JP3528331B2 - Antifouling composition for coating - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling composition for coating, and more specifically, it is excellent in antifouling property and anti-bleeding property of a filler present in a base material coated with a plasticizer and the like. And an antifouling composition for coating.

[0002]

2. Description of the Related Art In recent years, as the added value of materials has advanced, the antifouling property on the surface of various base materials has been strongly required, and many coating agents have been proposed.

As the coating, for example, polymers of various (meth) acrylic acid alkyl esters, copolymers of them with fluorine-based monomers and silicon-based monomers, and blends of these with binder resins are known. Has been. Among these, the introduction of a fluorine-based or silicon-based monomer into the coating agent has been considered as a powerful means (Japanese Patent Laid-Open No. 63-61032).
JP-A-63-137934).

However, for example, when the base material is plasticized polyvinyl chloride, a composition obtained by polymerizing by a conventionally known method using an appropriate amount of fluorine-based or silicon-based monomer commensurate with the cost, There is a problem that sufficient antifouling performance cannot be exhibited due to the influence of the plasticizer and the like.

Further, the introduction of the fluorine-based or silicone-based monomer has always been concerned about the problem of impairing the adhesion to the substrate. In particular, PVC leather or artificial leather with a high content of plasticizer among plasticized polyvinyl chloride,
Synthetic leather and the like are required to have a high degree of adhesion such as bending resistance and abrasion resistance.

Therefore, even when a fluorine-based or silicone-based monomer is introduced, there has been a demand for a surface coating agent having both adhesion to a substrate and antifouling property. Under these circumstances, JP-A-6-57196 proposes a vinylidene fluoride-based coating composition excellent in antifouling property and durability, but a vinylidene fluoride-based polymer is usually reacted. It has a drawback that it does not contain a functional group and lacks solvent resistance.

On the other hand, a fluorinated olefin-based coating material having a reactive functional group is known as a coating agent, but this coating material has a low fluorine content and therefore lacks antifouling property.

Further, when used, the surface coating agent may be required to have solvent resistance. For example, when using an organic solvent-based adhesive when applying a base material coated with various surface coating agents, it is essential to wipe off the excess adhesive with the organic solvent. Further, in order to completely remove graffiti caused by various paints outdoors, many kinds of organic solvents have to be used.

From the above, there has been a demand for a surface coating agent which is excellent in solvent resistance in addition to antifouling property and adhesion to a substrate.

[0010]

The object of the present invention is to provide, in addition to unprecedented excellent antifouling performance, the effect of preventing bleeding of resin internal additives such as plasticizers, pigments and dyes contained in the substrate, When a foreign substance comes into contact with it, it has the effect of preventing the migration of some or all of the compounds contained in the foreign substance, forms a tough film with excellent adhesion to the substrate, and resists problems such as during construction. An object of the present invention is to provide an antifouling composition for coating which is also excellent in solvent property.

[0011]

The inventors of the present invention have diligently studied to solve the above-mentioned problems and found that (meta)
A composition comprising a polymer of monomers containing an acryloyl group, a fluorinated olefin-based polymer, bisphenol AF, and a bifunctional or more polyfunctional reactive compound capable of reacting with bisphenol AF is used. For example, they have found that the above problems can be solved by providing antifouling property and adhesiveness and adhesiveness between each component and with a substrate, and have completed the present invention.

That is, the present invention comprises a polymer (I) of a monomer containing a (meth) acryloyl group, a fluorinated olefin polymer (II), and a bisphenol AF (III) represented by the following formula: The present invention relates to a coating antifouling composition comprising a bifunctional or higher functional polyfunctional reactive compound (IV) capable of reacting with the bisphenol AF (III).

[0013]

[Chemical 2]

By the way, the polymer (I) of a monomer containing a (meth) acryloyl group and the fluoroolefin polymer (II) have good compatibility, and a composition obtained by mixing this polymer is used for various paints. Although it is used in compositions, etc., the film after coating on the substrate has a fluorine component on the air side,
It is known that the film has a concentration gradient in which a large amount of acrylic component is present on the substrate side. However, it is inferior in solvent resistance, and the present invention solves this point by crosslinking each component.

That is, the present invention relates to polymers (I) and (II)
In this system, a cross-linking system comprising bisphenol AF (III) and a bifunctional or more polyfunctional reactive compound (IV) capable of reacting with bisphenol AF (III) is introduced. It becomes possible to provide an antifouling composition for coating which has both stain resistance, substrate adhesion and solvent resistance.

Examples of the polymer (I) containing a (meth) acryloyl group include methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate. , Octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, hydroxybutyl acrylate, hydroxyethyl acrylate, glycidyl methacrylate, dibutyl fumarate ester, dimethyl fumarate ester, acrylic acid, methacrylic acid homopolymers or copolymers Can be mentioned.

Needless to say, the present invention is not limited to these specific examples. Here, in order to strengthen the formed film and improve solvent resistance, it is preferable to introduce a reactive functional group into the polymer (I). The selection of the reactive functional group is not particularly limited as the type of the functional group, for example, hydroxyl group, thiol group, carboxyl group, amino group, isocyanate group, aziridinyl group, glycidyl group, alkoxysilyl group, silanol group, cyclocarbonate group. , Acid anhydride groups, vinyl groups, enol ether groups, thioether groups, active ester groups, acetoacetate groups, metal salts, metal oxides and those functional groups are blocked with various blocking agents,
It is determined by the reactivity with a bifunctional or higher polyfunctional reactive compound (IV) capable of reacting with bisphenol AF described later. Further, these functional groups may be monofunctional or polyfunctional, and the type of functional group contained may be one type or two or more types.

The method of introducing these functional groups is not particularly limited, and for example, a method of directly synthesizing the polymer (I) using a monomer having these functional groups, or the polymer (I) in advance. After synthesizing the compound, a method of reacting the compound (I) with a compound having a desired functional group, a method of subjecting the polymer (I) to plasma treatment, and further a polymerization initiator and a desired function in the chain transfer agent. Examples include a method of introducing using a group-containing one.

Needless to say, the present invention is not limited to these specific examples. The bifunctional or higher polyfunctional reactive compound (IV) capable of reacting with bisphenol AF will be described later for reasons such as availability and diversity of raw materials, ease of cross-linking reaction, and improvement of adhesion to a substrate. Organic polyisocyanate compounds are preferred. Therefore, the functional group introduced into the polymer (I) is preferably a functional group which reacts with an isocyanate group. The functional group which reacts with the isocyanate group is not particularly limited as long as it is a functional group having active hydrogen, and examples thereof include functional groups having active hydrogen such as amino group, hydroxyl group, carboxyl group and active methylene. It is also possible to introduce an isocyanate group into the polymer (I) and react the isocyanate groups with each other to form a buret structure or crosslink alohanate.

Of these, in view of reactivity with isocyanate groups, polymerization of acrylic polymers, and availability of raw materials, crosslinking with hydroxyl groups is particularly preferable. There is no particular limitation on the method of introducing the hydroxyl group into the polymer (I), and the same method as the method of introducing the various functional groups described above can be mentioned, but among them, it is the simplest in the reaction process and the introduction amount can be easily controlled. Therefore, the method of synthesizing the polymer (I) using a monomer having a hydroxyl group is preferable.

Specific examples of the monomer containing a hydroxyl group include:
Examples thereof include hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate and modified products thereof. The hydroxyl group-containing monomer to be introduced into the polymer (I) may be one type or two or more types.

Needless to say, the present invention is not limited to these specific examples. Next, the fluorinated olefin-based polymer (II) according to the present invention, when a film is formed together with the polymer (I), as described above,
There is more on the air surface side, infiltration of dirt from the outside and transfer to the inside, that is, part of the base resin, or additives such as pigments, dyes and plasticizers contained in the base resin to the coating layer. Play a role in preventing

The fluorinated olefin polymer (II) is
A polymer containing a fluorinated olefin monomer, which is dispersed or dissolved in an organic solvent. As specific examples thereof, for example, polytetrafluoroethylene, polyvinylidene fluoride, (ethylene / tetrafluoroethylene) copolymer, (vinylidene fluoride / tetrafluoroethylene) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer Coalesce, polyvinyl fluoride ether, polychlorotrifluoroethylene, (ethylene / chlorotrifluoroethylene) copolymer, (vinyl fluoride ether / tetrafluoroethylene) copolymer and Lumiflon [Asahi Glass Co., Ltd.], Fluoronate [Dainippon Ink and Chemicals, Inc.], Sepular coating [Central Glass Co., Ltd.],
Fluorine paints such as Zeffle [Daikin Industry Co., Ltd.], Zaflon [Toagosei Co., Ltd.], Triflon [Mitsui Petrochemical Industry Co., Ltd.], Cytop [Asahi Glass Co., Ltd.], Teflon- AF [DuPont Co., Ltd.] or its analogs having a fluorinated cyclic ether in the side chain can be mentioned, but it has both processability such as compatibility with other acrylic components and solubility in solvents, and antifouling properties. In terms of,
Particularly, a vinylidene fluoride polymer is preferable.

As the vinylidene fluoride polymer, polyvinylidene fluoride, (vinylidene fluoride / tetrafluoroethylene) copolymer, (vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene) copolymer,
Examples thereof include (tetrafluoroethylene / hexafluoropropylene) copolymer and (vinylidene fluoride / hexafluoropropylene) copolymer.

Needless to say, the present invention is not limited to these specific examples. The vinylidene fluoride polymer not only shows excellent compatibility with other acrylic resins in solution, but also forms a barrier layer to prevent foreign substances from entering or foreign substances from entering when forming a film. By doing so, it becomes possible to improve the antifouling property of the entire film. Furthermore, since a flexible film having a very high elongation rate is formed as a film, when it is coated on a substrate, it has excellent conformability to the substrate and is easily applied to applications involving bending and bending.

The ratio of the above-mentioned polymers (I) and (II) contained in the coated antifouling composition according to the present invention is preferably 1 to 99/99 to 1, more preferably 10 by weight.
-80 / 90-20.

First, as the proportion of polymer (I) increases,
The antifouling property is lowered, and when the proportion of the polymer (II) is increased, the adhesion to the substrate is often lowered and the cost is increased. Therefore, if the types and introduction amounts of the above-mentioned polymers (I) and (II) are determined in consideration of the target degree of antifouling property, the adhesiveness associated with the type of substrate, and the cost, It is possible to obtain a coating agent that exhibits the existing antifouling performance.

By the way, the antifouling performance can be roughly classified into the ease of removal after dirt is attached and the difficulty of adhesion of dirt. By forming the barrier layer, the fluorinated olefin polymer (II) described above mainly contributes to the ease of removal after dirt is attached. However, in recent years, it has been increasingly demanded that the stain-resistant property is strongly adhered to in pursuit of higher antifouling properties.

According to the knowledge of the present inventors, fluorinated (meth) acrylate (A) and / or polysiloxane group-containing (meth) acrylate (B) and (meth) other than (A) and (B). It was clarified that by using the copolymer (V) obtained by polymerizing the acrylate (C) in combination, it is possible to exhibit the difficulty of getting stains.

That is, when the polymer (V) is used in combination with the above-mentioned polymer (I) and (II) systems, the polymer (V) is arranged on the outermost surface (air surface side) to prevent adhesion of dirt. It has an effect. Furthermore, by using the polymer (V) in combination, the compatibility between the polymer (I) and the polymer (II) is increased, and a highly transparent film is formed.

As the fluorinated (meth) acrylate (A), those containing an acrylic ester group and its related group are suitable from the viewpoints of availability of raw materials, compatibility with other components, and antifouling property. And a fluorinated (meth) acrylate represented by the following general formula (A-1).

[0032]

[Chemical 3]

In the formula, R _f is a perfluoroalkyl group having 1 to 20 carbon atoms or a partially fluorinated alkyl group, which is linear, branched, or has an oxygen atom intervening in the main chain, for example,

[0034]

[Chemical 4]

Etc., R ₁ is H, CH ₃ , Cl, F or CN, X is a divalent linking group, and specifically,
(CH ₂ ) _n ,

[0036]

[Chemical 5]

[0037]

[Chemical 6]

[0038]

[Chemical 7]

(However, n is an integer of 1 to 10, and R ₂
Is H or an alkyl group having 1 to 6 carbon atoms. ),

[0040]

[Chemical 8]

[0041]

[Chemical 9]

[0042]

[Chemical 10]

[0043]

[Chemical 11]

[0044]

[Chemical 12]

[0045]

[Chemical 13]

Etc. and a is 0 or 1. ] It is a compound represented by. Hereinafter, unless otherwise specified, methacrylate, acrylate, haloacrylate and cyanoacrylate are collectively referred to as (meth) acrylate.

Fluorinated (meth) acrylate (A-1)
The following may be mentioned as specific examples. A-1-1: CH ₂ = CHCOOCH ₂ CH ₂ C ₈ F ₁₇ A-1-2: CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ C ₈ F ₁₇ A-1-3: CH ₂ = CHCOOCH ₂ CH ₂ C ₁₂ F ₂₅ A-1-4: CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ C ₁₂ F ₂₅ A-1-5: CH ₂ = CHCOOCH ₂ CH ₂ C ₁₀ F ₂₁ A-1-6 : CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ C ₁₀ F ₂₁ A-1-7: CH ₂ = CHCOOCH ₂ CH ₂ C ₆ F ₁₃ A-1-8: CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ C ₆ F ₁₃ A-1-9: CH ₂ = CHCOOCH ₂ CH ₂ C ₄ F ₉ A-1-10: CH ₂ = CFCOOCH ₂ CH ₂ C ₆ F ₁₃ A-1-11: CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ C ₂₀ F ₄₁ A-1-12: CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ C ₄ F ₉ A-1-13: CH ₂ = C (CH ₃ ) COO ( CH ₂ ) ₆ C ₁₀ F ₂₁ A-1-14: CH ₂ = C (CH ₃ ) COOCH ₂ CF ₃ A-1-15: CH ₂ = CHCOOCH ₂ CF ₃ A-1-16: CH ₂ = CHCOOCH ₂ C ₈ F ₁₇ A-1-17: CH ₂ = C (CH ₃ ) COOCH ₂ C ₈ F ₁₇ A-1-18: CH ₂ = C (CH ₃ ) COOCH ₂ C ₂₀ F ₄₁ A-1-19: CH ₂ = CHCOOCH ₂ C ₂₀ F ₄₁ A-1-20: CH ₂ = C (CH ₃ ) COOCH ₂ CF (CF ₃ ) ₂ A-1-21: CH ₂ = C (CH ₃ ) COOCH ₂ CFHCF ₃ A -1-22: CH ₂ = CFCOOCH ₂ C ₂ F ₅ A-1-23: CH ₂ = CHCOOCH ₂ (CH ₂ ) ₆ CF (CF ₃ ) ₂ A-1-24: CH ₂ = C (CH ₃ ) COOCHCF ₂ CFHCF ₃ A-1-25: CH ₂ = C (CH ₃ ) COOCH (C ₂ H ₅ ) C ₁₀ F ₂₁ A-1-26: CH ₂ = CHCOOCH ₂ (CF ₂ ) ₂ H A-1-27: CH ₂ = C (CH ₃ ) COOCH ₂ (CF ₂ ) ₂ H A-1-28: CH ₂ = CHCOOCH ₂ (CF ₂ ) ₄ H A-1-29: CH ₂ = CHCOOCH ₂ CF ₃ A-1-30: CH ₂ = C (CH ₃ ) COO (CF ₂ ) ₄ H A-1-31 : CH ₂ = CHCOOCH ₂ (CF ₂ ) ₆ H A-1-32: CH ₂ = C (CH ₃ ) COOCH ₂ (CF ₂ ) ₆ H A-1-33: CH ₂ = CHCOOCH ₂ (CF ₂ ) ₈ H A-1-34: CH ₂ = C (CH ₃ ) COOCH ₂ (CF ₂ ) ₈ H A-1-35: CH ₂ = CHCOOCH ₂ (CF ₂ ) ₁₀ H A-1-36: CH ₂ = CHCOOCH ₂ (CF ₂ ) ₁₂ H A-1-37: CH ₂ = CHCOOCH ₂ (CF ₂ ) ₁₄ H A-1-38: CH ₂ = CHCOOCH ₂ (CF ₂ ) ₁₈ H A-1-39: CH ₂ = CHCOOC (CH ₃ ) ₂ (CF ₂ ) ₄ H A-1-40: CH ₂ = CHCOOCH ₂ CH ₂ (CF ₂ ) ₇ H A-1-41: CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ ( CF ₂ ) ₇ H A-1-42: CH ₂ = C (CH ₃ ) COOC (CH ₃ ) ₂ (CF ₂ ) ₆ H A-1-43: CH ₂ = CHCOOCH (CF ₃ ) C ₈ F ₁₇ A -1-44: CH ₂ = CHCOOCH ₂ C ₂ F ₅ A-1-45: CH ₂ = CHCOOCH ₂ CH (OH) CH ₂ C ₈ F ₁₇ A-1-46: CH ₂ = C (CH ₃ ) COOCH ₂ CH (OH) (CH ₂ ) ₄ C ₁₈ F ₃₇ A-1-47: CH ₂ = CHCOOCH ₂ CH ₂ N (C ₃ H ₇ ) SO ₂ C ₈ F ₁₇ A-1-48: CH ₂ = C (CH ₃ ) COOCH ₂ CH ₂ N (CH ₃ ) SO ₂ C ₆ F ₁₃ A-1-49: CH ₂ = C (Cl) COO (CH ₂ ) ₆ NHSO ₂ C ₁₂ F ₂₅ A-1-50: CH ₂ = CHCOOCH ₂ CH ₂ N (C ₂ H ₅ ) COC ₇ F ₁₅ A-1-51: CH ₂ = CHCOO (CH ₂ ) ₈ N (CH ₃ ) COC ₁₂ F ₂₅ A-1-52: CH ₂ = CHCOO (CH ₂ ) ₂ (CF ₂ ) ₈ CF (CF ₃ ) ₂ Antifouling property of the coating resin composition according to the present invention, and From the viewpoint of improving the durability, the carbon number of the perfluoroalkyl group or the partially fluorinated alkyl group of the fluorinated (meth) acrylate (A-1) is preferably 4 or more, more preferably 6 or more.

Further, the fluorinated (meth) acrylate (A) contains a fluorinated alkyl group from the economical point of view, efficient compatibility with other components, and antifouling property.
A polymerizable ethylenically unsaturated monomer having at least two valent groups, all of which have a skeleton bonded to the same carbon atom or nitrogen atom, and at least a monovalent group containing a fluorinated alkyl group. It is preferable that one is a monovalent group having an ester bond or a urethane bond between the carbon atom or nitrogen atom and the fluorinated alkyl group. Examples of such a fluorinated (meth) acrylate include those represented by the general formula

[0049]

[Chemical 14]

[In the formula, Rf is a fluorinated alkyl group having 1 to 20 carbon atoms, and Z is-(CH ₂ ) _X- , -CH ₂ CH.
_{(OH) (CH 2) X} -, - (CH 2) X N (R 1) SO 2
_{-, - (CH 2) X} N (R 1) CO- ( where X is 1 or 2, R ₁ is H or an alkyl group having 1 to 6 carbon _{atoms), - CH (CH 3)} - _{, -CH (C 2 H 5)} -, -
_{C (CH 3) 2 -,} - CH (CF 3) - or - (CF _{3) 2}
A divalent linking group such as-, R ₂ is H, Cl, CH ₃ ,
F, or _{- (CH 2) X Rf (} . However, X, Rf are as defined above), and, A is _{R 3 C (CH 2 -)} 3, R 3 is H, methyl, ethyl, Or a nitro group. ), Or _{N (CH 2 CH 2) 3} -, N (CH 2 CH (CH 3)) 3 -
Is a trivalent linking group represented by and B is -OCONHY
₁ NHCOO- (However, Y ₁ has 15 or less carbon atoms, and D
It is a divalent linking group having a weight ratio of 35 to 65%. ) Is a divalent linking group represented by Z ₁
It is - (CH _{2) m} - (where, m is an integer from 2 to 6.) Or -CH ₂ CH (CH ₃₎ - is. ] The compound represented by these is mentioned.

In the general formula (A-2), two contained Z are different from each other selected from the group of the above divalent linking groups.
It may be a kind of linking group. A typical example of the Y ₁ group in the divalent linking group B is:

[0052]

[Chemical 15]

And the like. Also the general formula

[0054]

[Chemical 16]

[Wherein Rf, Z, Z₁, Is the same as above
Rf ′ is a fluorinated alkyl group having 1 to 20 carbon atoms
And Z'is-(CH₂)_X-, -CH₂CH (OH)
(CH₂) _X-,-(CH₂)_XN (R₁) SO₂-,-
(CH₂)_XN (R₁) CO- (where X is 1 or 2)
Yes, R₁Is H or an alkyl group having 1 to 6 carbon atoms
), -CH (CH₃)-, -CH (C₂H_Five)-, -C
(CH₃)₂-, -CH (CF₃) -Or- (CF₃)₂−
R is H or F. X
₁, X₂, And X₃Is -OCOCH₂CH (R_Four) COO
-(However, R_FourIs H or alkyl having 1 to 36 carbon atoms
It is a group or an alkenyl group. ) Or

[0056]

[Chemical 17]

A is a divalent linking group selected from the group consisting of: A ₁ is R ₅ C (CH ₂ OCH ₂ CH (OH) CH ₂ )
_{3 -, R 5 C (CH} 2 OCH 2 CH 2 OCH 2 CH (OH) C
H _{2) 3} -. (Where, R ₅ is H, hydroxymethyl group, a methyl group, an ethyl group, or a nitro group), N (CH _{2
CH 2 OCH 2 CH (OH)} CH 2) 3 -, or N (CH _{2
CH (CH 3) OCH 2 CH} (OH) CH 2) 3 - is a trivalent linking group represented by. ) A compound represented by the general formula

[0058]

[Chemical 18]

[Wherein Rf, Rf, Z, Z ', and R
Is the same as above, and X ₄ and X ₅ are -C00-, -OCO.
_{CH 2 CH (R 4) COO-} ( where, R ₄ is as defined above.)

[0060]

[Chemical 19]

Alternatively, it is a divalent linking group represented by -OCONHY ₁ NHCOO- (Y ₁ is the same as defined above). And a divalent linking group selected from ], A compound represented by the general formula

[0062]

[Chemical 20]

[Wherein Rf, Rf ′, Z, Z ₁ and R are the same as defined above, and Rf ″ is Rf or Rf ′.
, Which may be the same or different, Z ″ is the same as Z or Z ′, which may be the same or different, X ₆ , X ₇ , X ₈
May be the same or different and may be -O- or -OCON.
HY ₁ NHCOO- (however, Y ₁ is the same as above).
Is a divalent linking group represented by and X ₉ is -OCONH
A divalent linking group represented by Y ₁ NHCOO- (where Y ₁ is the same as above) or -OCONH (CH ₂ ) _a- (where a is an integer of 0 to 2). And Z ₁ is the same as above. ] It is a compound represented by.

Monomers (A-2), (A-3), (A-
Specific examples of 4) and (A-5) include, for example, the followings, but it goes without saying that the present invention is not limited to these specific examples.

[0065]

[Chemical 21]

[0066]

[Chemical formula 22]

[0067]

[Chemical formula 23]

[0068]

[Chemical formula 24]

[0069]

[Chemical 25]

[0070]

[Chemical formula 26]

[0071]

[Chemical 27]

[0072]

[Chemical 28]

[0073]

[Chemical 29]

[0074]

[Chemical 30]

[0075]

[Chemical 31]

The fluorinated (meth) acrylate (A) may be a mixture of two or more kinds of compounds having different structures. According to the knowledge of the present inventor, in order to impart antifouling property, it is effective to introduce a polysiloxane group-containing (meth) acrylate in addition to the fluorinated (meth) acrylate. The fluorinated (meth) acrylate and the polysiloxane group-containing (meth) acrylate may be either one or both depending on the compatibility with the polymer (I) or the polymer (II) or the application. Their antifouling properties are maintained at a high level.

A polysiloxane group-containing (meth) acrylate means that a polysiloxane chain has two ends at one end or both ends.
A group in which either an acryloyl group or a methacryloyl group is linked via a valent linking group, and specific examples thereof include the general formula (B-1)

[0078]

[Chemical 32]

[Wherein, R ₆ and R ₇ are alkyl groups having 1 to 20 carbon atoms or phenyl groups, which may be the same or different, and may be the same or different for each siloxy unit; Is an integer of 3 to 520, q is 0 or 1, Y ₂ is a divalent linking group, —CH ₂ CH (OH) CH.
_{2 OCO -, - (CH 2} ) n1 NHCH 2 CH (OH) CH 2
_{OCO -, - (CH 2)} n1 OCO -, - (CH 2) n1 -O
- (CH _{2) m1} OCO-, or -OCH ₂ CH (OH) C
H ₂ OCO- [where, n _1, m ₁ is an integer from 2 to 6. ], R ₁ is the same as above, Z ₂ is C _n H
An alkyl group represented by _{2n + 1} , a phenyl group, or CH ₂ =
_{C (R) - (Y 2} ) q - is. ] The compound represented by
Or general formula (B-2)

[0080]

[Chemical 33]

[Wherein R ₆ ′, R ₆ ″, R ₆ ″ ″, R ₇ ′,
R ₇ ″, R ₇ ″ ″, R ₈ ′, R ₈ ″, R ₈ ″ ″ have 1 to 20 carbon atoms
Which may be the same or different, r, s and t are integers of 1 to 200, which may be the same or different, and Y ₂ , q and R are the same as those described above. It is the same meaning. ] The compound represented by these is mentioned.

The following are more specific examples of the monomer containing a polysiloxane chain.

[0083]

[Chemical 34]

[0084]

[Chemical 35]

[0085]

[Chemical 36]

[0086]

[Chemical 37]

However, in both cases, Me and Ph represent a methyl group and a phenyl group, respectively. Needless to say, the present invention is not limited to the above specific examples.

In the present invention, the fluorinated (meth) acrylate (A) and / or the polysiloxane group-containing (meth) acrylate (B) is a preferable monomer component for exhibiting antifouling property. If both are missing, the above performance deteriorates.

On the other hand, the above-mentioned fluorinated (meth) acrylate (A) and / or polysiloxane group-containing (meth)
As (meth) acrylate (C) other than (A) and (B) copolymerized with acrylate (B), methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, dodecyl acrylate, methyl methacrylate , Ethyl methacrylate, butyl methacrylate, octyl methacrylate, dodecyl methacrylate, acrylonitrile, hydroxybutyl acrylate, hydroxypropyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl methacrylate, dibutyl fumarate, dimethyl fumarate, etc. be able to. The (meth) acrylate (C) other than (A) and (B) may be a polymer of one type of monomer or a polymer of two or more types of monomers. .

Needless to say, the present invention is not limited to these specific examples. According to the knowledge of the present inventors, from the viewpoints of compatibility of the polymers (I) and (II), toughness of the film, etc., as the (meth) acrylate (C) other than (A) and (B), , Methyl methacrylate is preferred. Copolymerization of methyl methacrylate not only improves the compatibility with other polymers, but also contributes to antifouling properties as a hard component of the film, and further because the homopolymer has a high glass transition point, The toughness of the coating can be improved.

According to the knowledge of the present inventors, from the viewpoint of toughness of the film and imparting of solvent resistance, a reactive functional group is added to the polymer (V) as in the case of the polymer (I). It is preferable to introduce. There is no particular limitation on the type of reactive functional group, but the selection is made by the bisphenol AF described later.
It is determined by the reactivity with a bifunctional or higher polyfunctional reactive compound (IV) capable of reacting with. The type of reactive functional group that can be introduced and the method of introducing the reactive functional group are the same as in the case of the polymer (I).

The copolymerization composition ratio of the monomer (A) and / or (B) and the monomer (C) in the polymer (V) according to the present invention is usually 100: 0 to 0 by weight. 1: 1000, preferably in the range of 2: 1 to 1: 100, 49:51
To 1: 100 are various properties as a coating agent shown in the present invention, that is, solvent solubility of the polymer (V) of the present invention related to coating workability, antifouling property, film characteristics and further in the polymer (V). It is more preferable in terms of economic efficiency related to the fluorine content.

When the polymer (V) is used in combination, the amount introduced is 0.0 with respect to the total amount of the polymers (I) and (II).
The amount is 1% by weight to 100% by weight, preferably 1% by weight to 50% by weight.

The method for producing the polymers (I) and (V) according to the present invention is not limited at all, and based on known methods, that is, radical polymerization method, cationic polymerization method, anionic polymerization method and the like, It can be produced by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method or the like, but a radical polymerization method is particularly simple and industrially preferable.

In this case, as the polymerization initiator, those known in the art can be used, for example, peroxides such as benzoyl peroxide and diacyl peroxide, azobisisobutyronitrile, phenylazotriphenylmethane and the like. Azo compounds, metal chelate compounds such as Mn (acac) _{3 and the} like. Further, if necessary, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, ethylthioglycolic acid, octylthioglycolic acid, or a coupling group-containing thiol such as γ-mercaptopropyltrimethoxysilane. It is possible to use chain transfer agents of the following compounds:

According to the knowledge of the present inventors, when such a coupling group-containing chain transfer agent is used in combination, it is possible to improve the adhesion to a substrate and the durability as a coating agent. . The fluorine-based random or block copolymer according to the present invention can also be obtained by photopolymerization in the presence of a photosensitizer or a photoinitiator, or polymerization using radiation or heat as an energy source.

The polymerization can be carried out in the presence or absence of a solvent, but it is preferable in the presence of a solvent from the viewpoint of workability. Examples of the solvent include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as methyl acetate, ethyl acetate and butyl acetate, polar solvents such as dimethylformamide and dimethyl sulfoxide, 1,1,1-trichloroethane and chloroform. Halogen-based solvent, ethers such as tetrahydrofuran and dioxane, aromatics such as benzene, toluene and xylene,
Further, any of fluorinated inner liquids such as perfluorooctane and perfluorotri-n-butylamine can be used.

The resin composition, role and effect of the antifouling composition for coating have been described above. Next, the present system for enhancing the adhesiveness, solvent resistance and adhesion between the respective components is described. The cross-linking system will be described.

First, the fluorinated olefin polymer (II)
Conventionally, in the field of fluororubber, bisphenol A
It is known to be crosslinked by F. Therefore, if a polymer (II) that can be crosslinked with bisphenol AF is selected, the polymers (II) can be crosslinked with each other.

Next, in order to enhance the adhesiveness between the polymer (I) [the polymer (V) if necessary] and the polymer (II), a reaction with the hydroxyl group of bisphenol AF is carried out in the polymer (I). Method with a reactive functional group, or bisphenol A
Bifunctional or higher polyfunctional reactive compound (IV) capable of reacting with F
A method of cross-linking the polymers (I) and (II) via the polymer can be considered, but the latter is industrially more useful in consideration of the reactivity of bisphenol AF and the reactive functional group in the polymer. When cross-linked by this method, a polyfunctional reactive compound (I
There is no particular limitation on the type of V), bisphenol AF
Also, any polymer having two or more reactive functional groups in the molecule, which reacts with the functional groups introduced into each polymer as described above, may be used.

As the reactive functional group, those similar to those introduced into each polymer can be used.
Hydroxyl group, thiol group, carboxyl group, amino group, isocyanate group, aziridinyl group, glycidyl group, alkoxysilyl group, silanol group, cyclocarbonate group, acid anhydride group, vinyl group, enol ether group, thioether group, active ester group, Examples include acetoacetate groups, metal salts, metal oxides, and functional groups obtained by blocking these functional groups with various blocking agents. The type of the functional group contained may be one type or two or more types. Moreover, as long as it is a bifunctional or more compound containing these functional groups, it may be a low molecular compound or a high molecular compound.

As the polyfunctional reactive compound, organic epoxy compounds and organic polyisocyanate compounds are industrially used for the reasons such as availability and variety of raw materials, toughness of formed film, and improvement of adhesion to substrate. It is useful. In addition, organic polyisocyanate compounds are particularly useful because of the ease of the crosslinking reaction.

Examples of the organic epoxy compound include compounds containing two or more glycidyl groups in the molecule. For example, various epoxy resins and low molecular weight compounds having two or more glycidyl groups include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, polyethylene glycol. Diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether,
Examples thereof include 1,6 hexanediol diglycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, spiroglycol diglycidyl ether, but are not particularly limited thereto.

As the organic polyisocyanate compound,
For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate. , 3,3'-dimethyl-4,4'biphenylene diisocyanate, 3,3'-dimethoxy-
4,4 'biphenylene diisocyanate 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,
5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, Xylylene diisocyanate, tetramethyl xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate, and these compounds Dimers, trimers or phenols, oximes, alcohols, active Ren acids, mercaptans,
Examples thereof include acid amides, imides, amines, imidazoles, ureas, carbamates, imines or polyisocyanates partially blocked with sulfites.

Needless to say, the present invention is not limited to these specific examples. Other than these, isocyanate prepolymers having an isocyanate group at the terminal obtained by the reaction of the above-mentioned various isocyanate compounds with various active hydrogen compounds as described below, and the like.

The active hydrogen compound is not particularly limited as long as it is a compound having a group capable of reacting with an isocyanate group, that is, an active hydrogen atom, and any compound can be used. Generally, a compound having an alcoholic hydroxyl group is used. Is used. Examples of the compound having an alcoholic hydroxyl group include ethylene glycol, propylene glycol, 1,3- or 1,4-butylene glycol,
Various diols such as 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol or dipropylene glycol, or various polyols such as glycerin, trimethylolpropane or pentaerythritol, or various diols thereof and / or Polyester diols obtained from polyols and various aliphatic polycarboxylic acids, further various polyether diols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, and further polycarbonate diols, etc. This is a typical example.

These organic polyisocyanate compounds may be used alone or in a mixture of two or more kinds.
Needless to say, the present invention is not limited to these specific examples.

Further, as a matter of course, the bifunctional or higher polyfunctional reactive compound (IV) capable of reacting with the bisphenol AF is converted into the polymer (I) [including the polymer (V) if necessary]. Since it also reacts with the introduced reactive functional group, crosslinking between the polymers (I) [in some cases, the polymers (I) and (V) or between the polymers (V)] can be performed simultaneously. further,
The polyfunctional reactive compound (IV) also improves the adhesion between the coating composition and the substrate due to the anchoring effect by permeation into the substrate or the reaction with the functional group in the substrate.

Bisphenol AF and Bisphenol AF
There is no particular limitation on the method of introducing the bifunctional or higher functional reactive compound (IV) capable of reacting with the compound into the composition of the present invention. That is, bisphenol AF and the reactive compound (IV) may be mixed in the composition and applied on the substrate to cause a crosslinking reaction, or bisphenol AF and the polyfunctional reactive compound (I
V) is reacted in advance to synthesize a compound in which the reactive functional group in the polyfunctional reactive compound (IV) is present at one or both ends of bisphenol AF, and the compound is added to the composition to form a group. After coating on the material, a crosslinking reaction may occur. Here, the reaction conditions for preliminarily reacting the bisphenol AF and the polyfunctional reactive compound (IV) are determined by the reactivity between the functional groups of both and are not particularly limited, and the polyfunctional reactive compound (IV) When the reactivity of is low, various catalysts may be used together.

Also, in the composition, bisphenol AF
The cross-linking reaction after compounding the bifunctional or higher functional reactive compound (IV) capable of reacting with bisphenol AF or its reaction product can be carried out in the same manner as the cross-linking reaction of fluororubber. That is, a crosslinking reaction proceeds by adding a quaternary phosphonium salt as a catalyst, an inorganic oxide such as calcium hydroxide or magnesium oxide as an acid acceptor, and applying heat.

Bisphenol AF and Bisphenol AF
The amount of the bifunctional or more polyfunctional reactive compound (IV) capable of reacting with the compound introduced into the composition depends on the amount of functional groups in the resin and the hardness of the target film, but both are related to the resin. It is 0.01% to 30% by weight, preferably 0.1% to 10% by weight, based on the composition solid. If it is less than this, the solvent resistance to various organic solvents and the film strength will be reduced, and conversely if it is too much, the film will become brittle.

As described above, by using the bifunctional or more polyfunctional reactive compound (IV) capable of reacting with bisphenol AF and bisphenol AF, adhesion between each component, between each component and with the substrate can be improved. It becomes possible to strengthen, and as a result, toughness of the film, solvent resistance, and substrate adhesion are improved.

Various additives can be introduced into the antifouling composition for coating according to the purpose. For example, when the base material is coated, a silane-based, titanium-based, zirco-aluminate-based coupling agent or the like can be used together for the purpose of improving the adhesion to the base material. As the coupling agent, among these, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, dimethylvinylmethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ −
Silane coupling agents such as aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane and γ-mercaptopropyltrimethoxysilane are particularly preferable. Further, a fluorine atom-containing alkoxysilane compound,
A fluorine-based coupling agent such as a fluorine atom-containing titanium acylate compound or a fluorine atom-containing alkoxyzirconium compound can also be used.

If necessary, the coating composition according to the present invention may include pigments, dyes, colorants such as carbon, silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, calcium carbonate and the like. It is possible to appropriately add inorganic powder, higher fatty acid, organic fine powder such as poly (vinylidene fluoride), poly (tetrafluoroethylene), and polyethylene, and various fillers such as light resistance improver and weather resistance improver. is there.

Examples of the base material according to the present invention include inorganic materials such as glass, quartz and silica, metals such as iron, copper, ferrite, cobalt, nickel and aluminum and alloys thereof, polyethylene, polystyrene, methyl polymethacrylate, and the like. Thermoplastic resin typified by polyvinyl chloride,
Polyesters such as polyethylene terephthalate and polyethylene 2,6-naphthalate, engineering plastics such as polyparaphenylene sulphite, polyamide resin and polyimide resin, urethane resin, alkyd resin, phenol resin, epoxy resin, silicone resin, polycarbonate resin and the like. . These substrates can be subjected to a primer treatment known in the art, if necessary, when they are coated with good adhesion.

The coating composition according to the present invention is adjusted to a suitable concentration or viscosity with a solvent suitable for the purpose, if necessary, and then coated with various bases by a method such as gravure coater, knife coater, dipping coating or spray coating. It can be applied to a material, and after application, post-processing such as foaming, embossing, embossing, pressing, printing, and welding can be performed. Needless to say, the present invention is not limited to the above specific examples.

The coating composition according to the present invention is, for example, a wall covering, a floor covering, a marking film, a reflecting sheet, a polyvinyl chloride steel sheet, an agricultural vinyl film, a decorative paper, a polyvinyl chloride sheet, a polyvinyl chloride leather, an artificial material. It can be used as an antifouling coating agent for leather, synthetic leather, paper, wood, artificial marble, tarpaulins, tents, nets, table cloths, desk mats and the like. It can also be used as a top coat agent for various paints. As the paint, a paint using a natural resin, for example, a petroleum resin paint, shellac paint, rosin paint, cellulose paint,
Rubber-based paints, lacquer, cashew resin paints, oil-based vehicle paints, etc., and paints using synthetic resins such as phenol resin paints, alkyd resin paints, unsaturated polyester resin paints, amino resin paints, epoxy resin paints, vinyl resin paints Examples thereof include acrylic resin paints, polyurethane resin paints, silicone resin paints, fluororesin paints, and the like, but are not particularly limited thereto.

Needless to say, the present invention is not limited to the above specific examples. The coating composition according to the present invention has, in addition to the intended use, surface lubricity, scratch resistance, oil resistance, smoothness, water / oil repellency, water resistance, moisture resistance, rust resistance, peelability, and low water absorption. Since it forms a film having excellent properties, it can be used as a protective coating film for various materials and substrates.

For example, non-magnetic metals such as copper, aluminum and zinc, polyesters such as polyethylene terephthalate and polyethylene-2,6-naphthalate, polyolefins such as polypropylene, cellulose acetate and the like. Ferromagnetic alloys (iron, cobalt and / or nickel) deposited on plastics such as cellulosic derivatives, polycarbonates and optionally ceramics such as glass, paper, wood, fibers, porcelain and pottery. A main component that contains a small amount of aluminum, silicon, chromium, manganese, molybdenum, titanium, various heavy metals, rare earth metals, etc.) or a magnetic material such as iron, cobalt, chromium, etc. in the presence of a trace amount of oxygen, and a plastic film such as polyester Magnetic tape deposited on the surface or protective coating of the magnetic layer of the magnetic disk, and anti-friction property Particularly required, magnetic tape - flop, floppy - also suitable as surface and back surface treating agent for a magnetic recording medium such as a disk.

Furthermore, it is also suitable as a protective coating for a solar cell protective film, an optical fiber, an optical fiber cable, an optical disk, a magneto-optical disk, etc., which is particularly required to have a moisture-proof property. Furthermore, since it is excellent in scratch resistance, antifouling property and moisture resistance, it can be used as surface protection for medical devices and instruments, teeth, surface protection of dentures and tooth cavities, and can also be used as a mold, and the coating composition of the present invention, Since a film having excellent scratch resistance can be formed, it can be used as a hard coat agent for various molded products, films, sheets and the like.

Furthermore, the coating composition of the present invention can form a paint or ink excellent in antifouling property or non-tackiness by incorporating a pigment and a dispersant. Therefore, it is also useful as a ship bottom paint and an anti-icing snow paint.

[0122]

EXAMPLES Next, reference examples, examples and comparative examples are given in order to explain the present invention in more detail, but it goes without saying that the present invention is not limited to these examples. "Parts" in the text are by weight unless otherwise specified.

Reference Example 1 (Synthesis of Polymer I-1) 5 parts by weight of ethyl acrylate, 92 parts by weight of methyl methacrylate, 3 parts by weight of 2-hydroxyl ethyl methacrylate were added to a glass flask equipped with a stirrer, a condenser and a thermometer. 233 parts by weight of -n-butyl acetate were charged, and 0.4 parts by weight of azobisisobutyronitrile (hereinafter abbreviated as AIBN) as a polymerization initiator was added under reflux in a nitrogen gas stream, and then at 6 ° C at 85 ° C. React for time, then 0.2
After adding a weight part, it was made to react at 85 degreeC for 5 hours, and superposition | polymerization was completed.

Reference Examples 2 to 4 (Polymer I-2, V-1, V-
2 Synthesis) Each polymer solution was obtained in the same manner as in Reference Example 1. Reference example 5
The following was used as 7. Table 1 shows reference examples 1 to 1.
7 is shown collectively.

[0125]

[Table 1] The abbreviations in the table are as follows. EA: Ethyl Methacrylate MMA: Methyl Methacrylate 2-HEMA: 2-Hydroxylmethylmethacrylate Kiner ADS: (Product name: Elf Atchem Japan, vinylidene fluoride-4 fluoroethylene-6 fluoropropylene copolymer) ) Kainer 2801: (trade name: Elf Atochem Japan, vinylidene fluoride-6-propylene propylene copolymer) Bernock DN-950: (trade name: Dainippon Ink and Chemicals, Inc., organic polyisocyanate) (Solid content concentration: 76% by weight, NCO content: 13% by weight) Polymer (I), polymer (II), polymer (V) and bisphenol AF and polyfunctional reactive compound (I
V) and benzyltriphenylphosphonium chloride (BTPP) necessary for the crosslinking reaction of bisphenol AF (III)
CL), calcium hydroxide and magnesium oxide are each mixed in a predetermined amount, and the non-volatile content is 15%, and the solvent composition is methyl ethyl ketone / methyl isobutyl ketone / n-butyl acetate = 35/5/60 with each solvent. It was adjusted.

The prepared solution was applied to the applicator (100
μm) to a polyurethane sheet and dried at 70 ° C. for 1 minute, then 170 ° C. for 5 minutes, then 50 ° C. for 1 minute.
A test piece was prepared by performing heat treatment for 8 hours.

Table 2 collectively shows the mixing ratio of each sample. All numbers in the table indicate parts by weight.

[0128]

[Table 2] <Test Method and Evaluation Criteria> The antifouling property and the bleeding prevention property of the filler were evaluated by the magic stain property.

The magic stain resistance is the adhesion of the magic ink when the test piece is drawn with red, blue and black oil-based magic, and the adhered test piece is left at room temperature for 24 hours and then wiped with ethanol-impregnated absorbent cotton. The degree of stain was visually evaluated in five levels.

The anti-bleeding property of the filler is such that, in the above-mentioned magic contamination test, the leaving temperature after the attachment of the magic is 50 ° C., the mobility of the filler is increased, and the influence of the filler is strong. Was set and compared with the one left at room temperature.

Evaluation of abrasion resistance and adhesion is 5 cm × 10 cm
Using a Scott type chaff wear tester [Toyo Seiki Seisakusho, Ltd.] using the above test piece, a load of 1 kg and a moving speed of 120
The state of the coating after 2000 times at a speed of 5 times / minute was judged by a 5-level evaluation.

The solvent resistance was evaluated in five stages by the state of the film after the test piece was rubbed 100 times with absorbent cotton soaked with toluene and methyl ethyl ketone (MEK). Table 3 collectively shows these evaluation results. It should be noted that the larger the numerical value of the five-level evaluation in the table, the better the performance.

As is apparent from Table 3, the antifouling composition for coating of the present invention has extremely remarkable stain resistance and bleed preventive property of the filler, but also has excellent wear resistance, adhesion and solvent resistance. It turns out to be excellent.

[0134]

[Table 3]

[0135]

EFFECTS OF THE INVENTION By using the composition of the present invention, it is possible to provide a coating agent for various base materials which has excellent adhesion to the base material, film characteristics, and a long-life antifouling effect.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-2-300390 (JP, A) JP-A-63-234068 (JP, A) JP-A-5-24160 (JP, A) JP-A-6- 57196 (JP, A) JP-A-3-119065 (JP, A) JP-A-7-76667 (JP, A) JP-A-5-117479 (JP, A) JP-A-6-41379 (JP, A) JP-A-7-34060 (JP, A) JP-A-61-275365 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 127/00-127/24 C08L 27/00 -27/24 C09D 5/16 C09D 133/00-133/26 C08L 33/14-33/26

Claims (5)

(57) [Claims] 1. A polymer (I) of a monomer having a (meth) acryloyl group and a fluorinated olefin polymer (II).
And bisphenol AF (III) represented by the following formula: And an antifouling composition for coating, comprising a bifunctional or higher polyfunctional reactive compound (IV) capable of reacting with the bisphenol AF (III). 2. The composition according to claim 1, wherein the polymer (I) of the monomer containing a (meth) acryloyl group contains a hydroxyl group. 3. Further, a fluorinated (meth) acrylate (A) and / or a polysiloxane group-containing (meth) acrylate (B) is polymerized with a (meth) acrylate (C) other than (A) and (B). The copolymer (V) thus obtained is used in combination, and the composition according to claim 1 or 2. 4. The (meth) acrylate (C) other than (A) and (B) of the copolymer (V) is a hydroxyl group-containing (meth) acrylate.
The composition as described. 5. A polyfunctional reactive compound (IV) having two or more functional groups.
Is an organic polyisocyanate compound, The composition according to any one of claims 1 to 4, wherein