JP6693403B2 - Curable resin composition - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a curable resin composition which shows good water and oil repellency to various base materials and forms a cured film having excellent releasability, transparency, adhesiveness, heat resistance and rust resistance. More specifically, a perfluoroalkyl group having 6 or less carbon atoms that is said to have low bioaccumulation (more specifically, a perfluoroalkyl-substituted ethyl group having 4 to 6 carbon atoms or a perfluoroalkyl group having 4 to 6 carbon atoms). A copolymer of a monomer mixture containing a polyfluoroalkyl vinyl monomer having a C4-6 perfluoroalkyl-substituted alkyl group such as an alkyl-substituted propyl group) at one end of the molecular chain and an aluminum chelate. A curable resin composition containing the same.

  Conventionally, in order to exert a surface modifying function such as water / oil repellency and release performance, for example, Japanese Patent Publication No. 1-42983 (Patent Document 1) and Japanese Patent Laid-Open No. 7-109317 (Patent Document 2). As shown in, a polymer of a fluorine-based acrylic monomer or a methacrylic monomer has been used. Further, it has been considered that a long-chain perfluoroalkyl group having 8 or more carbon atoms is indispensable for exerting a surface-modifying function such as high mold release performance and water / oil repellency performance. However, in recent years, the accumulation of perfluorooctanoic acid (hereinafter, PFOA) having a perfluoroalkyl group having 8 or more carbon atoms in the human body has attracted attention, and in March 2003, the US Environmental Protection Agency (USEPA) Published the preliminary risk survey report on the safety of PFOA detected in various environments including blood of wild animals and humans. Furthermore, in January 2006, we proposed a plan to reduce environmental emissions of PFOA, its related substances, and their precursors, and to reduce their content in products, and announced the participation of eight fluororesin manufacturers. ing.

  When the number of carbon atoms in the perfluoroalkyl group is 6 or less, the risk to the living body and the environment is greatly reduced, but surface modification such as mold release performance and water / oil repellent performance due to the perfluoroalkyl group in the polymer is reduced. Quality function is significantly reduced. This is because a perfluoroalkyl group having a carbon number of 8 or more forms a crystal structure, but a perfluoroalkyl group having a carbon number of 6 or less does not form a crystal structure, so that a sufficient surface modifying function cannot be exhibited. ..

Japanese Patent Publication No. 1-42983 JP-A-7-109317

  Therefore, the present invention has a low risk to the living body and the environment, exhibits good water and oil repellency to various base materials, and has excellent releasability, transparency, adhesion, heat resistance, and rust resistance. It aims at providing the curable resin composition which forms.

  As a result of earnest studies to achieve the above object, the present inventor has found that a perfluoroalkyl group having 6 or less carbon atoms (more specifically, having 4 to 6 carbon atoms) is said to have low bioaccumulation potential. A perfluoroalkyl-substituted alkyl group having 4 to 6 carbon atoms such as a perfluoroalkyl-substituted ethyl group or a perfluoroalkyl-substituted propyl group having 4 to 6 carbon atoms) is attached to one end of the molecular chain, and the following general formula (I ) Good water and oil repellency, heat resistance, when using a composition containing a copolymer of a monomer mixture containing a polyfluoroalkyl vinyl monomer represented by and an aluminum chelate as various base materials, The present invention has been completed by finding that a cured film having excellent releasability, transparency, adhesion and rust prevention is formed.

Therefore, the present invention provides the following curable resin composition.
[1]
(A) (1) The following general formula (I)

(In the formula, Rf is a perfluoroalkyl group having 4 to 6 carbon atoms, and A is an alkylene group having 1 to 6 carbon atoms .)
A polyfluoroalkyl vinyl monomer represented by: 50 to 99.5% by mass,
(2) partial one selected from a vinyl monomer having at least one carboxyl group in the vinyl monomer and the molecule having at least one hydroxyl group in the child or two or more vinyl monomers: 0.5 to 50% by mass, and
(3) The above (1) and (2) which are copolymerizable with the above components (1) and (2) and do not contain a hydrolyzable group bonded to a silicon atom, a hydroxyl group and a carboxyl group in the molecule. ) Non-silicon or organosilicon vinyl monomers other than the component: 0 to 49% by mass
Curable resin composition containing the copolymer of the monomer mixture which consists of these, and (B) aluminum chelate.
[2]
(A) The curable resin composition according to [1], wherein in the general formula (I) of (1), A is an alkylene group having 2 to 4 carbon atoms.
[ 3 ]
The curable resin composition according to [1] or [2] , which contains 0.1 to 50 parts by mass of the component (B) with respect to 100 parts by mass of the component (A).
[ 4 ]
Furthermore, the curable resin composition according to any one of [1] to [3], which contains an organic solvent.

  The curable resin composition of the present invention has a perfluoroalkyl group having 6 or less carbon atoms (more specifically, a perfluoroalkyl-substituted ethyl group having 4 to 6 carbon atoms and a carbon number of 4 to 6) with low bioaccumulation at the end of the molecular chain. Use of a copolymer of a monomer mixture containing a polyfluoroalkyl vinyl monomer having a C4-6 perfluoroalkyl-substituted alkyl group such as a C4-6 perfluoroalkyl-substituted propyl group) Therefore, it does not pollute the environment, and since the copolymer has the same performance as a conventional fluorine-containing polymer when combined with an aluminum chelate, the surface modification of water and oil repellent agents, release agents, etc. It can be suitably used as a substance.

The curable resin composition of the present invention comprises a copolymer (A) of a monomer mixture of the following components (1) to (3) and an aluminum chelate (B) as active ingredients.
The copolymer of the component (A) is preferably contained in the composition of the present invention (that is, in the total of the components (A) and (B)) in an amount of 66.7 to 99.9% by mass, and 76.9% by mass. ˜99.5 mass% is more preferable, and 90 to 99 mass% is more preferable.

(A) Copolymer of monomer mixture of the following components (1) to (3) (1) The following general formula (I)

(In the formula, Rf is a perfluoroalkyl group having 4 to 6 carbon atoms, and A is a divalent organic group.)
Polyfluoroalkyl vinyl monomer represented by: 50 to 99.5 mass%
(2) Organosilicon vinyl monomer having a hydrolyzable group bonded to at least one silicon atom in the molecule, vinyl monomer having at least one hydroxyl group in the molecule, and at least one in the molecule One or more vinyl monomers selected from vinyl monomers having one carboxyl group: 0.5 to 50% by mass
(3) The above (1) and (2) which are copolymerizable with the above components (1) and (2) and do not contain a hydrolyzable group bonded to a silicon atom, a hydroxyl group and a carboxyl group in the molecule. ) Non-silicon or organosilicon vinyl monomers other than the component: 0 to 49% by mass
(B) Aluminum chelate

（式中、Ｒｆは炭素数４〜６のパーフルオロアルキル基、Ａは２価の有機基である。）
で表され、一方の分子鎖末端に炭素数４〜６のパーフルオロアルキル基を有し、もう一方の分子鎖末端にメタクリロキシ基を有するものである。
ここで、炭素数４〜６のパーフルオロアルキル基（Ｒｆ）として、具体的には、パーフルオロブチル基（Ｃ₄Ｆ₉）、パーフルオロペンチル基（Ｃ₅Ｆ₁₁）、パーフルオロヘキシル基（Ｃ₆Ｆ₁₃）が挙げられ、また、２価の有機基（Ａ）としては、例えば、メチレン基、エチレン基、プロピレン基（トリメチレン基）、テトラメチレン基、ヘキサメチレン基等の、炭素数１〜６、好ましくは炭素数２〜４のアルキレン基などが挙げられる。
式（Ｉ）中、分子鎖の片方の末端に存在する「Ｒｆ−Ａ−」で示される構造としては、パーフルオロヘキシルエチル基（Ｃ₆Ｆ₁₃ＣＨ₂ＣＨ₂−）、パーフルオロペンチルエチル基（Ｃ₅Ｆ₁₁ＣＨ₂ＣＨ₂−）、パーフルオロブチルエチル基（Ｃ₄Ｆ₉ＣＨ₂ＣＨ₂−）、パーフルオロヘキシルプロピル基（Ｃ₆Ｆ₁₃ＣＨ₂ＣＨ₂ＣＨ₂−）、パーフルオロブチルプロピル基（Ｃ₄Ｆ₉ＣＨ₂ＣＨ₂ＣＨ₂−）等の炭素数４〜６のパーフルオロアルキル置換アルキル基などが挙げられる。 Component (A1) The polyfluoroalkylvinyl monomer of component (1) that constitutes the copolymer that is component (A) of the present invention has the following general formula (I).

(In the formula, Rf is a perfluoroalkyl group having 4 to 6 carbon atoms, and A is a divalent organic group.)
Which has a perfluoroalkyl group having 4 to 6 carbon atoms at one molecular chain end and a methacryloxy group at the other molecular chain end.
Here, as the C 4-6 perfluoroalkyl group (Rf), specifically, a perfluorobutyl group (C ₄ F ₉ ), a perfluoropentyl group (C ₅ F ₁₁ ), a perfluorohexyl group ( C ₆ F ₁₃ ), and the divalent organic group (A) includes, for example, a methylene group, an ethylene group, a propylene group (trimethylene group), a tetramethylene group, a hexamethylene group, and the like. -6, Preferably a C2-C4 alkylene group etc. are mentioned.
In the formula (I), the structure represented by the presence on one end of the molecular chain "Rf-A-", perfluorohexyl ethyl _{(C 6 F 13 CH 2 CH} 2 -), perfluoro pentyl ethyl _{(C 5 F 11 CH 2 CH} 2 -), perfluorobutyl ethyl group _{(C 4 F 9 CH 2 CH} 2 -), perfluorohexyl-propyl group _{(C 6 F 13 CH 2 CH} 2 CH 2 -), perfluoro butyl propyl _{(C 4 F 9 CH 2 CH} 2 CH 2 -) perfluoroalkyl-substituted alkyl group having 4 to 6 carbon atoms and the like, such as.

  The component (1), a polyfluoroalkylvinyl monomer, is a perfluoroalkyl group having 4 to 6 carbon atoms (more specifically, a perfluoroalkyl group having 4 to 6 carbon atoms) with low bioaccumulation at one end of the molecular chain. A C4-6 perfluoroalkyl-substituted alkyl group such as an alkyl-substituted ethyl group or a C4-6 perfluoroalkyl-substituted propyl group), and a copolymer containing the monomer is Since it does not pollute the environment and has a performance equivalent to that of a conventional fluoropolymer, it can be suitably used as an active ingredient of a surface modifier such as a release agent or a water / oil repellent agent. ..

  Examples of the vinyl monomer having such a polyfluoroalkyl group include those represented by the following formula.

  A plurality of polyfluoroalkylvinyl monomers represented by the general formula (I) are considered as in the above formula, but in the present invention, they may be a single kind or a mixture of two or more kinds.

  The mass ratio of the polyfluoroalkyl vinyl monomer (1) in the monomer mixture (that is, the component mixture of the component (1), the component (2) and the component (3) described later) is the monomer. When the mass ratio of (1) is less than 50% by mass, the releasing effect of the curable resin composition containing the copolymer of the monomer mixture as an active ingredient on adhesive materials such as silicone adhesive is insufficient. Or impair the water and oil repellency. On the other hand, when the mass ratio exceeds 99.5 mass%, high water / oil repellency is exhibited and a releasing effect can be expected, but adhesion to a substrate for applying the resin composition to form a cured film. Therefore, the mass ratio must be in the range of 50 to 99.5 mass%, and a more preferable range is 70 to 99.5 mass%.

Component (A2) Next, the component (2) constituting the copolymer which is the component (A) of the present invention is an organosilicon-based compound having a hydrolyzable group bonded to at least one silicon atom in the molecule. One or more vinyl monomers selected from vinyl monomers, vinyl monomers having at least one hydroxyl group in the molecule, and vinyl monomers having at least one carboxyl group in the molecule Is. In addition, the organosilicon vinyl monomer in the component (2) is a vinyl monomer having at least one silicon atom bonded to an organic substituent in the molecule, and the organopolyvinyl monomer as the above-mentioned component (1) is used. A vinyl group (including an allyl group, an acryloxy group, and a methacryloxy group) for copolymerizing with a fluoroalkyl vinyl monomer, and at least one, preferably two or more, and more preferably three or more silicon atoms in the molecule. It has a hydrolyzable group bonded to an atom, and is preferably a vinylsilane monomer or a partially hydrolyzed condensate thereof.

  Examples of the hydrolyzable group include acetoxy group, octanoyloxy group, acyloxy group such as benzoyloxy group, dimethylketoxime group, methylethylketoxime group, ketoxime group such as diethylketoxime group, methoxy group, ethoxy group, propoxy group. Groups such as alkoxy groups, isopropenyloxy groups, 1-ethyl-2-methylvinyloxy groups such as alkenyloxy groups, dimethylamino groups, diethylamino groups, butylamino groups, cyclohexylamino groups, and other amino groups, dimethylaminoxy groups , Aminoxy groups such as diethylaminoxy group, amide groups such as N-methylacetamide group, N-ethylacetamide group, N-methylbenzamide group and the like. Since these hydrolyzable groups themselves must be liberated from the silicon atom, avoid those that are electronically stable, have large steric hindrance, and produce high-boiling substances after hydrolysis. Preferably.

  Therefore, examples of the organosilicon-based vinyl monomer having a hydrolyzable group include those represented by the following formula, and partial hydrolyzed condensates thereof.

  Further, the vinyl monomer having at least one hydroxyl group in the molecule is a vinyl monomer having at least one hydroxyl group in the molecule, and the polyfluoroalkyl vinyl unit amount as the above-mentioned (1) component A vinyl group (including an allyl group, an acryloxy group, and a methacryloxy group) for copolymerizing with the polymer and at least one, preferably 1 to 3 hydroxyl groups in the molecule. Examples of the vinyl monomer included include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.

  Further, the vinyl monomer having at least one carboxyl group in the molecule is a vinyl monomer having at least one carboxyl group in the molecule, and the polyfluoroalkylvinyl unit amount as the component (1) described above. A vinyl group (including an allyl group, an acryloxy group, and a methacryloxy group) for copolymerization with the body, and at least one, preferably 1 to 3 carboxyl groups in the molecule. As the vinyl monomer to be possessed, 1,4-di (meth) acryloxyethyl pyromellitic acid, 4- (meth) acryloxyethyl pyromellitic acid, N- (meth) acryloyl-p-aminobenzoic acid, N- (Meth) acryloyloxybenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, acrylic acid, methacrylic acid and the like are exemplified. .

  The organosilicon vinyl monomer, the vinyl monomer having a hydroxyl group, and the vinyl monomer having a carboxyl group as the component (2) may be one kind of the above compounds or a mixture of two or more kinds. Good.

  In addition, the mass ratio in the monomer mixture of the component (2) (that is, the component mixture of the component (1), the component (2) and the component (3) described later) is the same as that of the monomer (2). If the mass ratio is less than 0.5% by mass, the coating film obtained from this copolymer may not exhibit sufficient performance. On the other hand, if the mass ratio exceeds 50 mass%, the crosslink density is too high and the coating film becomes brittle, which may cause gelation during the polymerization reaction. Therefore, the mass ratio is in the range of 0.5 to 50 mass%, more preferably 0.5 to 30 mass%.

Component (A3) Next, a non-silicon type (that is, having no silicon atom in the molecule) or an organic silicon type (that is, the following) as the component (3) constituting the copolymer which is the component (A) of the present invention: The vinyl monomer (having a silicon atom substituted with an organic group in the molecule) is an optional component that may be blended if necessary, and is copolymerizable with the above components (1) and (2). In addition, the vinyl monomer does not contain a hydrolyzable group bonded to a silicon atom, a hydroxyl group and a carboxyl group in the molecule (that is, does not contain the above-mentioned components (1) and (2)). It is added for the purpose of adjusting the strength, hardness, adhesion to a base material, stain resistance, etc. of the combined film (cured film).

  Examples of the non-silicon-based or organosilicon-based vinyl monomer as the component (3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and 2-ethylhexyl. Acrylates such as (meth) acrylates, methacrylates, γ-tris (trimethylsiloxy) silylpropyl (meth) acrylate, γ-bis (trimethylsiloxy) silylpropyl (meth) acrylates having a silicon group, methacrylates, styrene , Aromatic vinyl compounds such as vinyltoluene, diesters of unsaturated carboxylic acids such as maleic acid and fumaric acid with monohydric alcohols having 1 to 18 carbon atoms, vinyl ethers such as n-butyl vinyl ether and cyclohexyl vinyl ether. It is illustrated.

  When the non-silicon-based or organosilicon-based vinyl monomer as the component (3) is used, it may be a single compound of the above compounds or a mixture of two or more compounds.

  The mass ratio in the monomer mixture of the non-silicon or organosilicon vinyl monomer (3) (that is, the monomer mixture of the component (1), the component (2) and the component (3)) is The mass ratio of the monomer (3) may be up to 49 mass% in the copolymer. That is, it is preferably 0 to 49% by mass, and particularly preferably 0 to 20% by mass in the monomer mixture. If the mass ratio of the monomer (3) exceeds 49 mass%, the surface characteristics of the composition containing the copolymer of the monomer mixture will be insufficient.

  The copolymer (A), which is the main component of the composition of the present invention, is obtained by subjecting the monomer mixture of the above-mentioned components (1) to (3) to solution polymerization (solution radical polymerization reaction) using, for example, a radical reaction initiator. It can be obtained by copolymerizing by a conventionally known method such as).

Reaction initiator As the radical reaction initiator, azobisisobutylnitrile, 2,2′-azobis (2-methylbutyronitrile), di-t-butylperoxide, dibenzoylperoxide, t-butylperbenzoate, Examples are t-butylperoxy 2-ethylhexanate and methyl ethyl ketone peroxide.

Solvent Since this reaction has a large content of a fluorine-containing vinyl monomer, a partial fluorinated solvent such as Novec 7200, 7300 (trade name of Sumitomo 3M Ltd.), m-xylene hexafluoride, ethyl acetate, butyl acetate, etc. It may be carried out in an organic solvent such as acetic acid ester and ketones such as methyl ethyl ketone and methyl isobutyl ketone, and in some cases, in a mixed solvent of a lower monohydric alcohol such as methanol, ethanol, propanol and butanol and the above solvent. Alternatively, it may be carried out in the presence of a chain transfer agent such as mercaptans.

  The weight average molecular weight (Mw) of the copolymer (A) thus obtained is determined by high performance liquid chromatography (for example, the solvent used in the above-mentioned copolymerization reaction or other fluorine-based or non-fluorine-based solvent). The value of the solvent measured by gel permeation chromatography (GPC) analysis by polystyrene conversion weight average molecular weight, etc.) is preferably about 2,000 to 2,000,000, more preferably 10,000 to 500, It is 000.

Component (B) Next, the aluminum chelate which is the component (B) acts as a condensation catalyst for the hydrolyzable groups in the copolymer (A) and as a crosslinking agent for hydroxyl groups and carboxyl groups. It is a thing. Specific examples of the aluminum chelate include ethyl acetoacetate aluminum diisopropylate, ethyl acetoacetate aluminum dibutyrate, diethyl acetoacetate aluminum butyrate, aluminum tris (ethylacetoacetate) alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate. Examples thereof include bis (ethyl acetoacetate).
These may be used alone or as a mixture of two or more.

  The blending amount of the aluminum chelate which is the component (B) is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, and still more preferably 100 parts by mass of the component (A). It is 1 to 10 parts by mass. If the blending amount of the component (B) is too small, the curing rate will be slow, the crosslink density will decrease, and the cured film obtained may not have the desired heat resistance and durability. If the blending amount of the component (B) is too large, the crosslink density increases, but the surface characteristics of the obtained cured film may deteriorate.

  The composition of the present invention comprises the above-mentioned copolymer (A) and aluminum chelate (B), but usually, preferably the above-mentioned components (A) and (B) are further combined with an organic solvent. Is provided as a solution (composition) containing In this case, examples of the organic solvent include Novec7200, Novec7300 (trade name of Sumitomo 3M Ltd.), and partially fluorinated hydrocarbon solvents such as m-xylene hexafluoride. Here, the amounts of the copolymer (A) and the aluminum chelate (B) in the solution containing the organic solvent (that is, the content of the composition of the present invention in the solution) are these (A) and (B). It is preferable that the total amount of the components is 0.01 to 50% by mass, particularly 0.05 to 30% by mass of the whole solution containing the organic solvent.

  The composition of the present invention can be easily prepared by uniformly mixing the above-mentioned components (A) and (B), and optionally, an organic solvent as an optional component.

  The composition of the present invention easily and firmly adheres to a substrate such as glass, paper, plastic, or metal to form a cured film. This cured film exhibits excellent water and oil repellency due to the fact that the copolymer contains fluorine atoms, and is non-adhesive. Therefore, it can be used as a water / oil repellent agent for fibers, papers, porous materials, resins; an antifouling coating agent; a protective agent for outer walls; a release paper, a release agent for molds and the like. The composition of the present invention may be used as a transparent coating agent without adding a pigment or the like, or may be used as a coating agent to which a pigment or the like is added.

  Various methods can be applied as a method for forming a cured film of the above composition, and for example, a coating method using brush coating, spray coating, dip coating, coater or the like is used. With these coating means, it is possible to coat the substrate with an arbitrary coating amount. After being applied to the substrate, it may be dried at room temperature or may be heat-cured. Preferably, when it is cured by heating at 80 ° C. or higher, the effect of promoting the curing of the present invention is remarkable.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The parts in the following examples are parts by mass. The weight average molecular weight (Mw) of the obtained copolymer was measured by a high performance liquid chromatography method.

[Example 1]
In a 300 ml four-necked flask equipped with a thermometer, an inert gas inlet, a reflux condenser, and a stirrer, CHEMINOX FAMAC-6 (trade name of Unimatec) 2- (perfluorohexyl) ethyl methacrylate 118.4. Parts, γ-methacryloxypropyltriethoxysilane, 1.6 parts, Novec7300 (trade name, manufactured by Sumitomo 3M Limited) as a fluorinated solvent, and V-59 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) as a radical reaction initiator 2, 0.77 parts of 2'-azobis (2-methylbutyronitrile) was charged, and the mixture was reacted at 65 to 75 ° C for 5 hours while a nitrogen gas was passed through. Then, the mixture is aged at the same temperature for 15 hours to give 98% by mass of a polyfluoroalkylvinyl monomer (A) represented by the following formula.

及び下記式のγ−メタクリロキシプロピルトリエトキシシラン２質量％

And 2% by mass of γ-methacryloxypropyltriethoxysilane of the following formula

からなる共重合体（重量平均分子量Ｍｗ：１８０，０００）の溶液をＮｏｖｅｃＨＦＥ−７３００で共重合体濃度が１０質量％となるように希釈して母液を調製した。

A mother liquor was prepared by diluting a solution of a copolymer (weight average molecular weight Mw: 180,000) consisting of the above with Novec HFE-7300 so that the copolymer concentration would be 10% by mass.

  Next, to 100 parts of the obtained mother liquor, 2.5 parts of an aluminum chelate (Kelope S, a trade name of Hope Pharmaceutical Co., Ltd.) diluted to 10 mass% with MXHF (m-xylene hexafluoride), a fluorine-based diluent (FS thinner, trade name of Shin-Etsu Chemical Co., Ltd.) 397.5 parts was added to prepare a treatment liquid of the curable resin composition. Dip coating (immersion for 10 seconds → pull-up speed 150 mm / min) of the treatment solution on an aluminum base material (length 50 mm x width 25 mm x thickness 0.5 mm) whose surface is plated with silver, and heat treatment at 150 ° C for 5 minutes did.

<Salt spray test>
The treated base material was subjected to a salt spray test under the following conditions, and the corrosion state of the surface after the test was visually observed based on the following evaluation criteria. The results are shown in Table 1.
(conditions)
Test temperature: 35 ° C
Salt water concentration: 5%
pH: 6.5-7.2
Test time: 72 hours spray (evaluation standard)
○ (Good): No corrosion △ (Fair): Partially corroded × (Poor):> 50% corroded

<Contact angle>
Before and after washing the obtained base material with the fluorine-based solvent AK-225 (trade name, manufactured by Asahi Glass Co., Ltd.), contact with pure water using a fully automatic contact angle meter DM-700 (manufactured by Kyowa Interface Science Co., Ltd.). The angle was measured. The results are shown in Table 1.

[Examples 2 to 8 and Comparative Examples 1 and 2]
Examples 2 to 8 and Comparative Examples 1 and 2 were prepared in the same manner as in Example 1 with the compositions shown in Table 1.

  The following formulas A, B and C were used as the polyfluoroalkyl vinyl monomer.

  The following formulas 1, 2 and 3 were used as the vinyl monomer having a functional group.

  I and ii were used as the vinyl monomer containing no functional group (non-functional vinyl monomer).

  In Example 1, in addition to the aluminum chelate (Kelope S, hereinafter abbreviated as aluminum chelate <a>) diluted to 10% by mass with MXHF, Kelope EP-12 (trade name of Hope Pharmaceutical Co., Ltd.) as aluminum chelate <b>. The contact angle to pure water was examined for the compositions diluted with FS thinner in the same manner except that was used. The results are shown in Table 1.

Claims (4)

(A) (1) The following general formula (I)

(In the formula, Rf is a perfluoroalkyl group having 4 to 6 carbon atoms, and A is an alkylene group having 1 to 6 carbon atoms .)
A polyfluoroalkyl vinyl monomer represented by: 50 to 99.5% by mass,
(2) partial one selected from a vinyl monomer having at least one carboxyl group in the vinyl monomer and the molecule having at least one hydroxyl group in the child or two or more vinyl monomers: 0.5 to 50% by mass, and
(3) The above (1) and (2) which are copolymerizable with the above components (1) and (2) and do not contain a hydrolyzable group bonded to a silicon atom, a hydroxyl group and a carboxyl group in the molecule. ) Non-silicon or organosilicon vinyl monomers other than the component: 0 to 49% by mass
Curable resin composition containing the copolymer of the monomer mixture which consists of these, and (B) aluminum chelate.   (C) The curable resin composition according to claim 1, wherein in the general formula (I) of (1), A is an alkylene group having 2 to 4 carbon atoms. (A) according to claim 1 or 2 curable resin composition described for 100 parts by weight of component (B) is the component are those which contain 0.1 to 50 parts by weight. Furthermore, the curable resin composition according to any one of claims 1 to 3, which further comprises an organic solvent.