatic organisms from adhering, but also can easily remove the aquatic organisms even if they adhere and grow to some extent. Can provide molded products. For example, it is possible to provide an article or a structure having a residual ratio of less than 2%, and preferably zero%, in the following flushing water removal test. Wear .

 Record

Test sample: Structural sample subjected to the above-mentioned Fujipo adhesion test for 60 days

Rinse conditions: Dispense tap water at right angles to the sample surface for 20 seconds so that the water pressure is 0.3 ± 0.05MPa on the sample surface.

 The present invention also relates to a medical member, film, or sheet having a coating layer obtained from the resin composition of the present invention on the surface as described above. The present invention relates to a medical member comprising a molded article having a shape such as a tube or a tube.

 Further, the resin composition is used on the surface of water or in water, or is obtained from the resin composition on one surface of a medical marking film, that is, one surface of a resin film. The present invention also relates to a film having a coating layer and a pressure-sensitive adhesive layer on the other surface.

The resin film used as the base material for such a marking film is not particularly limited as long as it has excellent water resistance, strength, and flexibility. No. A specific example is salt, for example. Vinyl resin, polyester resin, silicone resin, elastomer class, fluorine resin, urethane resin, polyamide resin, poly resin Refines (Polyethylene, Polypropylene, etc.) are required.

 As the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer, conventionally known pressure-sensitive adhesives can be used. Typical examples thereof include epoxy resin-based, amino resin-based, and acrylic resin-based pressure-sensitive adhesives. Adhesives such as lilyl resin, vinyl resin (such as vinyl acetate polymer), curable acrylic resin, and silicone resin are exfoliated. .

 Since the composition of the present invention can be applied to various types of base materials, it prevents bio-adhesion to a wide range of materials and structures and prevents bio-substance adhesion. Can be imparted with durability. Examples of the substrate include a metal-based substrate, a cement-based substrate, a plastic-based substrate, and the like.

 Examples of the metal base material include iron and its chemical conversion products or plating materials, aluminum and its chemical conversion products, stainless steel and the like. And the chemicals to be treated.

 Examples of the cement-based material include cements, limes, cements, concrete, cement cement, and asbestos. Rate, gypsum board, etc. are excavated.

 Examples of the plastic base include polychlorinated vinyls, polyesters, polycarbonates, and acrylics. , Polyolefins, Polystyrenes, Polyurethanes, Polyamides, Nylons, Natural rubbers, Urethanes Such as rubber and ABS resin.

When the base material is a metal-based material, the undercoat paint or the middle paint is applied, for example, and then the paint composition of the present invention is applied. This is because of the anti-corrosion properties and adhesion between phases. I like it. In this case, zinc paint is preferred as the primer. Other examples of the undercoating paint and the intermediate coating paint are preferably epoxy resins (including those having an evening change and a urethane change), vinyls. At least one resin selected from the group consisting of resin (including tar modification and acrylic resin), rubber chloride, polyurethane resin, and phenol resin. It is obtained by kneading commonly used coloring pigments, extender pigments, sedimentation inhibitors, dispersants, curing agents, curing accelerators, diluents, solvents, etc., to the synthetic resin of the species. Paint. In this case, the thickness of each of the base coat and the middle coat is 1! A thickness of up to 2 mm, preferably 5 to 500 μm, is suitable.

 Even when the base material is a plastic base material, the base material used for the metal base material, the cement base material, and the undercoat paint and the intermediate coat paint are applied. Thereafter, the coating composition of the present invention can be applied.

 If the base material is a plastic base material, even if it is a film or a sheet, the coating method is, for example, Gravia Co., Ltd. There are various methods such as the ringing method, doctor blade method, roll coat method, linole roll method, and Jay-Nay coat method. In the case of these coating methods, the coating film thickness should be from 1 to 25111, preferably from 1 to 15 μm, in terms of coating appearance and paintability. It is.

 Next, the present invention will be described based on synthetic examples and embodiments, but the present invention is not limited to only such embodiments. In the following, “parts” and “%” are weight parts and weight%, respectively.

Example 1

As resin (b), TFE-based hardening resin Varnish (Daikin Industries Zeffle GK-500 manufactured by Co., Ltd. Resin concentration 60%, resin hydroxyl value eOmgKOHZga or less, called “TFE copolymer”), and a polyisocyanate curing agent (LTI manufactured by Kyowa Hakko Co., Ltd.) ) In such an amount that the NCOZ OH equivalent ratio becomes 1.0, and further as a hydrolyzable group-containing organometallic compound of the formula (V):

 OR

RO- ^ i O ^ — R

 OR

(Wherein R is CH ₃ and CH ₂ C ₂ F ₅ and the ratio of CH ₂ C ₂ F ₅ Z CH ₃ is 0.3) to 1.5 PHR (resin (b ) 100 parts by weight (parts by weight) Same as below)

(To be described later) was added to 0.015 PHR (the composition of the mixture is shown in Table 1). This resin varnish was diluted with butyl acetate until the NK2 cup viscosity became 15 seconds to prepare a paint varnish.

 AM-712 treated chemical aluminum plate is coated three times with Nippon Paint Co., Ltd. epoxy resin paint (Hibon 20 Ace) to dry film thickness of about 100 / zm. The undercoat layer of DuPont SF, which is a urethane intermediate paint manufactured by Nippon Paint Co., Ltd., is applied twice and dried. Medium coated (dry film thickness of about 70 μπι). The paint varnish obtained above was spray-painted (overpainted) on the middle coat, cured for 1 hour at room temperature, and dried at 80 for 20 minutes. As a result, a test coated plate (dry film thickness: about 30 / m) was prepared.

The degree of hydrophilicity of the coating film (contact angle with water) of this coated plate, prevention of bioadhesion (adhesion of fusipo, adhesion of diatoms, etc.), removal of living organisms (fusipo water washing test, Diatoms, etc.) and environmental impacts (eg, mortality of zippo, heavy metal emissions, etc.) Each method was examined. Table 2 shows the results.

Degree of hydrophilicity of coating film

 Measure the contact angle with water after leaving it outdoors for 7 days (measuring instrument; contact angle meter manufactured by Kyowa Interface Science Co., Ltd.). The smaller the value, the more hydrophilic.

Biofouling prevention

 (Fujibo adhesion test)

 Put the painted plate (150mm x 150mm) in a water tank (150mm x 100mm x 200mm (inner dimensions)) containing 3 liters of filtered seawater in a bag of Mirasse gauze. Place at an angle and soak. 600 dwarf zippo (Balanus kondakovi) larvae are released into the seawater, and a certain amount of diatoms, which is the food of fujippo, is added to the seawater. The larvae of Fujipo are cultivated in 22-24.

 After 60 days from the start of the test, the coated plate is pulled up, and the number of fuspo adhered to the coated plate is measured with a stereoscopic microscope, and the number (n) and the adhesion ratio ((n / 600) ) X 100%].

 (Diatom adhesion)

 Since diatoms are bait for fusipo, the adhesion rate of diatoms on the coated plate 60 days after the fuspo adhesion test was visually observed and the color difference (ΔΕ) Check with.

Visual appearance criteria:

 : Almost no change (no adhesion) from before the test.

 〇: Slightly adhered and deposited, but little change in appearance.

Δ: Slightly adhering and accumulating, and slight change in appearance.

X: Adhesion and deposition were clearly observed, and the initial appearance was impaired. Color difference (ΔE):

Using a color difference meter CR-300 manufactured by Minoru Yu, Inc., the color difference of the painted plate before and after 60 days of the test can be examined. The larger the color difference, the more dirty the surface of the painted board is with diatoms.

Biological removal

 (Fujibo water washing test)

 The coated plate (including all that had no fuspo attached) that had been subjected to the above-mentioned fusippo adhesion test for 60 days was coated with 0.3 ± 0 water on the surface of the lacquered plate. Water was released at a right angle for 20 seconds so that the water pressure became 05 MPa, and washed, and then adhered in the same manner as in the bioadhesion test (remaining). The number of zippo bodies (m), the residual ratio of Fujibo [(mZ600) X 100%], and the residual degree of diatoms (visual appearance and color difference) can be examined.

Environmental impact

 The effects on the seawater side can be examined from the following three viewpoints.

 (Visual appearance)

 Coloring of seawater in the aquarium 60 days after the test for fujipo adhesion test The presence or absence of release of oil can be examined using the following criteria.

 ◎: Coloring and release of oil are not observed.

 X: Coloring and turbidity occur, and release of oil is observed. (Discharge Fujippo Death Rate)

 The number of killed individuals of Fujipo that released the effects of the harmful components eluted from the painted board (k. The killed bodies on the bottom, side, and surface of the painted board) Number) and mortality [(k / 600) X 100%].

 (Amount of metal eluted)

The amount of harmful metals (Cu, Sn, and Zn) harmful to the environment was determined by the high frequency induction plasma method (306 Super, manufactured by Hitachi, Ltd.). Scan. Adjust the concentration of the sample so that the detection limit is 0.1 ppm).

Examples 2 to 9 and Comparative Example 1

 A coating resin resin varnish was prepared in the same manner as in Example 1 except that the components shown in Table 1 were used in the amounts shown in the table. Next, each varnish was coated on a chemically treated aluminum plate (those treated with the same undercoating as in Example 1) as in Example 1 and subjected to the test. A painted plate was prepared. In the same manner as in Example 1, the test coating plate was examined for the degree of hydrophilicity of the coating film, the ability to prevent bioadhesion, the ability to remove the living body, and the degree of environmental impact. Table 2 shows the results.

 In Table 1 and Tables 3, 5, 7, 9, 11, 13, 15, 15 and 17 to 22 described below, the abbreviations are the following substances.

Hydrolyzable organometallic compound (a)

Equation (VI):

 OR

A: p is Ri Ah at 4, R is Ri Oh in CH ₃ your good beauty CH ₂ C ₂ F _5, Ru Oh in CH ₂ C ₂ F ₅ CH ₃ ratio is 0.3 compounds.

B: p is Ri Ah with 4, R is Ri Ah in CH ₃ Contact good beauty _{CH 2 C 2 F 5, CH} 2 C 2 F 5 / CH 3 ratio Ah Ru compound 0.5.

C: A compound in which p is 4, R is CH ₃ and CH ₂ CF ₂ CFHCF ₃ , and the ratio of CH ₂ CF ₂ CFHCF ₃ Z CH ₃ is 0.3.

D: p is Ri Ah with 4, R is Ri Ah in CH ₃ Contact good beauty _{CH 2 CF 2 CFHCF 3, CH} 2 CF 2 CFHCF 3 Z CH 3 ratio Ah Ru compound 0.5.

E: Formula: OR R

R〇 S i O) _ις (S i O

 I I OR OR

(Where R is CH ₃ )

Hydrolysis accelerator (hydrophilizing agent)

 Alumichelate D: Alumichelate compound manufactured by Kawaken Fine Chemicals Co., Ltd.

Surface conditioner

F: In the above formula (VI), p is 4, R is CH ₃ and C ₂ H ₄ (CF ₂ ) ₇ CF ₃ , and C ₂ H ₄ (CF ₂ ) CF A compound having a CH ratio of 0.5.

G: In the above formula (VI), p is 4, R is CH ₃ and C ₂ H ₄ (CF ₂ ) ₇ CF ₃ , and C ₂ H ₄ (CF ₂ ) Compounds with a CF ratio of 0.3.

Example Resin (b) Hardener Organometallic compound (a) Hydrolysis Surface conditioner No. Quantity (PHR) Accelerator (PHR) Amount (PHR)

1 TFE-based polyisosia A 1.5 F 0.015 copolymer

 2 Same as above Same as above A 15 F 0.15

3 Same as above Same as above A 15 1.5 F 0.15

4 Same as above Same as above B 15 G 0.15

5 Same as above Same as above C 15

 6 Same as above Same as above C 15 1.5 F 0.15

7 Same as above Same as above D 15 G 0.15

8 Same as above Same as above E 1.5

 9 Same as above Same as above E 15 1.5

Comparative Example 1 Same as above Same as above Table 2

 Fujibo adhesion test Fujibo washing removal test

 Degree of hydration

 Example organic metal

 Fujitsubo adhesion Diatom adhesion Deposition of diatoms Diatom removal of Fujitsubo mortality

 No.Compound (a)

 Contact with water Visual amount of metal eluted Adhesion Residual residual rate Visual death

 Antenna (degree) Adhesion rate Visual

 Color difference (Δ Ε) Color difference (Δ Ε) Appearance (ppm) Number of individuals _ (%). Number of individuals _ (%) · Number of individuals _ (%) _

 1 A 54 3 0.50 2.12 0 0.00 0.48 0 0.00 ND-(1.5)

 2 A 25 0 0.00 〇 1.88 0 0.00 ◎ 0.39 ◎ 0 0.00 ND (15)

 3 A 23 0 0.00 〇 1.76 0 0.00 ◎ 0.37 ◎ 0 0.00 ND (15)

 4 B 24 1 0.17 〇 1.86 0 0.00 ◎ 0.39 ◎ 0 0.00 ND

(15)

 5 C 25 0 0.00 〇 1.85 0 0.00 ◎ 0.39 ◎ 0 0.00 ND

(15)

 6 C 22 0 0.00 〇 1.77 0 0.00 ◎ 0.37 ◎ 0 0.00 ND

(15)

 7 D 24 0 0.00 〇 1.68 0 0.00 ◎ 0.35 ◎ 0 0.00 ND

(15)

 8 E 57 3 0.50 Δ 2.25 0 0.00 〇 0.68 ◎ 0 0.00 ND (1.5)

 9 E 44 2 0.33 〇 1.88 0 0.00 ◎ 0.39 ◎ 0 0.00 ND

(15)

I Comparative Example ι | 93 135 22.50 X 12 122 20.33 X 10.2 ◎ 0.00 ND

Examples 10 to 18 and Comparative Example 2

 As the resin (b), a thermoplastic VdF copolymer varnish (LC 930 manufactured by Daikin Industries, Ltd., resin concentration: 45%; hereinafter, referred to as “VdF copolymer A”) A coating varnish was prepared in the same manner as in Example 1 except that the components shown in Table 3 were used in the amounts shown in the same table (NK2 cup viscosity: 15 seconds). . Then, each varnish was applied to a chemical conversion-treated aluminum plate (the same undercoating treatment as in Example 1) as in Example 1 to prepare a test coated plate. . In the same manner as in Example 1, the test coated plate was examined for the degree of hydrophilicity of the coating film, the ability to prevent bioadhesion, the ability to remove living organisms, and the degree of environmental impact. Table 4 shows the results. Table 3

 Example Resin (b) Curing agent Organometallic compound (a) Hydrolysis Surface conditioner No. Quantity (PHR) Accelerator (PHR) Type Quantity (PHR)

10 VdF None A 1.5 F 0.015 Copolymer A

 11 Same as above None A 15 F 0.15

12 Same as above None A 15 1.5 F 0.15

13 Same as above None B 15 G 0.15

14 Same as above None C 15

 15 Same as above None C 15 1.5 F 0.15

16 Same as above None D 15 G 0.15

17 Same as above None E 1.5

 18 Same as above None E 15 1.5

Comparative Example 2 Same as above None Table 4

 Coating parent

 Fujibobo adhesion test Fujibobo washing removal test Environmental impact degree Degree of hydration

Example organic metal

 Fujitsubo adhesion Diatom adhesion Deposition of diatoms Diatom removal of Fujitsubo mortality

 No.Compound (a) Water contact Visual metal elution amount Antenna (degree) Attached pieces Attached rate Visually remaining Residual rate Visually killed Rate of death

 Color difference (Δ Ε)

 Number of bodies Knowledge Color difference (m E) Appearance ヽ (ppm)

 iLI A bo 3 0.50 〇 2.00 0 0.00 0.46 ® 0 0.00 ND (1.5)

 1 丄 U 0 0.00 〇 1.80 0 0.00 0.38 CQ) 0 0.00 ND

(15)

 丄 Δ 1 0 0.00 〇 1.70 0 0.00 0.36 0 0.00 ND

(15)

 B 32 1 0.17 〇 1.85 0 0.00 0.39 ◎ 0 0.00 ND

(15)

 14 0 0.00 〇 1.85 0 0.00 0.39 ◎ 0 0.00 ND

(15)

 15 C 24 0 0.00 〇 1.65 0 0.00 0.35 ◎ 0 0.00 ND

(15)

 16 D 24 0 0.00 〇 1.68 0 0.00 0.35 ◎ 0 0.00 ND

(15)

 17 E 58 4 0.67 Δ 2.32 0 0.00 〇 0.70 ◎ 0 0.00 ND (1.5)

 18 E 46 2 0.33 〇 1.80 0 0.00 0.38 ◎ 0 0.00 ND

(15)

Comparative Example 2 94 121 20.17 X 11.45 110 18.33 X 9.73 ◎ 0 0.00 ND

Examples 19 to 27 and Comparative Example 3

 As the resin (b), a thermoplastic VdF-based copolymer (THV-200P, manufactured by Sleem Co., Ltd .; hereinafter, referred to as “VdF-based copolymer B”) is used as methylethyl ketone Z butyl acetate. (9Z1) A varnish with a resin concentration of 25% was prepared by dissolving in a mixed solvent. A coating varnish was prepared in the same manner as in Example 1 except that this varnish and the components shown in Table 5 were used in the amounts shown in the same table (the viscosity was methylethyl ketone butyl acetate (butyl acetate). 9 1) The viscosity of NK2 cup was adjusted to 15 seconds using a mixed solvent.) Next, each varnish was coated on a chemically treated aluminum plate (those treated with the same undercoating as in Example 1) in the same manner as in Example 1, and the test coated plate was used. Was prepared. Using this test coated plate, the degree of hydrophilicity of the coating film, the ability to prevent bioadhesion, the ability to remove living organisms, and the degree of environmental impact were examined in the same manner as in Example 1. Table 6 shows the results.

 Table 5

 Example Resin (b) Curing agent Organometallic compound (a) Hydrolysis Surface conditioner No. Quantity (PHR) Accelerator (PHR) Type Quantity (PHR)

19 VdF-based polyisosia A 1.5 F 0.015 copolymer B nate

 20 Same as above None A 15 F 0.15

21 Same as above None A 15 1.5 F 0.15

22 Same as above None B 15 G 0.15

23 Same as above None C 15

 24 Same as above None C 15 1.5 F 0.15

25 Same as above None D 15 G 0.15

26 Same as above None E 1.5

 27 Same as above None E 15 1.5

Comparative Example 3 Same as above None Table 6

 Coating parent Fujibobo adhesion test Fujibobo washing removal test

 Degree of hydration

Example organic metal

 Fujibobo adhesion Diatom adhesion Fujibobo removal 裸 :: Bare 际 ΐϊ Fujibobo mortality

 No.Compound (a) Water contact Visual metal elution amount

 Filh-Ffrl adhered pieces Adhesion rate Visual Residual Residual rate

 Color difference (Δ Ε) Eye planting Color difference (Δ Ε) r L Death mortality (ppm) Body (%) Appearance 侗 Body (%) z ^ ^ t 倜 Body (%)

 19 A 59 3 0.50 〇 2.15 0 0.00 ◎ 0.71 ◎ 0 0 ND (1.5)

 20 A 42 1 0.17 〇 1.8 0 0.00 ◎ 0.38 ◎ 0 0 ND (15)

 21 A 33 0 0.00 〇 1.66 0 0.00 ◎ 0.35 ◎ 0 0 ND (15)

 22 B 37 1 0.17 〇 1.44 0 0.00 ◎ 0.30 © 0 0 ND

(15)

 23 C 40 1 0.17 〇 1.65 0 0.00 ◎ 0.35 ◎ 0 0 ND (15)

 24 C 35 0 0.00 〇 1.54 0 0.00 ◎ 0.32 ◎ 0 0 ND

(15)

 25 D 34 0 0.00 〇 1.55 0 0.00 ◎ 0.33 ◎ 0 0 ND

(15)

 26 E 62 5 0.83 Δ 2.35 0 0.00 〇 0.71 ◎ 0 0 ND (1.5)

 27 E 45 4 0.67 〇 1.86 0 0.00 ◎ 0.39 ◎ 1 0.17 ND

(15)

Comparative Example 3 102 132 22.00 X 11.12 122 20.33 X 7.65 ◎ 0 0 ND

Examples 28 to 36 and Comparative Example 4

 As the resin (b), a thermosetting acrylic resin varnish (Acrylic A-801 manufactured by Dainippon Ink and Chemicals, Inc .; resin concentration 50%, resin hydroxyl group) 100 mg KOHZg, hereinafter referred to as “thermosetting acrylic resin”), and a polyisocyanate-based curing agent (Nippon Polyurethane Industrial Co., Ltd.) The varnish and the components shown in Table 7 were mixed in an amount such that the NCOZ OH equivalent ratio became 1.0, and the components shown in Table 7 were used in the amounts shown in the same table. A varnish for paint was prepared in the same manner as in Example 1 (NK2 cup viscosity: 15 seconds). Next, each varnish was coated on a chemically treated aluminum plate (those that had been subjected to the same undercoating as in Example 1) as in Example 1, and the test coated plate was applied. It was made. For this test coated plate, the degree of hydrophilicity of the coating film, the ability to prevent bioadhesion, the ability to remove living organisms, and the degree of environmental impact were examined in the same manner as in Example 1. Table 8 shows the results.

 Table 7

 Example Resin (b) Hardener Organometallic compound (a) Hydrolysis Surface conditioner No. Quantity (PHR) Accelerator (PHR) Planting amount (PHR)

28 Thermosetting polyisosia A 1 F 0.015 Acrylic resinate

 29 Same as above Same as above A 5 F 0.15

30 Same as above Same as above A 5 1.5 F 0.15

31 Same as above B 5 G 0.15

32 Same as above Same as C 5

 33 Same as above Same as above C 5 1.5 F 0.15

34 Same as above D5G 0.15

35 Same as above Same as E 1

 36 Same as above Same as above E 5 1.5

Comparative Example 4 Same as above Same as above Table 8

 涂 脫 腊 Celebration Fujibobo adhesion test Fujibobo washing removal test Environmental impact degree

Example organic metal

 Fujibobo adhesion Diatom adhesion Fujitsubo removal Fine removal Fujitsubo mortality

 No.Compound (a) Water contact Visual metal elution amount Antenna (degree) Adhesion Adhesion rate Visual Remaining Residual rate Deflection Death rate

 Color difference Α Ε) Color difference (Δ Ε) Appearance (, ppm) Population (%) Outer parent Purple () Outer parent population (%)

 28 A 56 4 0.67 〇 1.90 1 0.19 U.44 ◎ 0 0.00 J U

 (1)

 29 A 35 0 0.00 〇 1.45 0 0.00 U.U ◎ 0 0.00 JNL)

 (Five)

 30 A 24 0 0.00 〇 1.78 0 0.00 ® 0.37 ◎ 0 0.00 ND

 (Five)

 31 B 24 1 0.17 〇 1.44 0 0.00 U.U ◎ 1 0.17

 (Five)

 32 C 27 1 0.17 〇 0.15 0 0.00 ◎ 0.31 ◎ 0 0.00 ND

 (Five)

 33 C 23 0 0.00 〇 1.64 0 0.00 ◎ 0.34 ◎ 0 0.00 ND

 (Five)

 34 D 23 0 0.00 〇 1.68 0 0.00 ◎ 0.35 ◎ 0 0.00 ND

 (Five)

 35 E 60 6 1.00 Δ 2.26 1 0.19 〇 0.75 ◎ 0 0.00 ND

 (1)

 36 E 45 1 0.17 〇 1.79 0 0.00 ◎ 0.38 ◎ 0 0.00 ND

 (Five)

Comparative Example 4 85 128 21.33 X 10.10 124 20.67 X 8.59 ◎ 1 0.17 ND

Examples 3 7 to 4 5 and Comparative Example 5

 As the resin (b), thermoplastic acrylic resin (BR-773 manufactured by Mitsubishi Rayon Co., Ltd .; hereinafter, referred to as “thermoplastic acrylic resin”) was converted to butyl acetate. After dissolution, a varnish with a resin concentration of 35% was prepared. A paint varnish was prepared in the same manner as in Example 1 except that this varnish and the components shown in Table 9 were used in the amounts shown in the same table (NK2 cup viscosity 15 Seconds). Then, each of the paints was applied to a chemically treated aluminum plate (the same as in Example 1 that had been subjected to the undercoating and undercoating treatment) in the same manner as in Example 1; Was made. Using this test coated plate, the degree of hydrophilicity of the coating film, anti-bioadhesive properties, bioremovability, and environmental impact were examined in the same manner as in Example 1. The results are shown in Table 10. Table 9

 Example Resin (b) Hardener Organometallic compound (a) Hydrolysis Surface conditioner No. Quantity (PHR) Accelerator (PHR) Amount (PHR)

37 Thermoplastic None A 1 F 0.015 Acrylic resin

 38 Same as above None A 5 F 0.15

39 Same as above None A 5 1.5 F 0.15

40 Same as above None B 5 G 0.15

41 Same as above None C 5

 42 Same as above None C 5 1.5 F 0.15

43 Same as above None D 5 G 0.15

44 Same as above None E 1

 45 Same as above None E 5 1.5

Comparative Example 5 Same as above None Coating parent

 Le Fujibo adhesion test Fujibo water washing test Environmental impact degree Example Organic metal Fujibo adhesion

 Compound (a) Wetted diatom adherence Fujitsubo removal diatom removal Fujitsubo mortality

 No. Visual metal elution amount Antenna (degree) Adhesion Adhesion rate Visual color difference (Δ Ε) Remaining residual rate Deflection Color difference (Δ Ε) Appearance Die death rate (ppm) Brittle (%) Appearance Number of individuals (%) Appearance Number of individuals (% )

 37 A 57 5 0.83 〇 2.33 1 0.17 ◎ 0.51 ◎ 0 0.00 ND

 (1)

 38 A 30 1 0.17 〇 1.88 0 0.00 ◎ 0.39 ◎ 0 0.00 ND

 (Five)

 39 A 27 1 0.17 〇 1.76 0 0.00 ◎ 0.37 ◎ 0 0.00 ND

 (Five)

 40 B 28 0 0.00 〇 1.42 0 0.00 ◎ 0.3 ◎ 0 0.00 ND

 (Five)

 41 C 28 2 0.33 〇 1.85 0 0.00 ◎ 0.39 ◎ 1 0.17 ND

 (Five)

 42 C 24 0 0.00 〇 1.70 0 0.00 ◎ 0.36 ◎ 0 0.00 ND

 (Five)

 43 D 25 1 0.17 〇 1.68 0 0.00 ◎ 0.35 ◎ 0 0.00 ND

 (Five)

 44 E 61 6 1.00 Δ 2.20 1 0.17 〇 0.73 ◎ 0 0.00 ND

 (1)

 45 E 44 5 0.83 〇 1.88 0 0.00 ◎ 0.39 ◎ 0 0.00 ND

 (Five)

Comparative Example 5 82 124 20.67 X 10.27 120 20.00 X 8.73 ◎ 1 0.17 ND

Examples 46 to 54 and Comparative Example 6

 Epoxy resin varnish (Epicoat EP1001X70 manufactured by Yuka Shellepoxy Co., Ltd.) as resin (b), hereinafter referred to as "epoxy resin" ) And an amine-based curing agent (EpoMate S 2002, manufactured by Yuka Shiel Epoxy Co., Ltd.) in an amount such that the equivalent ratio becomes 1.0. A paint varnish was prepared in the same manner as in Example 1 except that this varnish and the components shown in Table 11 were used in the amounts shown in the table. Adjust the NK2 pump viscosity to 15 seconds with a ren and then apply each varnish in the same manner as in Example 1 to a chemically treated aluminum plate (undercoating in the same manner as in Example 1). The intermediate coating was applied) to prepare a test coated plate. Using this test coated plate, the degree of hydrophilicity of the coating film, the ability to prevent bioadhesion, the ability to remove living organisms, and the degree of environmental impact were examined in the same manner as in Example 1. The results are shown in Table 12. Example Resin (b) Hardener Organometallic compound (a) Hydrolysis Surface conditioner No. Type Amount (PHR) Accelerator (PHR) Amount (PHR)

46 Epoxy Amine A 1 F 0.015

47 Same as above Same as above A 5 F 0.15

48 Same as above Same as above A 5 1.5 F 0.15

49 Same as above Same as above B 5 G 0.15

50 Same as above Same as C 5

 51 Same as above C5 1.5 F 0.15

52 Same as above Same as above D 5 G 0.15

53 Same as above Same as E 1

 54 Same as above E 5 1.5

Comparative Example 6 Same as above Same as above

Example 5 5 to 6 3 and Comparative Example 7

 As the resin (b), a room temperature film-forming silicone resin varnish (KR-251 manufactured by Shin-Etsu Chemical Co., Ltd .; hereinafter, “Silicone Resin A ), And the varnish for paint was prepared in the same manner as in Example 1 except that this varnish and the components shown in Table 13 were used in the amounts shown in the same table. It was manufactured (adjusted to NK 2 force viscosity of 15 seconds with Xylene). Next, each varnish was coated on a chemically treated aluminum plate (the same as in Example 1 that had been subjected to the undercoating and intermediate coating) in the same manner as in Example 1. Then, a test coated plate was prepared. Using this test coated plate, the degree of hydrophilicity of the coating film, the ability to prevent bioadhesion, the ability to remove the living body, and the environmental impact were examined in the same manner as in Example 1. The results are shown in Table 14.

 Table 13

 Example Resin (b) Hardener Organometallic compound (a) Hydrolysis Surface conditioner No. Quantity (PHR) Accelerator (PHR) Amount (PHR)

55 Silicone None A 1 F 0.015 Resin A

 56 Same as above None A 10 F 0.15

57 Same as above None A 10 1.5 F 0.15

58 Same as above None B 10 G 0.15

59 Same as above None C 10

 60 Same as above None C 10 1.5 F 0.15

61 Same as above None D 10 G 0.15

62 Same as above None E 1

 63 Same as above None E 10 1.5

Comparative Example 7 Same as above None Four

 Coating parent

 Fujibo adhesion test Fujibo water washing test Environmental impact degree Example

 Organic metal

 ^ ： 县 Adhesion of Fujibbo Diatom adhesion Detachability of Fujibbo

 1 u α-) ¾¾ a J J Λ1¾ Diatom removal

 Say ¾ Fuji

 νί Metal elution amount Antenna (degree) Adhesion Adhesion rate Visual observation Λ F'l Remaining residual rate Visual observation Α ¾ (Λ Ε) Appearance Die death rate ρπι) Nana (%) Appearance Construction (%) Appearance Nana (%)

55 A 53 4 0.67 〇 1.90 0 '0.00 ◎ 0.48 ◎ 0 0 ND

 56 A 26 0 0.00 〇 1.45 0 0.00 ◎ 0.30 ◎ 0 0 ND (10)

 57 A 23 1 0.17 〇 1.66 0 0.00 ◎ 0.35 ◎ 1 0.17 ND (10)

 58 B 27 1 0.17 〇 1.44 0 0.00 ◎ 0.30 ◎ 0 0

 (Ten)

 59 c 27 1 0.17 〇 1.46 0 0.00 ◎ 0.31 ◎ 0 0 ND

(Ten)

 60 c 24 0 0.00 〇 1.55 0 0.00 ◎ 0.33 ◎ 0 0 ND

(Ten)

 61 D 24 0 0.00 〇 1.52 0 0.00 ◎ 0.32 ◎ 0 0 ND

(Ten)

 62 E 60 7 1.17 Δ 2.26 0 0.00 〇 0.68 ◎ 0 0 ND

 (1)

 63 E 44 5 0.83 〇 1.81 0 0.00 ◎ 0.38 ◎ 0 0 ND (10)

Comparative Example 7 99 126 21.00 X 11.76 120 20.00 X 10.00 ◎ 2 0.33 ND

Example 6 4 to 72 and Comparative Example 8

 As the resin (b), a room temperature film-forming silicone resin resin (X-040-175, manufactured by Shin-Etsu Iridaku Kogyo Co., Ltd.). And the components shown in Table 15 were used in the amounts shown in the table, except that this varnish was used in the same manner as in Example 1 to prepare a paint varnish. Prepared (adjusted to NK 2 force viscosity of 15 seconds with Xylene). Next, each varnish was coated on a chemically treated aluminum plate (which had been subjected to the same undercoating process as in Example 1) in the same manner as in Example 1 and subjected to the test. A painted plate was prepared. Using this test coated plate, the degree of hydrophilicity of the coating film, the ability to prevent bioadhesion, the ability to remove biomaterials, and the degree of environmental impact were examined in the same manner as in Example 1. The results are shown in Table 16.

 Table 15

 Example Resin (b) Hardener Organometallic compound (a) Hydrolysis Surface conditioner No. Type Amount (PHR) Accelerator (PHR) Amount (PHR)

64 Silicone None A 1 F 0.015 Resin B

 65 Same as above None A 10 F 0.15

66 Same as above None A 10 1.5 F 0.15

67 Same as above None B 10 G 0.15

68 Same as above None C 10

 69 Same as above None C 10 1.5 F 0.15

70 Same as above None D 10 G 0.15

71 Same as above None E 1

 72 Same as above None E 10 1.5

Comparative Example 8 Same as above None

Comparative Example 9

 As an anti-bioadhesive agent, a cuprous oxide paint (Captain AF Kuroshio Ichiban (1 liquid type) manufactured by Kansai Paint Co., Ltd.) was used as a NK 2 force pump with Xylene. After diluting to a viscosity of 15 seconds, apply it to a conversion-treated aluminum plate (one that had been subjected to the same undercoating process as in Example 1) as in Example 1 and tested. A painted plate was prepared. In the same manner as in Example 1, the test coated plate was examined for the degree of hydrophilicity of the coating film, the anti-bioadhesive property, the bioremovability, and the environmental impact. The results are shown in Table 17.

Comparative Example 10

 As an anti-bioadhesive agent, an oil-releasing silicone resin coating (Nyoclean DX (one-pack type) manufactured by Chugoku Paint Co., Ltd.) is applied to NK 2 with Xylene. Diluted to a viscosity of 15 seconds, and treated as in Example 1 with a chemically treated aluminum plate (the same as in Example 1 but with the special intermediate coating Sylbex applied after undercoating). ) To prepare a test coated plate. In the same manner as in Example 1, the test coated plate was examined for the degree of hydrophilicity of the coating film, the ability to prevent bioadhesion, the ability to remove the living body, and the degree of environmental impact. The results are shown in Table 17.

Comparative Example 1 1

A general-purpose hard vinyl chloride resin sheet (thickness: 2 mm) was used as a test sample, and this sheet was treated in the same manner as in Example 1 to prevent the coating from becoming hydrophilic and prevent bio-adhesion. , Bioremovability and environmental impact were examined. The results are shown in Table 17. Coating parent

 Fujibo adhesion test Fujibo washing removal test Environmental impact

 Organic metal

Comparative example

 Compound Fujitsubo adhesion Diatom adhesion Deposition of diatoms Diatom removal of Fujita mortality Metal elution amount No.

 (a)

 Antenna (degree) Adhesion rate Visual Remaining Residual rate Visual Visual appearance

 Color difference (Δ Ε) Color difference (Δ Ε) t, ppm) Number of individuals (%) Number of individuals (%) Number of individuals (%)

 9 None 84 0 (Dead) 0.00 X 10.24 0 0.00 X 8.70 χ (Water colored) 600 100 200

10 None 105 111 18.50 X 9.90 89 14.83 X 7.62 X (water oil) 11 10.83 ND

11 None 87 183 30.50 X 12.34 180 30.00 X 10.49 ◎ 5 0.83 ND

Example 73

 The test painted plate (150mm X 400mm) prepared in Example 2 was suspended in a model waterway (average tidal velocity of 20cmZ seconds) with almost constant flow velocity of seawater on the coastal area of Himeji, Hyogo, Japan. They were then immersed and examined for their ability to prevent and adhere to living organisms in a real marine environment, their ability to remove living organisms, and their environmental impact. The test was started in spring, when the activity period of Fujibo began, and was measured at 12, 24 and 42 months after the start of the test. Table 18 shows the results. The evaluation method for each test is the same as in Example 1.

Examples 74 to 96 and Comparative Examples 12 to 21

Using the coated plates prepared in Examples and Comparative Examples shown in Tables 18 and 19, in the same manner as in Example 73, the anti-bioadhesive property, bio-removability and bio-removal property in a real marine environment were used The environmental impact was investigated at 12 months, 24 months and 42 months after the start of the test, respectively. The results are shown in Tables 18 and 19.

8

Real marine environmental tests in the Modenole waterway

 Organic Gold Fujibo Adhesion Test Washing Removal Test Example

 Resin (b)

 No. Object (a) Degree of hydration Visual appearance Number of fujibos adhered Color difference (Δ Ε) Presence Diatom persistence

 (PHR) 12 Months 24 Months 42 Months 12 Months 24 Months 42 Months 12 Months 24 Months 42 Months Individual Visual Color Difference After After After After After After Number (Δ Ε)

88 Epoxy resin A (5) 36 〇 〇 〇 0 0 0 1.54 1.57 1.49 0 ◎ 0.45

89 Epoxy resin C (5) 30 〇 〇 〇 0 0 0 1.47 1.50 1.43 0 ◎ 0.43

90 Epoxy resin E (5) 45 〇 〇 〇 0 1 1 2.36 2.41 2.29 0 〇 0.62 Comparative example 17 Epoxy resin ― 85 XX X 95 152 157 9.28 10.55 12.70 153 X 10.76

91 Silicone resin A A (10) 26 〇 〇 〇 0 0 0 1.60 1.63 1.55 0 ◎ 0.47

92 Silicone resin A C (10) 27 〇 〇 〇 0 0 1 1.52 1.55 1.47 0 ◎ 0.44

93 Silicone resin A E (10) 44 〇 〇 〇 0 1 1 2.26 2.31 2.19 0 〇 0.55 Comparative example 18 Silicone resin A ― 99 X X X 101 162 166 10.30 11.76 14.10 163 X 12.00

94 Silicone resin B A (10) 28 〇 〇 〇 0 0 0 1.54 1.56 1.49 0 ◎ 0.45

95 Silicone resin B C (10) 24 〇 〇 〇 0 0 0 1.47 1.48 1.43 0 ◎ 0.43

96 Silicone resin BE (10) 45 〇 〇 〇 0 1 1 2.40 2.42 2.33 0 〇 0.61 Comparative example 19 Silicone resin B 99 XXX 103 165 170 10.20 11.58 13.90 166 X 11.81 Comparative example 20 Cuprous oxide paint 84 〇 〇 〇 0 9 180 9.01 10.24 12.30 176 X 10.44 Comparative Example 21 Oil-releasing silicone 105 〇 〇 〇 32 128 192 8.71 9.90 11.90 188 X 10.10 Comparative Example 21 Rigid vinyl chloride plate 87 〇 〇 〇 150 158 162 10.90 12.34 14.80 159 X 12.59

Example 97

 The test painted plate (150mm x 300mm) prepared in Example 2 was attached to the submerged area below the draft line of a ship with a displacement of 50 tons, and berthing and sailing were performed under the following conditions. After returning, the bioadhesion-preventing property was examined every 12 cycles, 24 cycles, and 36 cycles. After 36 cycles, the bioremovability was examined. The tests begin in the spring, when the activity period of FUJIPPO begins, and the evaluation method for each test is the same as in Example 1. Table 20 shows the results.

 One cycle: 14 days after mooring in the port of Himeji 巿, Hyogo, Japan, sailing outside the bay for 14 days (10 knots).

Examples 98 to: 120 and Comparative Examples 22 to 32

Using the coated plates prepared in Examples and Comparative Examples shown in Tables 20 and 21, the anti-bioadhesive property and bioremovability in a real marine environment were examined in the same manner as in Example 97. . The results are shown in Tables 20 and 21.

2 0

Ship actual marine environment test

 Coating film Fujibo adhesion test Rinse-out test Example Example

 Say no visual 每 1 number of Fujibos attached color difference (Δ Ε)

 Item No.a) Residual diatoms Residualization degree 12 rhi 24 rhi 36 rhi 12 rhi 24 rhi 36 rhi 12 rhi 24 rhi 36 rhi Individual Visual color difference

 Fine

 Kuru Kuru Kuru Knore Knore Knore Knore Knore Knore Number Appearance (ΔH)

112 Epoxy resin A (5) 36 ◎ ◎ ◎ 0 0 0 1.65 1.68 1.60 0 ◎ 0.48

113 Epoxy resin C (5) 30 ◎ ◎ ◎ 0 0 0 1.68 1.71 1.63 0 ® 0.49

114 Epoxy resin E (5) 45 ◎ ◎ ◎ 0 0 2 2.32 2.37 2.25 0 Li 0.68 Comparative example 27 Epoxy resin ― 85 XX 90 137 188 9.75 11.08 13.29 182 X 12.89

115 Silicone resin A A (10) 26 ◎ ◎ ◎ 0 0 0 1.54 1.57 1.49 0 ◎ 0.40

116 Silicone resin A C (10) 27 ◎ ◎ ◎ 0 0 1 1.55 1.58 1.50 0 ◎ 0.41

117 Silicone resin A E (10) 44 ◎ ◎ ◎ 0 0 1 2.35 2.40 2.28 0 Q.bZ Comparative example 28 Silicone resin A 99 X X X 96 145 200 10.87 12.35 14.82 194 X 14.37

118 Silicone resin B A '10; 28 ◎ ◎ ◎ 0 0 0 1.75 1.79 1.70 0 ◎ 0.51

119 Silicone resin B C (10) 24 ◎ ◎ ◎ 0 0 0 1.68 1.71 1.63 0 ◎ 0.49

120 Silicone resin BE (10) 45 ◎ ◎ ◎ 0 0 1 2.26 2.31 2.19 0 ◎ 0.66 Comparative example 29 Silicone resin B 99 XXX 98 148 204 10.70 12.16 14.59 198 X 14.15 Comparative example 30 Cuprous oxide paint 84 XXX 0 6 216 9.46 10.75 13.52 210 ◎ 12.84 Comparative Example 31 Oil-releasing silicone 105 XXX 38 115 230 8.28 10.40 13.07 223 ◎ 12.41 Comparative Example 32 Rigid vinyl chloride plate 87 XXX 143 142 195 12.49 13.57 16.29 189 ◎ 15.80

Examples 121 and 122

A composition (Example 121) in which the composition of Example 1 was blended with 1 PHR of NetKing 300 manufactured by Keiei Kasei Co., Ltd. as a diatom adhesion inhibitor (Example 121), a biological repellent and Then, a composition (Example 122) containing 1 PHR of Baydan GPA manufactured by Keiei Kasei Co., Ltd. was produced, and placed in a model channel under the same conditions as in Example 73. The marine environment test was conducted for 54 power months, and observations were made of Fujipo and diatom deposits. Table 22 shows the results.

Table 2 2

Example 123

 The resin (b) is silicone resin (one-pack type antibacterial sealant X31-1667 manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd .; hereinafter, "silicone resin (:)"). The compound A was added as a hydrolyzable group-containing organometallic compound (a) at 1.5 PHR, and the surface conditioner F was added at 0.015 PHR (mixed composition). The resin composition is shown in Table 23.) The resin composition was cast on an aluminum plate treated with AM-712 at 10 mil. After drying at room temperature for 7 days, a coated plate (dry film thickness: about ΙΟΟμΠ!) Was prepared.The coated plate was stored in a constant temperature / humidity (35, 95% RΗ) bath for 20 hours. Was made hydrophilic and used as a test coated plate (three sheets were prepared).

 To examine the performance as a medical material, the following two reagents were prepared.

 (a) Commercially available low-density lipoprotein (LDL) and ion-exchanged water are stirred and dispersed at 3000 rpm for 60 minutes at a HOMOSPA (manufactured by Tokushu Kika Kogyo Co., Ltd.). Then, an aqueous LDL dispersion having a concentration of 5% was prepared.

 (b) Commercially available cholesterol and ion-exchanged water are stirred and dispersed at 3000 rpm for 60 minutes at a homotespar (manufactured by Tokushu Kika Kogyo Co., Ltd.). An aqueous cholesterol dispersion having a concentration of 5% was prepared.

 (Adhesion test)

The test coated plate is vertically placed in the aqueous LDL dispersion (a) and the aqueous cholesterol dispersion (b) at 37, respectively, which are stirred in a glass container. After holding for 24 hours, the removed coated plate was dried with a 37 for 16 hours, and then the adhesion of LDL and cholesterol on the surface was examined with an electron microscope. Due to They were observed and evaluated according to the following criteria.

 〇: Adhesion area is less than 1 to 10 in the microscope field of view

 △: Attachment area is 110 ~ in the microscope field of view: I 3

 X: Attachment area exceeds 13 in the microscope field of view

 (Washing removal test)

 The coated plate subjected to the adhesion test was washed by spraying 3000 ml of ion-exchanged water (washing water was collected in a beaker), and the coated plate surface after water washing was evaluated in the same manner as above by an electron microscope. . Also, after adjusting the concentration of the washing water in the beaker used for washing so that the detection limit is 0.05 ppm, the atomic absorption spectrum method (Ltd.) The analysis was performed using an atomic absorption spectrum measuring instrument HI TACHI Z-5500 manufactured by Hitachi, Ltd.). The higher the detection amount, the better the removability.

 Table 24 shows the results of the above tests.

Examples 124 to 131 and Comparative Example 33

Using the coated plates prepared by using the compositions prepared in the examples and comparative examples shown in Tables 23 and 24, the adhesion test of physiological substances was carried out in the same manner as in Example 123. And a water removal test. The results are shown in Tables 23 and 24.

twenty three

実施例 132 twenty four

Example 132

 As the resin (b), silicone resin (elastic silicone KR_2038 manufactured by Shin-Etsu Chemical Co., Ltd.), hereinafter referred to as “silicone resin DJ” and a curing agent ( Shin-Etsu Chemical Co., Ltd.'s D2038) was mixed, and Compound A was added as a water-decomposable group-containing organometallic compound (a) with 1.5 PHR, and surface conditioner F was added. (The mixed composition is shown in Table 25.) This resin composition was diluted with mineral spirits to a concentration of 20%, and the mixture was mixed with Shin-Etsu Chemical Co., Ltd. Silicone resin tube manufactured by Co., Ltd.

(ST-TB; inner diameter 25 mm, wall thickness 5 mm, length 1000 mm), immerse the resin composition on the inner and outer surfaces, leave at 37: for 16 hours, and heat at 150 for 15 minutes After curing, a tube having a film thickness of 10 m was produced. This tube was stored in a constant temperature and humidity (35, 95% R 95) bath for 20 hours, and the surface was hydrophilized to prepare tubes for testing (three tubes were prepared). ).

 These test tubes were subjected to the following adhesion test and washing removal test. Table 26 shows the results.

 (Adhesion test)

 Test tubes for LDL aqueous dispersion (a) and cholesterol aqueous dispersion (b) prepared in the same manner as in Example 123 in a glass container One end of the tube was immersed, and the other end of the tube was connected to the pump. A polyethylene tube was arranged so that the dispersion from the pump returned to the glass container. After setting in this way, the dispersions (a) and (b) were circulated for 120 hours at a discharge pressure of 0.3 MPa. After stopping the pump, the tube was removed, dried at 37 for 16 hours, and a tube with an inner surface treated with a physiological substance was prepared (three tubes).

A part of this processing tube was cut, and the same as in Example 123 was cut. Then, observation and evaluation were performed using an electron microscope.

 (Washing removal test)

 Circulate ion-exchanged water for 120 minutes in the same manner except that 3000 ml of ion-exchanged water was used in place of the dispersion, using the equipment used for the adhesion test described above. Washed. A part of the tube after washing was cut out, and observed and evaluated with an electron microscope in the same manner as in Example 123. Further, the ion-exchanged water used for washing was analyzed by the atomic absorption spectral method in the same manner as in Example 123 (so that the detection limit was 0.05 ppm). The concentration of washing water was adjusted).

Examples 133 to 140 and Comparative Examples 34 and 35

 Using the tubes prepared using the compositions prepared in the examples and comparative examples shown in Tables 25 and 26, an adhesion test of physiological substances and a test were performed in the same manner as in Example 132. And a water removal test. An uncoated tube was also tested in the same manner (Comparative Example 35). The results are shown in Tables 25 and 26.

 Table 25

 Example Resin (b) Curing agent Organic gold scrap binding compound (a) Hydrolysis Surface conditioner No.

132 Silicone None A 1.5 F 0.015 Resin C

 133 Same as above None A 15 F 0.15

134 Same as above None A 15 1.5 F 0.15

135 Same as above None B 15 G 0.15

136 Same as above None C 15

 137 Same as above None C 15 1.5 F 0.15

138 Same as above None D 15 G 0.15

139 Same as above None E 1.5

 140 Same as above None E 15 1.5

Comparative Example 34 Same as above None 2 6

産業上 の利用 可能性

Industrial applicability

 According to the invention,

(1) Adhesion of aquatic organisms and physiological substances can be suppressed.

(2) Adhesion of hydrophobic dirt such as floating oil and body fat can be suppressed.

 (3) The attached living body or hydrophobic dirt can be easily removed.

(4) There is no dissolved component and there is no risk of polluting the environment.

 (5) Long-term effects can be maintained because there is no eluted component.

 (6) Since it is excellent in removing dirt, it can be self-cleaned when traveling on a ship or the like.

 (7) Since the surface is hydrophilic, water does not remain on the surface and drainage is excellent.

The above effect is achieved.

Claims

Scope of demand 1. An aquatic product or a resin composition for preventing the attachment of physiological substances, containing a water-decomposable organic metal compound (a) for surface hydrophilization and a resin (b) for a binder object .  2. The hydrolyzable organometallic compound (a) has the formula (I): X _b M (OR ¹ ) _a R ² _c (I) [Where a is an integer of 0 or 1 to 6, b is an integer of 0 or 1 to 5, c is an integer of 0 or 1 to 6 (where a + b + c ≥ 3 and a and c do not become 0 at the same time), and X is the same or different, even if it is an oxygen atom, a nitrogen atom, a fluorine atom or the like. Or a monovalent organic group or hydrogen atom having 1 to 5000 carbon atoms which may contain Z or chlorine atom, and M is a metal having at least trivalent valence The atom and R ¹ may be the same or different and may contain oxygen, nitrogen, fluorine and / or chlorine atoms. A monovalent organic group, a siloxane residue or a hydrogen atom, and R ² are the same or different, each of which is an oxygen atom, a nitrogen atom, a fluorine atom and Z or chlorine source Represents an organic group having 1 to 20 carbon atoms, which has a chelating ability which may contain a hydrolyzable organometallic compound represented by the formula: 2. The composition according to claim 1, wherein the composition is a cooler comprising two or more kinds of the organic metal compounds. 3. The hydrolyzable organometallic compound (a) is one or more of two or more hydrolyzable organometallic compounds represented by the formula (I) according to claim 2. Claim 1 which is a poly-gommer or a poly-go-mer obtained by the above condensation The composition of any of the preceding claims.  4. The composition according to any one of claims 1 to 3, wherein the resin (b) is a resin that is soluble in an organic solvent. 5. The composition according to any one of claims 1 to 4, wherein the composition further comprises a hydrolysis promoter (c).  6. The composition according to any one of claims 1 to 5, further comprising a diatom adhesion inhibitor and Z or a biological repellent.  7. A method according to any one of claims 1 to 6, wherein a curing agent is incorporated, and the resin (b) is a curable resin soluble in an organic solvent. Composition.  8. The composition according to any one of claims 1 to 7, which forms a coating layer or a film having a surface contact angle with water of less than 70 degrees. .  9. The composition according to any one of claims 1 to 7, which forms a coating layer or film having a surface contact angle with water of 55 degrees or less. .  10. On a water surface or in water having a coating layer obtained from the resin composition according to any one of claims 1 to 9 on the surface. The goods or structures used.  11. The article or structure according to claim 10 for use in a marine environment exceeding a flow rate of lOOmmZ seconds.  12. The article or structure according to claim 10, which is used in a marine environment having a flow velocity of 300 mmZ seconds or more.  13. The article or claim according to any one of claims 10 to 12, wherein the adhesion rate of the fusible is 15% or less in the following fuspo adhesion test. Structure. Record Fujipo adhesion test  Water tank: 150mm X 100mm X 200mm (inside dimensions)  Seawater: 3 liters  Test organism: Dr. zippo (Balanus kondakovi)  Population 600  Test temperature: 22-24t  Examination period: 60 days  14. The article or structure according to claim 13, wherein the adhesion rate of zippo is 5% or less.  15. The article or structure according to claim 13 or 14, wherein the residual ratio of the zippo is 2% or less in the zippo water washing test described below. object.  Record  Test sample: Structural sample that was subjected to the fujibo adhesion test described in Paragraph 12 of the claim for 60 days.  Rinse conditions: Dispense tap water at right angles to the test sample surface for 20 seconds so that the sample surface has a water pressure of 0.3 ± 0.05 MPa. 16. A medical member having on its surface a coating layer obtained from the resin composition according to any one of claims 1 to 9 in the claim.  17. A medical member obtained from the resin composition according to any one of claims 1 to 9.  18. The member according to claim 16 or 17, wherein said member is in the form of a film, sheet or tube. 19. One surface of the resin film has a coating layer obtained from the resin composition according to any one of claims 1 to 9 in the claims. A film that has an adhesive layer on the other surface and is used on the water surface or in water A marking film used for products or structures or medical parts. A coating film is formed by applying the resin composition according to any one of claims 1 to 9 to the surface of a product or a structure used in water or in water. A method of preventing aquatic organisms from adhering to the article or structure by causing the aquatic organisms to adhere to the article or structure. Applying the resin composition according to any one of claims 1 to 9 to the surface of a medical member that comes into contact with a physiological substance released from cells or living organisms. A method for preventing cells or physiological substances from adhering to the medical member by forming a membrane.