JP3449014B2 - 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 a coating composition having excellent antifouling properties and bleeding prevention properties such as plasticizers.

[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.

For example, those which coat polymers of various (meth) acrylic acid alkyl esters, those which coat copolymers of them with fluorine-based monomers and silicon-based monomers, and those and binder resins Those for coating a blended material are known. Above all,
The introduction of fluorine-based or silicon-based monomers has been considered to be an effective means (Japanese Patent Laid-Open No. 63-61032,
JP-A-63-137934).

However, when the base material is plasticized polyvinyl chloride, the composition obtained by a conventionally known method such as introduction and polymerization of an appropriate amount of fluorine-based or silicon-based monomer commensurate with the cost is There was a problem that sufficient antifouling performance could not be exhibited due to influences and the like. Further, there has always been a concern about the problem of impairing the adhesion to the substrate when introducing the fluorine or silicone-based monomer. In particular, PVC plastics with a high plasticizer content among plasticized polyvinyl chloride, artificial leather, synthetic leather, etc. are required to have a high degree of adhesion such as flex resistance and abrasion resistance. There has been a demand for a surface coating agent having both antifouling property and antifouling property.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the problem of adhesion of a fluorine-based or silicone-based composition to a substrate, which is a weak point of the composition. In addition to finding an antifouling performance that has not been found in the past, in addition to finding a composition that forms a bleeding-preventing effect of resin internal additives such as plasticizers, pigments, dyes, etc. contained in the base material and contact with foreign matter Another object of the present invention is to provide a coating resin composition having an excellent effect of preventing migration of some or all of the compounds contained in foreign matter.

[0006]

The inventors of the present invention have made extensive studies in order to solve the above-mentioned problems. As a result, a non-fluorinated acrylic polymer, a fluorinated acrylic polymer and a fluorinated olefin polymer have been identified. It has been found that the above problems can be solved by using a composition comprising an optimal combination with a curing agent, and the present invention has been completed.

That is, according to the present invention, a polysiloxane group-containing (me
A) acrylate (B) and fluorinated (meth) acryl
Other than the (A) and the (meth) acrylate (B)
A copolymer obtained by polymerizing with (meth) acrylate (C)
A protective coating for coating containing the polymer (I) , a polymer (II) of a monomer containing a (meth) acryloyl group, a fluorinated olefin polymer (III) and a curing agent (IV). A dirty composition is provided. Further, the present invention provides fluorine
(Meth) acrylate (A) and polysiloxane group
Existence (meth) acrylate (B) and the (meth) acryl
Other than the (A) and the (meth) acrylate (B)
A copolymer obtained by polymerizing with (meth) acrylate (C)
A polymer (I) and a monomer containing a (meth) acryloyl group
Polymer (II) and fluorinated olefin polymer
Antifouling property for coating containing (III) and curing agent (IV)
A composition is provided.

In the present invention, first, a polysiloxane group-containing (meth) acrylate (B) or fluorinated
Containing (meth) acrylate (A) and polysiloxane group
The copolymer (I) obtained by polymerizing the (meth) acrylate (B) and the (meth) acrylate (C) other than the (meth) acrylate (A) and the (meth) acrylate (B) is When the composition of the present invention is coated on a base material, it is a portion arranged on the outermost surface (air surface side), and therefore has a direct effect on contact and mixing of foreign matter from the outside. That is, it is a very important part in exhibiting antifouling properties. Further, a more economical fluorine content is exhibited at the maximum anti-blocking effect, or a (meth) acryloyl group-containing monomer polymer (II) and a fluorinated olefin polymer (III) are combined. In order to obtain excellent compatibility between the polysiloxane group-containing (meth) acrylate (B)
Or alternatively fluorinated (meth) acrylate (A) and polysiloxane group-containing (meth) acrylate (B),
It is preferable to use a polymer with a (meth) acrylate (C) other than (A) and (B).

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). Sana <br/> Why ,

[0010]

[Chemical 1]

(In the formula, Rf is a perfluoroalkyl group having 1 to 20 carbon atoms or a partially fluorinated alkyl group,
Linear, branched, or intervening oxygen atoms in the main chain, eg

[0012]

[Chemical 2]

And the like, R ₁ is H, CH ₃ , Cl, F or CN, and X is a divalent linking group, specifically:
(CH ₂ ) _n −

[0014]

[Chemical 3]

[0015]

[Chemical 4]

[0016]

[Chemical 5]

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

[0018]

[Chemical 6]

[0019]

[Chemical 7]

[0020]

[Chemical 8]

[0021]

[Chemical 9]

[0022]

[Chemical 10]

[0023]

[Chemical 11]

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) is a monovalent group containing a fluorinated alkyl group, from the viewpoints of economic efficiency, efficient compatibility with other components, and antifouling property. A polymerizable ethylenically unsaturated monomer having at least two skeletons, all of which are bonded to the same carbon atom or nitrogen atom, and at least one monovalent group containing a fluorinated alkyl group, A monovalent group having an ester bond or a urethane bond between the carbon atom or nitrogen atom and the fluorinated alkyl group is preferable. Examples of such a fluorinated (meth) acrylate include those represented by the general formula

[0027]

[Chemical 12]

[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 ( where R ₃
Is H, a methyl group, an ethyl group, 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-, B is -OCONH
Y ₁ NHCOO- (However, Y ₁ has 15 or less carbon atoms, and
It is a divalent linking group having a weight ratio of 35 to 65%. ) Is a divalent linking group represented by Z ₁
Is - (CH _{2) m} - (where, m is an integer from 2 to 6.)
Or -CH ₂ CH (CH ₃₎ - it 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 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:

[0030]

[Chemical 13]

And the like. Also the general formula

[0032]

[Chemical 14]

[In the formula, Rf, Z and Z ₁ are the same as defined above, Rf ′ is a fluorinated alkyl group having 1 to 20 carbon atoms, and Z ′ is — (CH ₂ ) _X —, —CH ₂ CH (OH) (C
_{H 2) X -, - (} CH 2) X N (R 1) SO 2 -, - (C
_{H 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 (C
_{H 3) 2 -, - CH} (CF 3) - or - (CF _{3) 2} - a divalent linking group such as, R is H or F. X ₁ ,
X ₂ and X ₃ are —OCOCH ₂ CH (R ₄ ) COO—
(However, R ₄ is H, or an alkyl group or an alkenyl group having 1 to 36 carbon atoms.) Or

[0034]

[Chemical 15]

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

[0036]

[Chemical 16]

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

[0038]

[Chemical 17]

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

[0040]

[Chemical 18]

[Wherein Rf, Rf ', Z, Z ₁ , and R
Is the same as above, Rf ″ has the same meaning as Rf or Rf ′, which may be the same or different, and Z ″ is the same as Z or Z ′, These may be the same or different, and X ₆ , X ₇ , and X ₈ may be the same or different, and are —O— or —OCONHY.
₁ NHCOO- (wherein Y ₁ is the same as the above) and is a divalent linking group, and X ₉ is -OCONHY ₁ N.
HCOO- (provided that Y ₁ is the same as above) or-
_{OCONH (CH 2) a - (} . However, a is an integer of 0 to 2) is a divalent linking group represented by, Z ₁ is the same as defined above. ] The compound represented by these can be mentioned.

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

[0043]

[Chemical 19]

[0044]

[Chemical 20]

[0045]

[Chemical 21]

[0046]

[Chemical formula 22]

[0047]

[Chemical formula 23]

[0048]

[Chemical formula 24]

[0049]

[Chemical 25]

[0050]

[Chemical formula 26]

[0051]

[Chemical 27]

[0052]

[Chemical 28]

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 are polymers (II),
Depending on the compatibility with the polymer (III) or the application, either one may be used, or even if both are included, their antifouling properties are maintained at a high level.

The polysiloxane group-containing (meth) acrylate is one in which either an acryloyl group or a methacryloyl group is linked to one end or both ends of a polysiloxane chain via a divalent linking group. As a specific example, the general formula (B-1)

[0056]

[Chemical 29]

[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) CH ₂ OCO- (however, n ₁ , m
₁ is an integer of 2 to 6. ), R ₁ is the same as above, Z ₁ is a methyl group, a phenyl group, or CH ₂ ═C (R)-(Y ₂ ).
_q- is. ] The compound represented by these, or general formula (B-
2)

[0058]

[Chemical 30]

[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.

More specific examples of the monomer containing a polysiloxane chain include the following.

[0061]

[Chemical 31]

[0062]

[Chemical 32]

[0063]

[Chemical 33]

However, in any of the above equations, Me, P
h represents 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 an essential monomer component for exhibiting antifouling property and stain removal property. Therefore, if both of these are missing, the above performance becomes poor.

On the other hand, the above-mentioned fluorinated (meth) acrylate (A) and / or polysiloxane group-containing (meth)
Examples of the (meth) acrylate (C) other than (A) and (B) copolymerized with the acrylate (B) include methyl acrylate, ethyl acrylate, butyl acrylate,
Octyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate,
Examples thereof include octyl methacrylate, dodecyl methacrylate, acrylonitrile, hydroxybutyl acrylate, hydroxypropyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl methacrylate, dibutyl fumarate and dimethyl fumarate. These may be used alone or in combination of two or more.

Needless to say, the present invention is not limited to these specific examples. According to the knowledge of the present inventors, from the viewpoint of the toughness of the film, when it is possible in the processing step, the adhesiveness between the respective components of the polymer (I), (II) and (III) and the base material In order to improve the adhesiveness of (1), it is preferable to introduce a reactive functional group that reacts with the curing agent (IV) also into the polymer (I).

The selection of the reactive functional group is determined by the reactivity with the curing agent (IV) described later, but the type of the functional group is not particularly limited, and examples thereof include a hydroxyl group, a thiol group,
Carboxyl group, amino group, isocyanate group, aziridinyl group, glycidyl group, alkoxysilyl group, silanol group, cyclocarbonate group, acid anhydride group, vinyl group,
Examples thereof include enol ether groups, thioether groups, active ester groups, acetoacetate groups, metal salts, metal oxides, and functional groups thereof blocked with various blocking agents. 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 examples thereof include a method of directly synthesizing the polymer (I) using a monomer having these functional groups, or a method of previously polymer (I). 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. Curing agent (IV)
The organic polyisocyanate compound is industrially available for the reasons such as availability and diversity of raw materials, ease of crosslinking reaction, toughness of formed film, and improvement of adhesion with a substrate. Useful for.

Therefore, the functional group which reacts with the isocyanate group introduced into the polymer (I) is not particularly limited as long as it is a functional group having active hydrogen, and an amino group, a hydroxyl group,
Examples thereof include a functional group having active hydrogen such as a carboxyl group and active methylene.

It is also possible to introduce an isocyanate group into the polymer (I) and react the isocyanates with each other to form a buret structure or to crosslink allohanate. Of these, crosslinking with a hydroxyl group is particularly preferable in consideration of reactivity with an isocyanate group, availability of a raw material, and film characteristics of a produced polymer. The method for introducing the hydroxyl group to be introduced into the polymer (I) is not particularly limited, and examples thereof include the same method as the method for introducing the various functional groups described above, but among them, it is the simplest in the reaction process and the introduction amount can be controlled. It is easy to use polymer (I) with monomers containing hydroxyl groups.
Is a method of synthesizing.

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 monomer containing a hydroxyl group introduced into the polymer (I) is 1
There may be two types or more.

Needless to say, the present invention is not limited to these specific examples. According to the knowledge of the present inventors, from the viewpoint of compatibility between the respective components of the polymers (I), (II) and (III), the toughness of the film, etc., (meta) other than (A) and (B) ) The acrylate (C) preferably contains methyl methacrylate. Copolymerizing methyl methacrylate not only improves compatibility with other polymers, but also contributes to antifouling properties as a hard component of the film, and homopolymer has a high glass transition point. Therefore, the toughness of the coating can be improved.

There is no limitation on the method for producing the fluoropolymer (I) obtained by polymerizing the monomer (A) and / or (B) and the monomer (C) according to the present invention. Known methods,
That is, it can be produced by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, etc. based on a polymerization mechanism such as a radical polymerization method, a cationic polymerization method, an anionic polymerization method, etc., 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, and if necessary, chain transfer such as lauryl mercaptan, 2-mercaptoethanol, ethylthioglycolic acid and octylthioglycolic acid. It is possible to use an agent and a coupling group-containing thiol compound such as γ-mercaptopropyltrimethoxysilane together with a chain transfer agent.

According to the knowledge of the present inventors, the combined use of such a coupling group-containing chain transfer agent makes it 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 more 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,
Furthermore, fluorinated inner trikids such as perfluorooctane and perfluorotri-n-butylamine can be used, and these can be used alone or in combination.

Monomer (A) of polymer according to the present inventionas well as
The copolymerization composition ratio of (B) and the monomer (C) is a weight ratio,
Usually 100: 0 to 1: 1000, 2: 1 to 1: 1
The range of 00 is preferable, and 49:51 to 1: 100 are the main
It is related to various properties as a coating agent shown clearly, that is, coating workability.
Solvent solubility, antifouling property, and film of the polymer (I) of the present invention
Related to properties, and also fluorine content in polymer (I)
It is more preferable in terms of economic efficiency.

Next, regarding the polymer (II) of a monomer containing a (meth) acryloyl group, which is the second essential component in the present invention, this polymer (II) is closely adhered to a substrate. It is an important component from the viewpoint of compatibility, compatibility with other components, and formation of a film that meets the needs.

Examples of the polymer (II) containing a (meth) acryloyl group include methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate and methacrylic acid. Butyl, octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, hydroxybutyl acrylate, hydroxyethyl acrylate, glycidyl methacrylate, dibutyl fumarate ester, dimethyl fumarate ester, acrylic acid, homopolymers such as methacrylic acid, or A copolymer can be mentioned.

Needless to say, the present invention is not limited to these specific examples. Further, also in the polymer (II), in the same manner as in the case of the polymer (I), in order to improve the adhesiveness between each component and the substrate and further strengthen the film, a curing agent (IV ) Among them, it is preferable to have a functional group that reacts with the organic polyisocyanate. The functional group that reacts with the organic polyisocyanate is not particularly limited, but a hydroxyl group is preferable for the same reason as in the case of the polymer (I). The method for introducing the hydroxyl group to be introduced into the polymer (II) is not particularly limited, and the polymer (I)
In the same manner as in the above case, the method is a method of synthesizing the polymer (II) using a monomer having a hydroxyl group. Specific examples of the monomer containing a hydroxyl group include, for example, hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate,
Examples thereof include hydroxyethyl (meth) acrylate and modified products thereof.

Needless to say, the present invention is not limited to these specific examples. Next, regarding the fluorinated olefin polymer (III), which is the third essential component, the present polymer (III) is an adhesive component with the polymer (I) that is the surface component in the cross-sectional direction of the film. Polymer (I
Located in the middle of I), it prevents the invasion of dirt from the outside and the inside, that is, a part of the base resin or the transfer of additives such as pigments, dyes and plasticizers contained in the base resin to the coating layer. Play a role in prevention.

The fluorinated olefin polymer (III) is a polymer containing a fluorinated olefin monomer,
It is one that 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 Combined, polyvinyl fluoride ether, polychlorotrifluoroethylene, (ethylene / chlorotrifluoroethylene) copolymer, (vinyl fluoride ether / tetrafluoroethylene) copolymer and Lumiflon [Asahi Glass Co., Ltd.], Fluoronate [Dainippon Ink and Chemicals, Inc.], Sepral Coat [Central Glass Co., Ltd.],
Fluorine paints exemplified by trade names such as Zeffle [Daikin Industry Co., Ltd.], Zaflon [Toagosei Co., Ltd.], and Triflon [Mitsui Petrochemical Industry Co., Ltd.] are listed. A vinylidene fluoride-based polymer is particularly preferable in terms of compatibility with components, processability such as solubility in a solvent, and antifouling property.

As the vinylidene fluoride polymer, for example, polyvinylidene fluoride, (vinylidene fluoride / tetrafluoroethylene) copolymer, (vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoro) Examples thereof include ethylene / hexafluoropropylene) copolymers and (vinylidene fluoride / hexafluoropropylene) copolymers.

Needless to say, the present invention is not limited to these specific examples. If a vinylidene fluoride-based polymer is used, it not only exhibits excellent compatibility with other acrylic resins in a solution state, but also forms a film to prevent dirt from entering or foreign particles from entering from the barrier layer. By forming, it becomes possible to improve the antifouling property of the entire film. In addition, because it forms a flexible film with a very high elongation rate as a film,
When the base material is coated, it has excellent followability to the base material and is easily applied to applications involving bending and bending.

The proportion of the above-mentioned polymers (I), (II) and (III) contained in the coated antifouling composition according to the present invention is
There is no particular limitation, but the weight ratio is 2 to 15/35 to 70/2.
It is preferably 0 to 50. The reason is considered as follows.

First, if the proportion of the polymer (I) is less than 2% by weight, the desired antifouling property cannot be obtained, and if it exceeds 15% by weight, not only the cost is increased but also the compatibility of the system is increased. Decreases, and the film strength decreases accordingly.

Next, when the proportion of the polymer (II) is less than 35% by weight, the adhesion to the substrate is poor and the durability of the film itself is also reduced. On the other hand, if the proportion exceeds 70% by weight, the flexibility of the film is reduced, resulting in a brittle film with little elongation, and as a result, the ability to follow the substrate is lost.

The proportion of the polymer (III) is 20% by weight.
When it is less than the above range, sufficient antifouling performance, particularly ability to prevent foreign substances from entering from the base material side, cannot be maintained, and further, the film itself loses flexibility. On the other hand, if it exceeds 50% by weight, the adhesion to the substrate will be significantly reduced.

From the above, according to the knowledge of the present inventors, the coatings exhibiting more excellent antifouling performance can be obtained by using the optimum ratio of the polymers (I), (II) and (III). It is possible to obtain the agent.

Finally, regarding the fourth component, the curing agent (IV), the introduction of the curing agent (IV) is a composition comprising the substrate to be coated and the above-mentioned compositions (I) to (III). It not only improves the adhesiveness with the above, but also enhances the adhesiveness between the components (I) to (III), and makes it possible to form a film having higher toughness and excellent solvent resistance.

There are no particular restrictions on the type of curing agent (IV) that can be used, and it has two or more reactive functional groups in the molecule that react with the functional groups introduced into each polymer as described above. Any reactive polyfunctional compound may be used.

The reactive functional group may be the same as that introduced into each polymer, and examples thereof include a hydroxyl group, a thiol group, a carboxyl group, an amino group, an isocyanate group, an aziridinyl group, a glycidyl group and an alkoxy group. Silyl group, silanol group, cyclocarbonate group, acid anhydride group, vinyl group, enol ether group, thioether group,
Examples thereof include active ester groups, acetoacetate groups, metal salts, metal oxides, and functional groups thereof blocked with various blocking agents. The type of the functional group contained may be one type or two or more types.

The curing agent (IV) may be a low molecular weight compound or a high molecular weight compound as long as it is a bifunctional or higher functional compound containing these functional groups. Further, the curing agent (IV) is a functional compound that reacts not only when the polymer (I) and / or (II) contains a functional group that reacts with the reactive functional group contained in the curing agent (IV). Even when it does not contain a group, it plays an important role in improving the adhesion to the substrate.

The curing agent (IV) is not particularly limited, but organic epoxy compounds, organic polyisocyanates, etc. are used for reasons such as availability of raw materials, versatility, toughness of formed film, and improvement of adhesion with a substrate. The compounds are industrially useful and preferred.

Examples of organic epoxy compounds 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, and spiroglycol diglycidyl ether, but are not particularly limited thereto.

Of these cross-linking agents, organic polyisocyanate compounds are more preferable because of the ease of the cross-linking reaction. Examples of the organic polyisocyanate compound include 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 Isocyanate, tetramethyl xylylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 3,3′-dimethyl-4,4′-dicyclohexylmethane diisocyanate, and 2 of these compounds.
Part of trimer, trimer or phenols, oximes, alcohols, active methylenes, mercaptans, acid amides, imides, amines, imidazoles, ureas, carbamates, imines or sulfites And polyisocyanates that have been blocked.

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, for example, various kinds such as ethylene glycol, propylene glycol, 1,3- or 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol or dipropylene glycol. Diols or various polyols such as glycerin, trimethylolpropane or pentaerythritol, polyester diols obtained from these various diols and / or polyols and various aliphatic polycarboxylic acids, and further poly Ji glycol, polypropylene glycol, such as various polyether diols polytetramethylene glycol, more include polycarbonate diols, and the like.

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.

According to the findings of the present inventors, among these,
Considering the compatibility with the polymers (I), (II) and (III), the organic polyisocyanate compound may be a monomer, dimer or trimer as described above, or a burette structure thereof. Or having the above-mentioned monomer is water,
A low molecular weight organic polyisocyanate such as an adduct type which is an adduct to trimethylolpropane or the like is particularly preferable.

The amount of the curing agent (IV) introduced is the polymer (I),
0.0 based on the total weight of the polymer (II) and the polymer (III)
001 to 200% by weight is preferable, and 0.001 to 100%
Weight percent is more preferred.

Various additives can be introduced into the antifouling composition for coating according to the purpose. For example,
When coating the substrate, a coupling agent such as a silane-based, titanium-based or zirco-aluminate-based coupling agent can be used in combination for the purpose of improving the adhesion to the substrate. Among the coupling agents, silane coupling agents are preferable. Examples of the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, dimethylvinylmethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, and γ.
-Aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like can be mentioned. Further, a fluorine-based coupling agent such as a fluorine atom-containing alkoxysilane compound, a fluorine atom-containing titanium acylate compound, or a fluorine atom-containing alkoxyzirconium compound can also be used.

If necessary, the coating resin composition of the present invention may contain pigments, dyes, colorants such as carbon, silica, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, calcium oxide, calcium carbonate. Inorganic powder, such as
Organic fine powders such as higher fatty acids, poly (vinylidene fluoride), poly (tetrafluoroethylene), and polyethylene, and various fillers such as a light resistance improver and a weather resistance improver can be appropriately added.

Examples of the substrate according to the present invention include inorganic substances such as glass, quartz and silica, metals such as iron, copper, ferrite, cobalt, nickel and aluminum and alloys thereof, polyethylene, polystyrene, polymethylmethacrylate, 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, if necessary after adjusting to a suitable concentration or viscosity with a solvent suitable for the purpose, for example, gravure coater, knife coater, dipping coating, spray coating and the like on various substrates It can be applied, and after application, post-processing such as foaming, embossing, embossing, pressing and printing 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, artificial marble, tarpaulins, tents, nets, table cloths, desk mats and the like.

It is also possible to use various paints as a top coat agent. As the paint, paint using natural resin, for example, petroleum resin paint, shellac paint, rosin paint, cellulose paint, rubber paint, lacquer, cashew resin paint, oil-based vehicle paint, etc., and paint using synthetic resin , For example, phenol resin paint, alkyd resin paint,
Examples thereof include unsaturated polyester resin paints, amino resin paints, epoxy resin paints, vinyl resin paints, acrylic resin paints, polyurethane resin paints, silicone resin paints, and fluororesin paints, but are not particularly limited thereto.

Needless to say, the present invention is not limited to the above specific examples. Therefore, if the coating composition according to the present invention is used, it is possible to form a coating agent for various base materials, which has excellent adhesion to a base material, film properties, and has an antifouling effect that cannot be achieved by a conventionally known composition, as is conventionally done. Can be provided.

The coating composition according to the present invention has surface lubricity, scratch resistance, oil resistance, smoothness, water / oil repellency, water resistance, moisture resistance, rust resistance, and peelability in addition to the above purposes. Since it forms a film excellent in low water absorption, 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.

Further, 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.

[0115]

EXAMPLES In order to describe the present invention in more detail, reference examples, examples and comparative examples are given below, 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) In a glass flask equipped with a stirrer, a condenser and a thermometer, 15 parts by weight of fluorinated monomer A-1-1, methyl methacrylate (hereinafter abbreviated as MMA). ) 75 parts by weight, 2-
Hydroxylethylmethacrylate (hereinafter 2-HE
MA) 5 parts by weight, B-1-10 5 parts by weight, and methyl isobutyl ketone (hereinafter abbreviated as MIBK) 2
33 parts by weight were charged, and azobisisobutyronitrile (hereinafter referred to as AI) was used as a polymerization initiator under reflux in a nitrogen gas stream.
0.5 parts by weight (abbreviated as BN) and 0.6 parts by weight of lauryl mercaptan as a molecular weight modifier were added, and the mixture was refluxed for 11 hours to complete the polymerization.

Reference Examples 2 to 5 (Polymer I-2, I-3, I-
Synthesis of 4) A polymer (I) solution was obtained in the same manner as in Reference Example 1.

[0118]

[Table 1] The abbreviations in Table 1 are as follows. n-BMA: n-butyl methacrylate EA: ethyl methacrylate AA: acrylic acid Reference Examples 7 to 13 (polymers II-1, II-2, II-3, III)
-1, III-2) Polymers II-1, II-2, II-3, III-1, and III-2 having the compositions shown in Table 2 were used.

[0119]

[Table 2] Kainer SL: (Product name: Elf Atchem Japan Co., vinylidene fluoride-4 fluoroethylene copolymer) Kainer ADS: (Product name: Elf Atchem Japan Co., vinylidene fluoride-4 fluoroethylene) -6 Fluorinated Propylene Copolymer) Reference Examples 14 to 16 (Curing Agents IV-1 and IV-2) Curing Agent IV-
The following were used as IV and IV-2.

[0120]

[Table 3] Bernock DN-950: (Brand name: Dainippon Ink and Chemicals Incorporated Organic isocyanate compound) (Solid content concentration: 76% by weight, NCO content: 13% by weight) Crisbon CL-10: (Brand name: Dainippon Ink and Chemicals Organic isocyanate compound manufactured by Kogyo Co., Ltd. (solid content concentration:
100% by weight: NCO content: 21% by weight) Epolite 100MF: (Product name: Kyoeisha Chemical Co., Ltd.
Epoxy resin) (solid content concentration: 100% by weight: epoxy equivalent: 150) Examples 1 to 14 and Comparative Examples 1 to 5 Polymer (I), polymer (II), polymer (I
II) and the curing agent (IV) are mixed in predetermined amounts, and prepared with each solvent so that the nonvolatile content is 15% and the solvent composition is methyl ethyl ketone / methyl isobutyl ketone / n-butyl acetate = 35/5/60. did.

The prepared solution was applied to an applicator (100
μm) plasticized polyvinyl chloride sheet (with a plasticizer content of 20% relative to polyvinyl chloride as substrate A, 6
The base material B is 0%. ) And dried at 70 ° C for 5 minutes, then at 140 ° C for 2 minutes and then at 50 ° C for 1 minute.
A test piece was prepared by performing heat treatment for 8 hours. Table 4
The mixing ratio of each sample is shown in the table.

[0122]

[Table 4]

The compound IV-1 has a solid content concentration of 76% by weight, and the numerical values in the table show the apparent values. All other numerical values represent the solid content ratio. <Test Method and Evaluation Criteria> The antifouling property and the anti-bleeding property of the plasticizer 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 sticked 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 plasticizer is determined by setting the environment for being strongly influenced by the plasticizer by setting the leaving temperature after attaching the magic in the above-mentioned magic staining test to 50 ° C. Compared to the one.

Evaluation of wear 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 scratch resistance was evaluated by visually observing the state of the film after the cotton cloth was contacted 1000 times with a load of 1 kg using a Gakushin-type friction fastness tester [Koa Shokai Co., Ltd.]. It was judged by a five-level evaluation.

Solvent resistance is 24 by immersing a film cast into a glass plate in toluene and methyl ethyl ketone.
It evaluated by measuring the gel fraction after time. The evaluation results of antifouling property, abrasion resistance, adhesion, scratch resistance, and solvent resistance are summarized in Table 5. It should be noted that the larger the numerical value of the five-level evaluation in the table, the better the performance.

[0129]

[Table 5]

As is clear from Table 5, the antifouling composition for coating has extremely remarkable stain resistance and anti-bleeding property of the plasticizer in the coating application of plasticized polyvinyl chloride, while It can be seen that it is also excellent in abrasion resistance, adhesion, scratch resistance, and solvent resistance.

[0131]

INDUSTRIAL APPLICABILITY Among the coating compositions of the present invention, the polymer (I)
Is a component for developing the anti-contamination property, the polymer (II) is the adhesion property to the substrate, and the polymer (III) is the component for preventing the permeation of contaminants. By blending in a ratio, a film having excellent anti-bleeding property and antifouling property of the plasticizer is formed. Furthermore, by adding the curing agent (IV), it is possible to improve the adhesion between the substrate and each component and form a tough film. Therefore, the composition according to the present invention can provide a coating agent for various base materials which has excellent adhesion to the base material, film characteristics, and a long-life antifouling effect.

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Claims (10)

(57) [Claims] 1. A (meth) acryl containing a polysiloxane group.
(B) and fluorinated (meth) acrylate (A)
And (meth) acryl other than the (meth) acrylate (B).
Copolymer (I) obtained by polymerizing with relate (C)
An antifouling composition for coating, comprising a polymer (II) of a monomer containing a (meth) acryloyl group, a fluorinated olefin polymer (III) and a curing agent (IV). 2. The copolymer (I) is fluorinated (meth).
) Acrylate (A) and polysiloxane group-containing (
A) acrylate (B) and the (meth) acrylate
(M) other than (A) and the (meth) acrylate (B)
Copolymer obtained by polymerizing acrylate (C)
The antifouling composition for coating according to claim 1, which is a body. 3. A curing agent (IV) is claimed in claim 1 or 2 composition wherein the organic polyisocyanate compound. 4. Any of claims 1-3 fluorinated olefin polymer (III) is <br/> vinylidene fluoride polymer
The composition according to item 1 . As wherein the fluorinated (meth) acrylate (A) and polysiloxane group-containing (meth) acrylate (B) other than (meth) acrylate (C), any of the claims 1-4 for use methyl methacrylate The composition according to item 1. 6. A curing agent (IV) as a (meth) acrylate (C) other than a fluorinated (meth) acrylate (A) and a polysiloxane group-containing (meth) acrylate (B).
Use a (meth) acrylate containing a functional group that reacts with
Any one composition according to claim 1-5 that. 7. The functional group which reacts with the curing agent (IV) is a hydroxyl group.
The composition according to claim 6, which is 8. (meth) polymers of monomers containing acryloyl groups as (II), any one of claims 1-7 for use functional group-containing polymer that reacts with the curing agent (IV) The composition according to the item. 9. The functional group which reacts with the curing agent (IV) is a hydroxyl group.
The composition according to claim 8, which is Wherein said copolymer (I), the polymer (I
And I), wherein the proportion of the polymer (III), 2 to 1 by weight
5: 35-70: any one composition according to claim 1-9 20-50.