JP6863569B2 - Surface conditioner for coating agents - Google Patents

Description

The present invention relates to a surface conditioner that imparts hydrophilicity and antifouling property to the surface of a coating film formed by the coating agent by blending a small amount with the coating agent forming the coating agent.

In recent years, as the added value of painted surfaces has increased, there has been a demand for making the surface of a coating film formed of various coating agents such as water-based / oil-based paints, baking paints, and inks hydrophilic to improve its antifouling property.

Generally, as a method of imparting hydrophilicity to a film, the resin itself contained in the coating agent forming the film and the crosslinkable component itself forming the film are made hydrophilic to make the surface of the formed film hydrophilic. In many cases (see, for example, Patent Documents 1 to 5 below). However, in this case, since the entire resin becomes hydrophilic by selecting a hydrophilic resin or hydrofunctionalizing the resin or the crosslinkable component, the resin or the crosslinkable component that can be used is limited depending on the application of the coating film. Will be done. In addition, as a result of imparting hydrophilicity to the resin of the coating agent and the crosslinkable component itself, the entire formed coating film becomes hydrophilic, so that moisture easily penetrates into the coating film, and there is concern about the durability of the coating film itself. Occurs. In order to improve the existing coating agent and impart hydrophilicity to it in this way, it is necessary to drastically improve the resin forming the film and the crosslinkable component, and each coating agent requires a large amount of resin or the like. It needs to be reviewed.

On the other hand, as a method of imparting hydrophilicity to the coating film without changing the resin or the crosslinkable component, there is a method of adding a hydrophilic surface conditioner to the existing coating agent. In this case, by adding a small amount of hydrophilic surface conditioner, the surface of the film can be made hydrophilic without changing the basic physical properties required for the film, such as the durability and hardness of the formed film. As the hydrophilic surface conditioner, silicates typified by ethyl silicate, which develops hydrophilicity by hydrolysis, are often used. Since silicates require about 2 to 3 months to hydrolyze on the surface of the film, the film becomes hydrophobic due to unhydrolyzed silicates immediately after the film is formed, and lipophilic stains adhere to it. It is easy to do. Hydrolysis of silicates enables long-term hydrophilicity development after hydrophilicity development, but long-term hydrophilicity may cause moisture to gradually invade the inside of the coating film and reduce the durability of the coating film itself. is there. Further, as a problem of the coating agent containing a hydrophilic surface conditioner such as silicates, there is a problem from the viewpoint of stability over time such as gelation of the hydrophilic surface conditioner itself and thickening of the coating agent by cross-linking with a resin. Is also likely to occur. The hydrophilic surface conditioner itself may be hydrolyzed by moisture in the air to become highly polar, lose the surface orientation due to the hydrophobicity of silicates, and reduce the hydrophilicity performance.

As a hydrophilic surface conditioner that develops hydrophilicity from the initial stage of film formation, there are those containing a hydrophilic segment, polyalkylene oxide or a quaternary salt. Coating agents containing a hydrophilic surface conditioner containing polyalkylene oxide are relatively suitable for forming a film at room temperature, but when forming a film by high temperature baking such as baking paint, polyalkylene oxide is used. Due to its low heat resistance, there is a tendency for hydrophilicity to develop, which is considered to be thermal decomposition or hydrolysis, and the weather resistance is not good. A coating agent containing a hydrophilic surface conditioner containing a quaternary salt has a considerably high hydrophilicity, but on the other hand, water easily penetrates into the cured film, and the cured film is easily deteriorated. The surface conditioner containing the polyalkylene oxide or the quaternary salt exhibits hydrophilicity, but if it is contained too much, these problems occur. Therefore, even if it is contained, it is desirable that the amount is small. In addition, since these hydrophilic surface conditioners easily stabilize the bubbles in the coating agent, the fine bubbles caught during the coating of the coating agent may generate foam marks (armpits) during baking. For this reason, in recent years, there have been many requests for making baked paints hydrophilic, and examples of such applications include storage for outdoor installation and pre-coated metal for roofs.

Further, in Patent Document 6 below, a hydrophilic surface conditioner having a hydrophilic organic functional silicone polymer in which a silicone macromonomer such as siloxy group-containing acrylates, an unsaturated polyether component, and acrylamide are radically polymerized. However, it is described. This hydrophilic surface conditioner needs to contain 30% or more of a polyether component in the polymer. The coating agent containing this hydrophilic surface conditioner tends to cause thermal decomposition of the polyether component in the high temperature baking step, and the scattered decomposition products contaminate equipment such as a baking oven. Further, the film formed by this coating agent has a hydrophobic silicone part and a hydrophilic polyether part, so that it becomes a highly polar amphipathic skeleton, and it is easy to stabilize air bubbles in the coating agent, and an armpit is generated. Easy to make.

On the other hand, Patent Document 7 describes a hydrophilic surface conditioner in which a siloxy group-containing mono (meth) acrylate and acrylamides are radically polymerized. This hydrophilic surface conditioner imparts hydrophilicity to the smoothly formed film surface and also prevents armpits generated during baking. This surface conditioner is an industrial baking paint using a resin such as polyester melamine, and can exhibit hydrophilicity.

The surface conditioner exerts its effect by orienting it on the surface of the coating film. The main component that exhibits orientation is the siloxy group. Sufficient surface orientation can be achieved with a coating agent such as polyester melamine described in the above patent gazette. However, in recent years, silicone-based resins or fluorine-based resins may be used as resins for highly weather-resistant paints. When a coating agent using a silicone-based resin has good compatibility between the siloxy group as an orientation group and the silicone-based resin, the surface orientation is not sufficiently exhibited, and as a result, sufficient hydrophilicity cannot be exhibited on the coating surface. There is. Further, in the case of a fluorine-based resin, the surface tension of the resin is lower than that of the syroxy group which is an orientation group, and a siroxy group cannot obtain sufficient surface orientation.

Further, even in the coating agent described in the above patent represented by polyester melamine, other surface adjusting agents represented by leveling agents contain a large amount of silicone-based surface adjusting agents and fluorine-based surface adjusting agents having strong surface orientation. In some cases, these other surface conditioners may be oriented to the outermost surface of the coating, and the hydrophilic surface conditioner may not reach the outermost surface, so that a sufficient effect may not be exhibited.

As a method for imparting hydrophilicity to a fluorinated resin paint, Patent Document 8 below describes a method of using a tetrafluorinated ethylene resin graft-polymerized with sulfonic acid as a paint component. This resin has an upper limit of baking temperature of 200 ° C. and is not suitable for coating such as pre-coated metal in which the baking temperature may reach 250 ° C. Moreover, when it comes to improvement, it is necessary to make a major review from the resin.

Japanese Unexamined Patent Publication No. 5-179145 Japanese Unexamined Patent Publication No. 7-196977 Japanese Unexamined Patent Publication No. 9-31401 JP-A-2002-80789 Japanese Unexamined Patent Publication No. 4-370176 Japanese Patent Application Laid-Open No. 2008-542462 Japanese Patent No. 5347523 Japanese Patent No. 5721753

The present invention has been made to solve the above problems, and is a strong surface typified by a coating agent such as a coating agent containing a silicone resin or a fluorine resin having a low surface tension, and / or a silicone leveling agent. By blending a small amount of other additives with orientation into a coating agent containing a large amount, it is possible to prevent armpits and impart hydrophilicity to the smoothly formed coating surface, and as a result, impart antifouling property. Provided are a surface conditioner for an agent, a coating agent, and a coating film formed by applying and curing the coating agent.

The surface conditioner for a coating agent of the present invention made to achieve the above object is at least one N, N-di-substituted (meth) acrylamide monomer selected from N, N-dialkyl (meth) acrylamides, and an N, N-di-substituted (meth) acrylamide monomer. / Or at least one unsaturated group-containing morpholinamide monomer selected from unsaturated group-containing morpholinamides, 65.00 to 99.99 parts by mass, and the following chemical formula (1).
CH ₂ = C (R ¹ ) -CO-O-R ^2- R ^F ... (1)
(In the formula (1), ^{R 1} represents a hydrogen atom or a methyl group, ^{R 2} is an alkylene group of 0-12 carbon atoms, ^{R F} is a perfluoroalkyl group having 1 to 12 carbon atoms, and / or perfluoropolyether group ), 35.00 to 0.01 parts by mass of the fluorine-containing (meth) acrylate monomer , the N, N-di-substituted (meth) acrylamide monomer and / or the unsaturated group-containing morpholinamide monomer and the fluorine-containing (. Meta) acrylate monomers and unsaturated copolymers, which are alkyl (meth) acrylates, (meth) acrylamides, and / or vinyl group-containing compounds, up to 30 parts by mass with respect to 100 parts of the total mass of those monomers. It is a copolymer of a comonomer composed of, and is composed of a copolymer having a weight average molecular weight of 1500 to 50,000 .
A coating agent containing a silicone-based resin or a fluorine-based resin, and / or a coating agent containing a surface-oriented additive that is a silicone-based leveling agent, and 0.1 to 10 in terms of solid content with respect to the total amount of the coating agent. a hydrophilic surface of the coating which is added a small amount is Gana formed by the coating agent is a mass%, the antifouling property and / or leveling properties, intended to impart a popping property during the formation of the film Is.

The surface conditioner for a coating agent comprises the N, N-di-substituted (meth) acrylamide monomer and / or the unsaturated group-containing morpholinamide monomer, the fluorine-containing (meth) acrylate monomer, and a total mass of 100 parts of these monomers. Contains the copolymer obtained by copolymerizing up to 30 parts by mass of alkyl (meth) acrylates, (meth) acrylamides, and / or unsaturated comonomer which is a vinyl group-containing compound. It may be the one that exists.

The surface conditioner for a coating agent contains the N, N-di-substituted (meth) acrylamide monomer and / or the unsaturated group-containing morpholinamide monomer, the fluorine-containing (meth) acrylate monomer, and a total mass of 100 parts of these monomers. Select from (meth) acrylate monomer having a maximum of 10 parts of blocked isocyanate, (meth) acrylate monomer having an alkoxy group, (meth) acrylate monomer having a hydroxyl group, and (meth) acrylamide containing a hydroxyl group. It may contain the copolymer obtained by copolymerizing with at least one of the functional group-containing comonomer.

The coating agent of the present invention made to achieve the above object contains the above-mentioned surface conditioner for a coating agent and a film-forming component.

The cured film of the present invention made to achieve the above object is formed on a base material by the above coating agent.

The cured coating is at the coating agent surface conditioner by said coating surface, said hydrophilic, and a said antifouling and / or the leveling, the popping of a time the formation of the film It is preferable to have.

According to the surface conditioner for a coating agent of the present invention, hydrophilicity can be imparted to the film surface immediately after the film is formed by adding a small amount to the coating agent without requiring a reaction such as subsequent hydrolysis. The contact angle can be reduced to improve the detergency with water such as rainwater, and antifouling property can be exhibited.

Further, the coating agent of the present invention containing this surface conditioner has excellent storage stability because there is no change in the performance of the surface conditioner during storage and / or a change in the viscosity of the coating agent due to the surface conditioner. .. Further, defoaming and defoaming by the defoaming agent blended in the coating agent are promoted, prevention of armpits is achieved, and a smooth film can be formed.

This surface conditioner exhibits sufficient surface orientation at the time of curing even in a coating agent having a low surface tension represented by a silicone resin or a fluorine resin, and imparts hydrophilicity to the film surface. Further, in a coating agent typified by polyester melamine or acrylic melamine that is relatively easy to surface-oriented, a hydrophobic component having low surface tension such as a silicone-based surface conditioner typified by a leveling agent or a fluorine-based surface conditioner. Among the coating agents containing a large amount of the above, this surface conditioner can exhibit sufficient surface orientation and exhibits hydrophilicity on the surface of the coating film. As a result, even if a coating agent containing a non-hydrophilic or non-hydrophilic resin or a film-forming component is used, sufficient antifouling property can be imparted to the film, and the cured film has a leveling property to form a film. It can have anti-armpit properties at times.

Since silicate-based hydrophilicity-imparting additives that have been widely used in the past have extremely high surface orientation, only silicate-based additives are present on the outermost layer of the coating even when used in combination with other surface modifiers that impart hydrophilicity. It was a material that was oriented and it was difficult to obtain a synergistic effect. However, the surface conditioner for coating agents of the present invention has strong surface orientation, is difficult to mix with silicate-based additives, and has stronger surface orientation than conventional additives, so that it is oriented toward the outermost surface at the same time. It is possible to combine both characteristics. Therefore, it can be used not only as a coating agent curable at room temperature but also as a coating agent for baking coating.

Further, the film formed by the coating agent added by using the surface conditioner for the coating agent of the present invention is smooth, has excellent topcoating characteristics, and has heat resistance without repellency or lumps during the baking process. Are better.

Hereinafter, embodiments for carrying out the present invention will be described in detail, but the scope of the present invention is not limited to these embodiments.

The surface conditioner for a coating agent of the present invention is at least an unsaturated group which is an N, N-di-substituted (meth) acrylamide monomer which is an N, N-dialkyl (meth) acrylamide and / or an unsaturated group-containing morpholinamide. It contains a copolymer obtained by copolymerizing a contained morpholine amide monomer and a fluorine-containing (meth) acrylate monomer.

More specifically, this surface conditioner for coating agents is exemplified by dimethyl (meth) acrylamides such as N, N-dimethylacrylamide and diethyl (meth) acrylamides such as N, N-diethylacrylamide. At least one acrylamide monomer selected from N, N-dialkyl (meth) acrylamides having linear, branched and / or cyclic alkyl groups having 1 to 3 carbon atoms 65.00 to 99.99 parts by mass. And a polymer containing 35.00 to 0.01 parts by mass of a fluorine-containing (meth) acrylate monomer. This surface conditioner is used to be added to and contained in various coating agents which are film forming compositions in order to cure and form a film.

(Meta) acrylic means acrylic and methacrylic.

When the amount of N, N-dialkyl (meth) acrylamide monomer and / or unsaturated group-containing morpholine amide monomer is less than 65 parts by mass, the obtained surface conditioner cannot exhibit sufficient hydrophilicity in the coating film. In addition, the compatibility with other components blended in the coating agent containing the surface conditioner becomes extremely poor, and cissing occurs when the coating agent is applied, dents are generated on the surface of the coating film, and the film is formed. The leveling property of the top coat on the coated film is deteriorated, and sufficient top coat adhesion cannot be obtained. It is preferable that the N, N-dialkyl (meth) acrylamide monomer and / or the unsaturated group-containing morpholine amide monomer is 70 to 99 parts by mass and the fluorine-containing (meth) acrylate monomer is 30 to 1 part by mass.

When the amount of the fluorine-containing (meth) acrylate monomer exceeds 35.00 parts by mass, the obtained surface conditioner has a large content of hydrophobic fluorine, and cannot exhibit sufficient hydrophilicity. On the other hand, when it is less than 0.01 parts by mass, the obtained surface conditioner cannot sufficiently obtain the surface orientation in the coating film due to fluorine having a low surface tension, and cannot sufficiently exhibit the hydrophilicity on the coating film surface. ..

The weight average molecular weight of this copolymer is in the range of 1500 to 50,000. If the weight average molecular weight is less than 1500, the problem of foaming is likely to occur when the coating agent containing the copolymer is applied. On the other hand, when the weight average molecular weight exceeds 50,000, the orientation to the coating surface is lowered and sufficient hydrophilicity cannot be obtained. The weight average molecular weight of the copolymer is preferably 1500 to 20000.

In the copolymer of the above-mentioned N, N-di-substituted acrylamide monomer and / or unsaturated group-containing morpholine amide monomer and fluorine-containing (meth) acrylate monomer, hydroxyl group-containing (meth) acrylates and hydroxyl group-containing (meth) acrylamide are contained. , At least any functional group-containing comonomer selected from alkoxy group-containing (meth) acrylates other than acrylate ester groups and blocked isocyanate group-containing (meth) acrylates may be copolymerized. The functional group-containing comonomer is 10 parts or less in mass ratio with respect to the total mass of 100 parts of the N, N-di-substituted (meth) acrylamide monomer and / or the unsaturated group-containing morpholinamide monomer and the fluorine-containing (meth) acrylate monomer. Is preferable. As a result, the surface of the coating film reacts with the resin in the paint, so that the surface conditioner is less likely to be dissolved by rainwater, which can be advantageous in antifouling property. If it exceeds 10 copies, the original performance may be impaired. These functional group-containing comonomer may be used alone or in combination as long as the total mass is less than or equal to the specified blending amount.

As a fluorine-containing (meth) acrylate monomer, the following chemical formula (1)
^{_{CH 2 = C (R 1)}} -CO-O-R 2 -R F (1)
(In the formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² is a straight, branched and / or cyclic alkylene group having 0-12 carbon atoms, R ^F is C 1 -C 12 of straight, branched chain and / or cyclic perfluoroalkyl group and / or a perfluoropolyether group. Incidentally, R ^F is a perfluoroalkyl group may be any one of the perfluoropolyether group Is a perfluoropolyether group-containing perfluoroalkyl group or a perfluoroalkyl group-containing perfluoropolyether group). An acrylate monomer is used.

Examples of the fluorine-containing (meth) acrylate monomer represented by the chemical formula (1) and containing a perfluoroalkyl group include perfluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, and perfluoropropyl (meth). ) Acrylate, perfluorobutyl (meth) acrylate, perfluoropentyl (meth) acrylate, perfluorohexyl (meth) acrylate, perfluoroheptyl (meth) acrylate, perfluorooctyl (meth) acrylate, perfluorononyl (meth) acrylate , Perfluorodecyl (meth) acrylate, perfluoroundecyl (meth) acrylate, perfluorododecyl (meth) acrylate,
Perfluoroiso-propyl (meth) acrylate, perfluoroiso-butyl (meth) acrylate, perfluorotert-butyl (meth) acrylate, perfluorosec-butyl (meth) acrylate, perfluoroiso-pentyl (meth) acrylate, Perfluoroiso-hexyl (meth) acrylate, perfluoroiso-heptyl (meth) acrylate, perfluoroiso-octyl (meth) acrylate, perfluoroiso-nonyl (meth) acrylate, perfluoroiso-decyl (meth) acrylate, Perfluoroiso-undecyl (meth) acrylate, perfluoroiso-dodecyl (meth) acrylate,
Perfluorocyclopentyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, perfluorocycloheptyl (meth) acrylate, perfluorocyclooctyl (meth) acrylate, perfluorocyclononyl (meth) acrylate, perfluorocyclodecyl (meth) Acrylate, perfluorocycloundecyl (meth) acrylate, perfluorocyclododecyl (meth) acrylate,
Perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, perfluoropropylmethyl (meth) acrylate, perfluorobutylmethyl (meth) acrylate, perfluoropentylmethyl (meth) acrylate, perfluorohexylmethyl ( Meta) acrylate, perfluoroheptylmethyl (meth) acrylate, perfluorooctylmethyl (meth) acrylate, perfluorononylmethyl (meth) acrylate, perfluorodecylmethyl (meth) acrylate, perfluoroundecylmethyl (meth) acrylate, Perfluorododecylmethyl (meth) acrylate, perfluoroiso-propylmethyl (meth) acrylate, perfluoroiso-butylmethyl (meth) acrylate, perfluorotert-butylmethyl (meth) acrylate, perfluorosec-butylmethyl (meth) acrylate, Perfluoroiso-pentylmethyl (meth) acrylate, perfluoroiso-hexylmethyl (meth) acrylate, perfluoroiso-heptylmethyl (meth) acrylate, perfluoroiso-octylmethyl (meth) acrylate, perfluoroiso-nonylmethyl ( Meta) acrylate, perfluoroiso-decylmethyl (meth) acrylate, perfluoroiso-undecylmethyl (meth) acrylate, perfluoroiso-dodecylmethyl (meth) acrylate, perfluorocyclopentylmethyl (meth) acrylate, perfluorocyclohexylmethyl (Meta) acrylate, perfluorocycloheptylmethyl (meth) acrylate, perfluorocyclooctylmethyl (meth) acrylate, perfluorocyclononylmethyl (meth) acrylate, perfluorocyclodecylmethyl (meth) acrylate, perfluorocycloundecyl Methyl (meth) acrylate, perfluorocyclododecylmethyl (meth) acrylate,
Perfluoromethylethyl (meth) acrylate, perfluoroethyl ethyl (meth) acrylate, perfluoropropylethyl (meth) acrylate, perfluorobutylethyl (meth) acrylate, perfluoropentylethyl (meth) acrylate, perfluorohexyl ethyl ( Meta) acrylate, perfluoroheptylethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, perfluorononylethyl (meth) acrylate, perfluorodecylethyl (meth) acrylate, perfluoroundecylethyl (meth) acrylate, Perfluorododecylethyl (meth) acrylate, perfluoroiso-propylethyl (meth) acrylate, perfluoroiso-butylethyl (meth) acrylate, perfluorotert-butylethyl (meth) acrylate, perfluorosec-butyl (meth) ethyl acrylate , Perfluoroiso-pentylethyl (meth) acrylate, perfluoroiso-hexylethyl (meth) acrylate, perfluoroiso-heptylethyl (meth) acrylate, perfluoroiso-octylethyl (meth) acrylate, perfluoroiso-nonylethyl (Meta) acrylate, perfluoroiso-decylethyl (meth) acrylate, perfluoroiso-undecylethyl (meth) acrylate, perfluoroiso-dodecylethyl (meth) acrylate, perfluorocyclopentylethyl (meth) acrylate, perfluorocyclohexyl Ethyl (meth) acrylate, perfluorocycloheptyl ethyl (meth) acrylate, perfluorocyclooctyl ethyl (meth) acrylate, perfluorocyclononylethyl (meth) acrylate, perfluorocyclodecylethyl (meth) acrylate, perfluorocycloun Decylethyl (meth) acrylate, perfluorocyclododecylethyl (meth) acrylate,
Perfluoromethylpropyl (meth) acrylate, perfluoroethylpropyl (meth) acrylate, perfluoropropylpropyl (meth) acrylate, perfluorobutylpropyl (meth) acrylate, perfluoropentylpropyl (meth) acrylate, perfluorohexylpropyl ( Meta) acrylate, perfluoroheptylpropyl (meth) acrylate, perfluorooctylpropyl (meth) acrylate, perfluorononylpropyl (meth) acrylate, perfluorodecylpropyl (meth) acrylate, perfluoroundecylpropyl (meth) acrylate, Perfluorododecylpropyl (meth) acrylate, perfluoroiso-propyl (meth) acrylate, perfluoroiso-butylpropyl (meth) acrylate, perfluorotert-butylpropyl (meth) acrylate, perfluorosec-butyl (meth) propyl Acrylate, perfluoroiso-pentylpropyl (meth) acrylate, perfluoroiso-hexylpropyl (meth) acrylate, perfluoroiso-heptylpropyl (meth) acrylate, perfluoroiso-octylpropyl (meth) acrylate, perfluoroiso- Nonylpropyl (meth) acrylate, perfluoroiso-decylpropyl (meth) acrylate, perfluoroiso-undecylpropyl (meth) acrylate, perfluoroiso-dodecylpropyl (meth) acrylate, perfluorocyclopentylpropyl (meth) acrylate, Perfluorocyclohexylpropyl (meth) acrylate, perfluorocycloheptylpropyl (meth) acrylate, perfluorocyclooctylpropyl (meth) acrylate, perfluorocyclononylpropyl (meth) acrylate, perfluorocyclodecylpropyl (meth) acrylate, per Fluorocycloundecylpropyl (meth) acrylate, perfluorocyclododecylpropyl (meth) acrylate,
Perfluoromethylbutyl (meth) acrylate, perfluoroethylbutyl (meth) acrylate, perfluoropropylbutyl (meth) acrylate, perfluorobutylbutyl (meth) acrylate, perfluoropentylbutyl (meth) acrylate, perfluorohexylbutyl ( Meta) acrylate, perfluoroheptylbutyl (meth) acrylate, perfluorooctylbutyl (meth) acrylate, perfluorononylbutyl (meth) acrylate, perfluorodecylbutyl (meth) acrylate, perfluoroundecylbutyl (meth) acrylate, Perfluorododecylbutyl (meth) acrylate, perfluoroiso-propylbutyl (meth) acrylate, perfluoroiso-butylbutyl (meth) acrylate, perfluorotert-butylbutyl (meth) acrylate, perfluorosec-butyl (meth) butyl acrylate , Perfluoroiso-pentylbutyl (meth) acrylate, perfluoroiso-hexylbutyl (meth) acrylate, perfluoroiso-heptylbutyl (meth) acrylate, perfluoroiso-octylbutyl (meth) acrylate, perfluoroiso-nonylbutyl (Meta) acrylate, perfluoroiso-decylbutyl (meth) acrylate, perfluoroiso-undecylbutyl (meth) acrylate, perfluoroiso-dodecylbutyl (meth) acrylate, perfluorocyclopentylbutyl (meth) acrylate, perfluorocyclohexyl Butyl (meth) acrylate, perfluorocycloheptylbutyl (meth) acrylate, perfluorocyclooctylbutyl (meth) acrylate, perfluorocyclononylbutyl (meth) acrylate, perfluorocyclodecylbutyl (meth) acrylate, perfluorocycloun Decylbutyl (meth) acrylate, perfluorocyclododecylbutyl (meth) acrylate,
Perfluoromethylpentyl (meth) acrylate, perfluoroethylpentyl (meth) acrylate, perfluoropropylpentyl (meth) acrylate, perfluorobutylpentyl (meth) acrylate, perfluoropentylpentyl (meth) acrylate, perfluorohexylpentyl ( Meta) acrylate, perfluoroheptylpentyl (meth) acrylate, perfluorooctylpentyl (meth) acrylate, perfluorononylpentyl (meth) acrylate, perfluorodecylpentyl (meth) acrylate, perfluoroundecylpentyl (meth) acrylate, Perfluorododecylpentyl (meth) acrylate, perfluoroiso-propylpentyl (meth) acrylate, perfluoroiso-butylpentyl (meth) acrylate, perfluorotert-butylpentyl (meth) acrylate, perfluorosec-butyl (meth) Pentyl acrylate, perfluoroiso-pentylpentyl (meth) acrylate, perfluoroiso-hexylpentyl (meth) acrylate, perfluoroiso-heptylpentyl (meth) acrylate, perfluoroiso-octylpentyl (meth) acrylate, perfluoroiso -Nonylpentyl (meth) acrylate, perfluoroiso-decylpentyl (meth) acrylate, perfluoroiso-undecylpentyl (meth) acrylate, perfluoroiso-dodecylpentyl (meth) acrylate, perfluorocyclopentylpentyl (meth) acrylate , Perfluorocyclohexylpentyl (meth) acrylate, perfluorocycloheptylpentyl (meth) acrylate, perfluorocyclooctylpentyl (meth) acrylate, perfluorocyclononylpentyl (meth) acrylate, perfluorocyclodecylpentyl (meth) acrylate, Perfluorocycloundecylpentyl (meth) acrylate, perfluorocyclododecylpentyl (meth) acrylate,
Perfluoromethylhexyl (meth) acrylate, perfluoroethylhexyl (meth) acrylate, perfluoropropylhexyl (meth) acrylate, perfluorobutylhexyl (meth) acrylate, perfluoropentylhexyl (meth) acrylate, perfluorohexylhexyl (meth) ) Acrylate, perfluoroheptylhexyl (meth) acrylate, perfluorooctylhexyl (meth) acrylate, perfluorononylhexyl (meth) acrylate, perfluorodecylhexyl (meth) acrylate, perfluoroundecylhexyl (meth) acrylate, per Fluorododecylhexyl (meth) acrylate, perfluoroiso-propylhexyl (meth) acrylate, perfluoroiso-butylhexyl (meth) acrylate, perfluorotert-butylhexyl (meth) acrylate, perfluorosec-butyl (meth) hexyl Acrylate, perfluoroiso-pentylhexyl (meth) acrylate, perfluoroiso-hexylhexyl (meth) acrylate, perfluoroiso-heptylhexyl (meth) acrylate, perfluoroiso-octylhexyl (meth) acrylate, perfluoroiso- Nonylhexyl (meth) acrylate, perfluoroiso-decylhexyl (meth) acrylate, perfluoroiso-undecylhexyl (meth) acrylate, perfluoroiso-dodecylhexyl (meth) acrylate, perfluorocyclopentylhexyl (meth) acrylate, Perfluorocyclohexylhexyl (meth) acrylate, perfluorocycloheptylhexyl (meth) acrylate, perfluorocyclooctylhexyl (meth) acrylate, perfluorocyclononylhexyl (meth) acrylate, perfluorocyclodecylhexyl (meth) acrylate, per. Fluorocycloundecylhexyl (meth) acrylate, perfluorocyclododecylhexyl (meth) acrylate,
Perfluoromethylheptyl (meth) acrylate, perfluoroethylheptyl (meth) acrylate, perfluoropropylheptyl (meth) acrylate, perfluorobutylheptyl (meth) acrylate, perfluoropentylheptyl (meth) acrylate, perfluorohexylheptyl (perfluorohexyl heptyl (meth) acrylate) Meta) acrylate, perfluoroheptyl heptyl (meth) acrylate, perfluorooctyl heptyl (meth) acrylate, perfluorononyl heptyl (meth) acrylate, perfluorodecyl heptyl (meth) acrylate, perfluoroundecyl heptyl (meth) acrylate, Perfluorododecylheptyl (meth) acrylate, perfluoroiso-propylheptyl (meth) acrylate, perfluoroiso-butylheptyl (meth) acrylate, perfluorotert-butylheptyl (meth) acrylate, perfluorosec-butyl (meth) Heptyl acrylate, perfluoroiso-pentyl heptyl (meth) acrylate, perfluoroiso-hexyl heptyl (meth) acrylate, perfluoroiso-heptyl heptyl (meth) acrylate, perfluoroiso-octyl heptyl (meth) acrylate, perfluoroiso -Nonyl heptyl (meth) acrylate, perfluoroiso-decyl heptyl (meth) acrylate, perfluoroiso-undecyl heptyl (meth) acrylate, perfluoroiso-dodecyl heptyl (meth) acrylate, perfluorocyclopentyl heptyl (meth) acrylate, per. Fluorocyclohexylheptyl (meth) acrylate, perfluorocycloheptylheptyl (meth) acrylate, perfluorocyclooctylheptyl (meth) acrylate, perfluorocyclononylheptyl (meth) acrylate, perfluorocyclodecylheptyl (meth) acrylate, perfluoro Cycloundecyl heptyl (meth) acrylate, perfluorocyclododecyl heptyl (meth) acrylate,
Perfluoromethyloctyl (meth) acrylate, perfluoroethyloctyl (meth) acrylate, perfluoropropyloctyl (meth) acrylate, perfluorobutyloctyl (meth) acrylate, perfluoropentyloctyl (meth) acrylate, perfluorohexyl octyl (perfluorohexyl octyl) Meta) acrylate, perfluoroheptyl octyl (meth) acrylate, perfluorooctyl octyl (meth) acrylate, perfluorononyl octyl (meth) acrylate, perfluorodecyloctyl (meth) acrylate, perfluoroundecyl octyl (meth) acrylate, Perfluorododecyloctyl (meth) acrylate, perfluoroiso-propyloctyl (meth) acrylate, perfluoroiso-butyloctyl (meth) acrylate, perfluorotert-butyloctyl (meth) acrylate, perfluorosec-butyl (meth) Octyl acrylate, perfluoroiso-pentyl octyl (meth) acrylate, perfluoroiso-hexyl octyl (meth) acrylate, perfluoroiso-heptyl octyl (meth) acrylate, perfluoroiso-octyl octyl (meth) acrylate, perfluoroiso -Nonyloctyl (meth) acrylate, perfluoroiso-decyloctyl (meth) acrylate, perfluoroiso-undecyloctyl (meth) acrylate, perfluoroiso-dodecyloctyl (meth) acrylate, perfluorocyclopentyloctyl (meth) acrylate , Perfluorocyclohexyloctyl (meth) acrylate, perfluorocycloheptyloctyl (meth) acrylate, perfluorocyclooctyloctyl (meth) acrylate, perfluorocyclononyloctyl (meth) acrylate, perfluorocyclodecyloctyl (meth) acrylate, Perfluorocycloundecyloctyl (meth) acrylate, perfluorocyclododecyloctyl (meth) acrylate,
Perfluoromethylnonyl (meth) acrylate, perfluoroethylnonyl (meth) acrylate, perfluoropropylnonyl (meth) acrylate, perfluorobutylnonyl (meth) acrylate, perfluoropentylnonyl (meth) acrylate, perfluorohexylnonyl ( Meta) acrylate, perfluoroheptylnonyl (meth) acrylate, perfluorooctylnonyl (meth) acrylate, perfluorononylnonyl (meth) acrylate, perfluorodecylnonyl (meth) acrylate, perfluoroundecylnonyl (meth) acrylate, Perfluorododecylnonyl (meth) acrylate, perfluoroiso-propylnonyl (meth) acrylate, perfluoroiso-butylnonyl (meth) acrylate, perfluorotert-butylnonyl (meth) acrylate, perfluorosec-butyl (meth) nonyl acrylate , Perfluoroiso-pentylnonyl (meth) acrylate, perfluoroiso-hexylnonyl (meth) acrylate, perfluoroiso-heptylnonyl (meth) acrylate, perfluoroiso-octylnonyl (meth) acrylate, perfluoroiso-nonylnonyl ( Meta) acrylate, perfluoroiso-decylnonyl (meth) acrylate, perfluoroiso-undecylnonyl (meth) acrylate, perfluoroiso-dodecylnonyl (meth) acrylate, perfluorocyclopentylnonyl (meth) acrylate, perfluorocyclohexylnonyl (meth) ) Acrylate, perfluorocycloheptylnonyl (meth) acrylate, perfluorocyclooctylnonyl (meth) acrylate, perfluorocyclononylnonyl (meth) acrylate, perfluorocyclodecylnonyl (meth) acrylate, perfluorocycloundecylnonyl ( Meta) acrylate, perfluorocyclododecylnonyl (meth) acrylate,
Perfluoromethyldecyl (meth) acrylate, perfluoroethyldecyl (meth) acrylate, perfluoropropyldecyl (meth) acrylate, perfluorobutyldecyl (meth) acrylate, perfluoropentyldecyl (meth) acrylate, perfluorohexyldecyl ( Meta) acrylate, perfluoroheptyl decyl (meth) acrylate, perfluorooctyl decyl (meth) acrylate, perfluorononyl decyl (meth) acrylate, perfluorodecyl decyl (meth) acrylate, perfluoroundecyl decyl (meth) acrylate, Perfluorododecyl decyl (meth) acrylate, perfluoroiso-propyl decyl (meth) acrylate, perfluoroiso-butyl decyl (meth) acrylate, perfluorotert-butyl decyl (meth) acrylate, perfluoro sec-butyl (meth) decyl acrylate , Perfluoroiso-pentyldecyl (meth) acrylate, perfluoroiso-hexyldecyl (meth) acrylate, perfluoroiso-heptyldecyl (meth) acrylate, perfluoroiso-octyldecyl (meth) acrylate, perfluoroiso-nonyldecyl ( Meta) Acrylate, Perfluoroiso-decyldecyl (meth) Acrylate, Perfluoroiso-Undecyldecyl (Meta) Acrylate, Perfluoroiso-Dodecyldecyl (Meta) Acrylate, Perfluorocyclopentyldecyl (Meta) Acrylate, Perfluorocyclohexyldecyl (Meta) ) Acrylate, perfluorocycloheptyl decyl (meth) acrylate, perfluorocyclooctyl decyl (meth) acrylate, perfluorocyclononyl decyl (meth) acrylate, perfluorocyclodecyl decyl (meth) acrylate, perfluorocycloundecyl decyl ( Meta) acrylate, perfluorocyclododecyldecyl (meth) acrylate,
Perfluoromethyl undecyl (meth) acrylate, perfluoroethyl undecyl (meth) acrylate, perfluoropropyl undecyl (meth) acrylate, perfluorobutyl undecyl (meth) acrylate, perfluoropentyl undecyl (meth) acrylate, Perfluorohexyl undecyl (meth) acrylate, perfluoroheptyl undecyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate, perfluorononyl undecyl (meth) acrylate, perfluorodecyl undecyl (meth) acrylate, Perfluoroundecyl undecyl (meth) acrylate, perfluorododecyl undecyl (meth) acrylate, perfluoroiso-propylundecyl (meth) acrylate, perfluoroiso-butylundecyl (meth) acrylate, perfluorotert-butyl Undecyl (meth) acrylate, perfluorosec-butyl (meth) undecyl acrylate, perfluoroiso-pentyl undecyl (meth) acrylate, perfluoroiso-hexyl undecyl (meth) acrylate, perfluoroiso-heptyl undecyl (Meta) acrylate, perfluoroiso-octyl undecyl (meth) acrylate, perfluoroiso-nonyl undecyl (meth) acrylate, perfluoroiso-decyl undecyl (meth) acrylate, perfluoroiso-undecyl undecyl (meth) acrylate, Perfluoroiso-dodecyl undecyl (meth) acrylate, perfluorocyclopentyl undecyl (meth) acrylate, perfluorocyclohexyl undecyl (meth) acrylate, perfluorocycloheptyl undecyl (meth) acrylate, perfluorocyclooctyl undecyl (meth) Meta) acrylate, perfluorocyclononyl undecyl (meth) acrylate, perfluorocyclodecyl undecyl (meth) acrylate, perfluorocycloundecyl undecyl (meth) acrylate, perfluorocyclododecyl undecyl (meth) acrylate,
Perfluoromethyldodecyl (meth) acrylate, perfluoroethyldodecyl (meth) acrylate, perfluoropropyldodecyl (meth) acrylate, perfluorobutyldodecyl (meth) acrylate, perfluoropentyldodecyl (meth) acrylate, perfluorohexyldodecyl (perfluorohexyldodecyl (meth) acrylate) Meta) acrylate, perfluoroheptyldodecyl (meth) acrylate, perfluorooctyldodecyl (meth) acrylate, perfluorononyldodecyl (meth) acrylate, perfluorodecyldodecyl (meth) acrylate, perfluoroundecyldodecyl (meth) acrylate, Perfluorododecyl dodecyl (meth) acrylate, perfluoroiso-propyl dodecyl (meth) acrylate, perfluoroiso-butyldodecyl (meth) acrylate, perfluorotert-butyldodecyl (meth) acrylate, perfluorosec-butyl (meth) Dodecyl acrylate, perfluoroiso-pentyldodecyl (meth) acrylate, perfluoroiso-hexyldodecyl (meth) acrylate, perfluoroiso-heptyl dodecyl (meth) acrylate, perfluoroiso-octyldodecyl (meth) acrylate, perfluoroiso -Nonyldodecyl (meth) acrylate, perfluoroiso-decyldodecyl (meth) acrylate, perfluoroiso-undecyldodecyl (meth) acrylate, perfluoroiso-dodecyldodecyl (meth) acrylate, perfluorocyclopentyldodecyl (meth) acrylate , Perfluorocyclohexyldodecyl (meth) acrylate, perfluorocycloheptyl dodecyl (meth) acrylate, perfluorocyclooctyldodecyl (meth) acrylate, perfluorocyclononyldodecyl (meth) acrylate, perfluorocyclodecyldodecyl (meth) acrylate, Examples thereof include perfluorocycloundecyldodecyl (meth) acrylate and perfluorocyclododecyldodecyl (meth) acrylate.

Examples of the fluorine-containing (meth) acrylate monomer represented by the chemical formula (1) and containing a perfluoropolyether group include, for example.
The following chemical formulas (2) and (3)
^{_{CH 2 = C (R 3)}} -CO-O-CH 2 -CF 2 -O- (CF 2 -CF 2 -O) n - (CF 2 -CF 2 -CF 2 -O) m - (CFCF 3 - CF _2- O) _p -R ^F2 ... (2)
(In the formula (2), R ³ represents a hydrogen atom or a methyl group, n, m, p represents a number of 0 to 8, and RF ² represents a perfluoroalkyl group having 1 to 6 carbon atoms.)
^{_{CH 2 = C (R 4)}} -CO-O- (CH 2) 2 -NH-CO-O-CH 2 -CF 2 -O- (CF 2 -CF 2 -O) q - (CF 2 -CF 2 -CF ₂ -O) _r- (CFCF ₃ -CF ₂ -O) _s -R ^F3 ... (3)
(In the formula (3), R ⁴ represents a hydrogen atom or a methyl group, q, r, s represents a number of 0 to 8, and R ^F3 represents a perfluoroalkyl group having 1 to 6 carbon atoms.) Can be mentioned.

The fluorine-containing (meth) acrylate monomer may be used alone or in combination of two or more.

The N, N-di-substituted acrylamide monomers are dimethyl (meth) acrylamides and diethyl (meth) acrylamides, for example, DMAA which is N, N-dimethylacrylamide, and DEAA (KJ Chemicals Co., Ltd.) which is N, N-diethylacrylamide. Product name).

Examples of the (meth) acryloyl morpholins as the unsaturated group-containing morpholine amide monomer include ACMO (product name of KJ Chemicals Co., Ltd.), which is acryloyl morpholine.

The hydroxyl group-containing (meth) acrylates include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy-. Examples include 3-phenoxypropyl (meth) acrylate, a monomer obtained by adding n mol (n is 1 to 5) of ε-caprolactone to (meth) acrylate having a hydroxyl group (for example, Praxel FM series: trade name manufactured by Daicel Co., Ltd.). Be done.

Examples of hydroxyl group-containing (meth) acrylamides include N-hydroxyethyl acrylamide and N-hydroxymethyl acrylamide.

The (meth) acrylates having an alkoxy group include, for example, an ester containing an alkoxysilyl group of (meth) acrylate, more specifically, 3-methacryloxypropylmethyldimethoxysilane (KBM-502), 3-methacryloxypropyltrimethoxy. Silane (KBM-503), 3-methacryloxypropylmethyldiethoxysilane (KBE-502), 3-methacryloxypropyltriethoxysilane (KBE-503), 3-acryloxypropyltrimethoxysilane (KBM-5103) ( Both are manufactured by Shin-Etsu Silicone Co., Ltd.).

Blocked isocyanate group-containing (meth) acrylates are (meth) acrylate monomers having an isocyanate group blocked with a blocking agent, and are, for example, 2-isocyanatoethyl (meth) acrylate as a blocking agent, such as ethyl alcohol and isopropyl. Examples thereof include those obtained by reacting alcohol, caprolactam, MEK-oxime, dimethylpyrazole, diethyl malonate, and the like. More specifically, 2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate (Karen's MOI-BM: manufactured by Showa Denko KK; registered trademark), 2-([3,] 5-Dimethylpyrazolyl] carbonylamino) Ethyl (Carens MOI-BP: manufactured by Showa Denko KK; registered trademark) and the like.

In the copolymer of the above-mentioned N, N-di-substituted (meth) acrylamide monomer and / or unsaturated group-containing morpholinamide monomer and fluorine-containing (meth) acrylate monomer, alkyl (meth) acrylates and (meth) acrylamide are contained. At least one unsaturated comonomer selected from the class and vinyl group-containing compounds may be copolymerized. However, the copolymerization amount of the unsaturated comonomer should be such that the obtained copolymer does not impair the hydrophilicity-imparting performance, and the N, N-di-substituted (meth) acrylamide monomer and / or unsaturated The mass ratio of the group-containing morpholinamide monomer and the fluorine-containing (meth) acrylate monomer to 100 parts in total is preferably 30 parts or less.

Alkyl (meth) acrylates are unsubstituted or substituted with at least one of an amino group, a monoalkylamino group, a dialkylamino group, a hydrocarbon aromatic ring, and a heterocyclic ring, or an acid anhydride is cleaved and added to the hydroxy group. A diluting monomer, eg, an alkyl acrylate, or an alkyl methacrylate, which is a linear, branched, and / or cyclic, unsubstituted or substituted alkyl (meth) acrylate having an alkyl group having 1 to 12 carbon atoms. , Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n -Octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 2- Examples thereof include acryloyloxyethyl-succinic acid, 2-acryloyloxyethyl-phthalic acid, tetrahydrofurfuryl (meth) acrylate and the like.

(Meta) acrylamides are other than N, N-dialkyl (meth) acrylamides such as dimethyl (meth) acrylamides and diethyl (meth) acrylamides and (meth) acryloylmorpholins, and are (meth) acrylamides and none. N-alkyl (meth) acrylamide or cyclic (meth) acrylamide with an alkyl group having 1 to 12 carbon atoms, which may be substituted or substituted with a ketone group, an amino group, a sulfonic acid group or a salt thereof, for example, dimethylaminopropyl (meth). ) Acrylamide, isopropyl (meth) acrylamide, diacetone acrylamide, (meth) acrylamide-tert-butylsulfonic acid, (meth) acrylamide-tert-butylsulfonic acid organic salt, (meth) acrylamide-tert-butylsulfonic acid inorganic salt, etc. However, it can be mentioned.

Vinyl group-containing compounds include linear, branched or cyclic alkyl vinyl EL monomers having 1 to 12 carbon atoms such as n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, cyclohexyl vinyl ether and lauryl vinyl ether; acetic acid. Examples include fatty acid vinyl ester monomers such as vinyl, vinyl propionate and vinyl laurate.

This copolymer can be obtained by a radical polymerization method. In the radical polymerization method, for example, with a predetermined amount of at least one N, N-di-substituted (meth) acrylamide monomer selected from dimethyl (meth) acrylamide and diethyl (meth) acrylamide and / or the unsaturated group-containing morpholinamide monomer. , A predetermined amount of fluorine-containing (meth) acrylate monomer and, if necessary, a predetermined amount of hydroxyl group-containing (meth) acrylate, alkoxy group-containing (meth) acrylate, hydroxyl group-containing (meth) acrylamide, and blocked isocyanate group. At least one functional group-containing comonomer selected from the contained (meth) acrylates, and if necessary, at least a predetermined amount of alkyl (meth) acrylates, (meth) acrylamides and vinyl group-containing compounds. It can be obtained by randomly copolymerizing a kind of unsaturated comonomer in a solvent in the presence of a radical polymerization initiator and, if necessary, a chain transfer agent. As the radical polymerization initiator, for example, tert-butylperoxy-2-ethylhexanoate can be used, and as the chain transfer agent, for example, dodecyl mercaptan can be used. Further, as the solvent, for example, an inert solvent such as cyclohexanone can be used. The copolymer may be obtained by radical polymerization or by ionic polymerization such as anionic polymerization. The copolymer may be a random copolymer, a block copolymer, a graft copolymer, or an alternating copolymer.

The surface conditioner containing the obtained copolymer may consist only of the copolymer, or the copolymer may be dissolved or suspended in an inert solvent before use. The inert solvent is one capable of dissolving or suspending this copolymer. Specifically, hydrocarbon solvents such as xylene, toluene and cyclohexane; ketone solvents such as cyclohexanone and methylisobutylketone; methylcellosolve, cellosolve, butylcellosolve, methylcarbitol, carbitol, butylcarbitol, diethylcarbitol, propylene Ether solvents such as glycol monomethyl ether; ester solvents such as n-butyl acetate, isobutyl acetate, n-amyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; n-butyl alcohol, sec-butyl Alcohol solvents such as alcohol, isobutyl alcohol, cyclohexanol, 2-ethylhexanol, 3-methyl-3-methoxybutanol can be mentioned. These solvents may be used alone or in combination of two or more.

The coating agent contains a surface conditioner and a film-forming component. When a coating agent is prepared by blending this surface conditioner, a known coating agent that does not contain the surface conditioner and contains a film-forming component is prepared in advance, and then the surface conditioner is blended and kneaded to obtain a desired coating agent. A coating agent is obtained. They may be mixed simultaneously or in any order. It is preferable that the coating agent is blended with a surface conditioner so as to be a copolymer of 0.1 to 10% by mass, preferably 0.5 to 5.0% by mass in terms of solid content with respect to the total amount of the coating agent. The coating agent may contain a third component other than the film-forming component and the inert solvent. The third component is not particularly limited, and examples thereof include colorants such as pigments and dyes, resins, diluting solvents, catalysts, and surfactants. Further, if necessary, a sensitizer, an antistatic agent, an antifoaming agent, a dispersant, and a viscosity modifier may be blended.

Examples of the resin which is a film-forming component blended in the coating agent include acrylic resin, polyester resin, urethane resin, alkyd resin, epoxy resin, polyamine resin, silicone resin, and fluorine resin. This resin can be used in the presence of a catalyst or as a catalyst, for example, heat-curable type, ultraviolet-curable type, electron beam-curable type, oxidation-curable type, photocation-curable type, peroxide-curable type, and acid / epoxy-curable type. It may be a resin that cures with a chemical reaction in the absence of the resin, or a resin having a high glass transition point, which does not involve a chemical reaction and may form a film only by volatilizing the solvent.

The diluting solvent is not particularly limited as long as it is generally used water or an organic solvent, but the organic solvent is, for example, a hydrocarbon solvent such as xylene, toluene or cyclohexane; and a ketone such as cyclohexanone or methylisobutylketone. Solvents; ether solvents such as methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol, carbitol, butyl carbitol, diethyl carbitol, propylene glycol monomethyl ether; n-butyl acetate, isobutyl acetate, n-amyl acetate, cellosolve acetate, Ester solvents such as propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; alcohols such as n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, cyclohexanol, 2-ethylhexanol, 3-methyl-3-methoxybutanol Solvents can be mentioned. These solvents may be used alone or in combination.

A coating agent containing this surface conditioner can be applied to the surface of the base material, and the obtained coating film can be dried or cured to form a film having a hydrophilic surface. Since the surface of this film is hydrophilic, it becomes easy to be compatible with water, and even if dust adheres, it is easy to be washed with water such as rainwater, which has an antifouling property.

The base material is not particularly limited, but is made of plastic, rubber, paper, wood, glass, metal, stone, cement, mortar, and ceramics, and is used for home appliances, automobile exterior materials, daily necessities, and building materials. Can be mentioned.

Examples of the coating agent application method include spin coating, slit coating, spray coating, dip coating, bar coating, doctor blade, roll coating, flow coating, and bell coating.

As described above, the coating film formed by applying the coating agent containing the surface adjusting agent of the present invention to the surface of the base material and curing the coating film is smooth with anti-arming achieved and imparts hydrophilicity to the surface immediately after the coating film is formed. As a result, the detergency with water such as rainwater is improved and antifouling property can be exhibited. That is, the surface conditioner does not require a reaction such as hydrolysis to impart hydrophilicity, and can impart a hydrophilic surface immediately after film formation. According to the film formed by the coating agent containing the surface conditioner as described above, the N, N-di-substituted (meth) acrylamide monomer and / or the unsaturated group-containing morpholinamide monomer and the fluorine-containing (meth) acrylate monomer are used. Even if a coating agent using a silicone-based resin or a fluorine-based resin, or a film-forming component having a low surface tension such as a silicone-based surface conditioner or a leveling agent typified by a fluorine-based surface conditioner is used. The surface of the formed coating film can be made hydrophilic, the wettability and spreading property when a coating agent having a high surface tension is overcoated can be improved, and the smoothness of the topcoat coating can be improved from the effect. Further, by making the surface of the coating hydrophilic, as a result, the hydrophilic surface has a lower water contact angle with respect to the base material, and the cleanability with water such as rainwater is improved, so that high antifouling property can be exhibited. This antifouling property also develops immediately after the film is formed.

At room temperature, this surface conditioner has a highly polar amphipathic skeleton similar to the hydrophilic organic functional silicone copolymer described in Patent Document 6 described above, and therefore has excellent compatibility with film-forming components, but bubbles. It is difficult to stabilize. The details of the reason are not always clear, but it is inferred as follows. This surface conditioner contains a copolymer containing N, N-dialkyl (meth) acrylamide as a main component. The copolymer has a hydrophobic polysiloxane segment and a hydrophilic / hydrophobic acrylamide-derived segment. Since N, N-dialkyl (meth) acrylamide has a hydrophobic part and a hydrophilic part in its structure, a segment derived from N, N-dialkyl (meth) acrylamide such as dimethyl and / or diethyl (meth) acrylamide. The copolymer having acrylamide becomes a temperature-sensitive polymer in an aqueous solution. This is also observed when the monomers are copolymerized to a certain ratio. The hydrophilicity / hydrophobicity of the acrylamide-based polymer undergoes a phase transition around the temperature sensitivity temperature. Due to this property, the surface conditioner changes from hydrophilic to hydrophobic during the baking process where armpits are generated, and the stabilized air bubbles become unstable due to the phase change of the surface conditioner, which is caused by the defoamer. Defoaming and defoaming are promoted, and armpit prevention is achieved. Moreover, when the temperature returns to room temperature after baking, the hydrophobicity becomes hydrophilic again, and the formed film has hydrophilicity.

When a coating agent containing this surface conditioner is applied onto a base material to form a film, the surface conditioner also has a high orientation to an interface, and a leveling property is also exhibited due to the effect of uniformizing the surface tension. , There are few defects on the film surface such as uneven coating and yuzu skin. Moreover, this coating does not cause uneven coating even when it is overcoated, and it adheres firmly without reducing the adhesion between the coating and the topcoat layer, and neither the coating nor the topcoat layer is peeled off. Good aesthetic appearance. In addition, since it has excellent heat resistance even when it is baked at a high temperature, such as when a coating agent for pre-coated metal is applied, it does not generate cissing or bumps on the surface of the coating film, has excellent smoothness, and is formed by curing. It has excellent durability without hindering the adhesion of the topcoat to the coating film.

Hereinafter, examples of preparing the surface conditioner of the present invention are shown in Examples 1 to 18, and examples of preparing a surface conditioner to which the present invention is not applied are shown in Comparative Examples 1 to 7.

<Example 1>
100 parts by mass of cyclohexanone was added to a 1000 mL reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen gas inlet, and the temperature was raised to 110 ° C. in a nitrogen gas atmosphere. The temperature of cyclohexanone was maintained at 110 ° C., and the dropping solution (a-1) shown in Table 1 below was dropped by a dropping funnel at a constant velocity for 2 hours to prepare a monomer solution. After completion of the dropping, the temperature of the monomer solution was raised to 115 ° C. and the reaction was carried out for 2 hours to synthesize a copolymer to obtain a surface conditioner. Using gel permeation chromatography that can separate molecules of different molecular weights (column is manufactured by Toso Co., Ltd. and product name is TSKGEL SUPERMULTIPORE HZ-M, elution solvent is THF (tetrahydrofuran)), the obtained surface conditioner is eluted for each molecular weight. Then, the molecular weight distribution was obtained. A calibration curve was obtained from a polystyrene standard substance having a known molecular weight in advance, and the weight average molecular weight of the surface conditioner was determined by comparing with the molecular weight distribution of the surface conditioner. As a result, the weight average molecular weight of this surface conditioner was 3500 in terms of polystyrene.

<Example 2>
Surface adjustment by synthesizing a copolymer in the same manner as in Example 1 except that the dropping solution in Example 1 was changed to (а-2) in Table 1 below and the dropping temperature was changed to 90 ° C. I got the agent. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Example 1, it was 8000 in terms of polystyrene.

<Example 3>
Surface adjustment by synthesizing a copolymer in the same manner as in Example 1 except that the dropping solution in Example 1 was changed to (а-3) in Table 1 below and the dropping temperature was changed to 90 ° C. I got the agent. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Example 1, it was 15,000 in terms of polystyrene.

<Example 4>
Surface adjustment by synthesizing a copolymer in the same manner as in Example 1 except that the dropping solution in Example 1 was changed to (а-4) in Table 1 below and the dropping temperature was changed to 90 ° C. I got the agent. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Example 1, it was 8000 in terms of polystyrene.

<Example 5>
A copolymer was synthesized in the same manner as in Example 1 except that the dropping solution in Example 1 was changed to (а-5) in Table 1 below to obtain a surface conditioner. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Example 1, it was 3500 in terms of polystyrene.

<Example 6>
Surface adjustment by synthesizing a copolymer by the same method as in Example 1 except that the dropping solution in Example 1 was changed to (а-6) in Table 1 below and the dropping temperature was changed to 90 ° C. I got the agent. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Example 1, it was 8000 in terms of polystyrene.

<Example 7>
A copolymer was synthesized in the same manner as in Example 1 except that the dropping solution in Example 1 was changed to (а-7) in Table 1 below to obtain a surface conditioner. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Example 1, it was 4000 in terms of polystyrene.

<Example 8>
Surface adjustment by synthesizing a copolymer in the same manner as in Example 1 except that the dropping solution in Example 1 was changed to (а-8) in Table 1 below and the dropping temperature was changed to 90 ° C. I got the agent. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Example 1, it was 8000 in terms of polystyrene.

<Example 9>
A copolymer was synthesized in the same manner as in Example 1 except that the dropping solution in Example 1 was changed to (а-9) in Table 1 below to obtain a surface conditioner. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Example 1, it was 2000 in terms of polystyrene.

<Example 10>
A copolymer was synthesized in the same manner as in Example 1 except that the dropping solution in Example 1 was changed to (а-10) in Table 1 below to obtain a surface conditioner. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Example 1, it was 3500 in terms of polystyrene.

<Example 11>
A copolymer was synthesized in the same manner as in Example 1 except that the dropping solution in Example 1 was changed to (а-11) in Table 2 below to obtain a surface conditioner. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Example 1, it was 2500 in terms of polystyrene.

<Example 12>
Surface adjustment by synthesizing a copolymer by the same method as in Example 1 except that the dropping solution in Example 1 was changed to (а-12) in Table 2 below and the dropping temperature was changed to 90 ° C. I got the agent. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Example 1, it was 45,000 in terms of polystyrene.

<Example 13>
A copolymer was synthesized in the same manner as in Example 1 except that the dropping solution in Example 1 was changed to (а-13) in Table 2 below to obtain a surface conditioner. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Example 1, it was 1500 in terms of polystyrene.

<Example 14>
A copolymer was synthesized in the same manner as in Example 1 except that the dropping solution in Example 1 was changed to (а-14) in Table 2 below to obtain a surface conditioner. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Example 1, it was 3500 in terms of polystyrene.

<Example 15>
The surface of the copolymer was adjusted by synthesizing the copolymer in the same manner as in Example 1 except that the dropping solution in Example 1 was changed to (а-15) in Table 2 below and the dropping temperature was changed to 90 ° C. I got the agent. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Example 1, it was 50,000 in terms of polystyrene.

<Example 16>
A copolymer was synthesized in the same manner as in Example 1 except that the dropping solution in Example 1 was changed to (а-16) in Table 2 below to obtain a surface conditioner. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Example 1, it was 4000 in terms of polystyrene.

<Example 17>
A copolymer was synthesized in the same manner as in Example 1 except that the dropping solution in Example 1 was changed to (а-17) in Table 2 below to obtain a surface conditioner. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Example 1, it was 3000 in terms of polystyrene.

<Example 18>
A copolymer was synthesized in the same manner as in Example 1 except that the dropping solution in Example 1 was changed to (а-18) in Table 2 below to obtain a surface conditioner. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Example 1, it was 4500 in terms of polystyrene.

<Comparative example 1>
100 parts by mass of cyclohexanone was added to a 1000 mL reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen gas inlet, and the temperature was raised to 110 ° C. in a nitrogen gas atmosphere. The temperature of cyclohexanone was maintained at 110 ° C., and the dropping solution (b-1) shown in Table 3 below was dropped by a dropping funnel at a constant velocity for 2 hours to prepare a monomer solution. After completion of the dropping, the temperature of the monomer solution was raised to 115 ° C. and the reaction was carried out for 2 hours to synthesize a copolymer to obtain a surface conditioner. Using gel permeation chromatography that can separate molecules of different molecular weights (column is manufactured by Tosoh Corporation, product name is TSKGEL SUPERMULTIPORE HZ-M, elution solvent is THF), the obtained surface conditioner is eluted for each molecular weight, and the molecular weight is increased. The distribution was calculated. A calibration curve was obtained from a polystyrene standard substance having a known molecular weight in advance, and the weight average molecular weight of the surface conditioner was determined by comparing with the molecular weight distribution of the surface conditioner. As a result, the weight average molecular weight of this surface conditioner was 4000 in terms of polystyrene. In Comparative Example 1, the acrylamide monomer was not added to the monomer solution.

<Comparative example 2>
The dropping solution in Comparative Example 1 was changed to (b-2) in Table 3 below, and a copolymer was synthesized in the same manner as in Comparative Example 1 to obtain a surface conditioner. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Comparative Example 1, it was 10000 in terms of polystyrene. In Comparative Example 2, the acrylamide monomer in the monomer solution was less than 65 parts by mass, and the fluorine-containing (meth) acrylate monomer was more than 35 parts by mass.

<Comparative example 3>
Surface adjustment by synthesizing a copolymer in the same manner as in Comparative Example 1 except that the dropping solution in Comparative Example 1 was changed to (b-3) in Table 3 below and the dropping temperature was changed to 90 ° C. I got the agent. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Comparative Example 1, it was 70,000 in terms of polystyrene. In Comparative Example 3, the weight average molecular weight of the obtained surface conditioner exceeded 50,000.

<Comparative example 4>
The dropping solution in Comparative Example 1 was changed to (b-4) in Table 3 below, and a copolymer was synthesized in the same manner as in Comparative Example 1 to obtain a surface conditioner. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Comparative Example 1, it was 6000 in terms of polystyrene. In Comparative Example 4, the acrylamide monomer was not added to the monomer solution.

<Comparative example 5>
The dropping solution in Comparative Example 1 was changed to (b-5) in Table 3 below, and a copolymer was synthesized in the same manner as in Comparative Example 1 to obtain a surface conditioner. When the weight average molecular weight of the obtained surface conditioner was determined by gel permeation chromatography in the same manner as in Comparative Example 1, it was 5000 in terms of polystyrene. In Comparative Example 4, the fluorine-containing (meth) acrylate monomer was not added to the monomer solution.

<Comparative Example 6>
Ethyl silicate 48 (manufactured by Corcote) was used as the surface conditioner.

<Making an evaluation coated plate>
The surface conditioners obtained in Examples 1 to 18 and Comparative Examples 1 to 6 were blended with the prepared paint prepared in advance to obtain a test paint as a coating agent. The characteristics of the cured film obtained by applying this test paint to the substrate and the stability of the test paint over time were evaluated.

(Preparation of preparatory paint 1)
Beckolite M-6154-40 (polyester polyol resin, non-volatile content: 50%, hydroxyl value 50; manufactured by Dainippon Ink and Chemicals Co., Ltd.) 324 parts by mass and CR-93 (titanium oxide manufactured by Ishihara Sangyo Co., Ltd.) 270 parts by mass Glass beads were added to the mill base of the above, and the mixture was stirred with a paint shaker for 6 hours. Further, 594 parts by mass of this mill base, 135 parts by mass of Beckolite M-6154-40 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), Super Beccamin L-117-60 (butylated melamine resin, NV60%, Dainippon Ink) 22 parts by mass (manufactured by Kagaku Kogyo Co., Ltd.), Super Beccamin L-105-60 (methylated melamine resin NV60%, manufactured by Dainippon Ink and Chemicals Co., Ltd.) 45 parts by mass and thinner (Solbesso 150 / cyclohexanone = 50/50) 204 After blending the red down consisting of parts by mass, the glass beads were filtered off to obtain the preparatory paint 1.

(Preparation of preparatory paint 2)
Fluoronate K700 (hydroxyl resin containing hydroxyl group, non-volatile content: 50%, hydroxyl value 50; manufactured by Dainippon Ink and Chemicals Co., Ltd.) 324 parts by mass and CR-93 (titanium oxide manufactured by Ishihara Sangyo Co., Ltd.) 270 parts by mass Glass beads were added, and the mixture was stirred with a paint shaker for 6 hours. Further, in 594 parts by mass of this mill base, 135 parts by mass of Fluonate K700 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), Super Beccamin L-117-60 (butylated melamine resin, NV60%, manufactured by Dainippon Ink and Chemicals Co., Ltd.) ) 22 parts by mass, Super Beccamin L-105-60 (methylated melamine resin NV60% manufactured by Dainippon Ink and Chemicals Co., Ltd.) 45 parts by mass and thinner (Solvesso 150 / cyclohexanone = 50/50) 204 parts by mass Red After blending the down, the glass beads were filtered off to obtain a preparatory paint 2.

(Preparation of test paint 1 and preparation of coating film)
The obtained preparatory paint 1 contains 0.5% of an antifoaming agent (Floren AC-300, manufactured by Kyoeisha Chemical Co., Ltd.) and a silicone-based leveling agent (Polyflow) which has a low surface tension and is considered to inhibit the surface orientation of the hydrophilic agent. KL-700) 0.5% and 1.5% of the surface conditioners obtained in Examples 1 to 18 and Comparative Examples 1 to 6 as solid contents were added, and the mixture was stirred in a lab disper for 2000 rpm for 2 minutes. A test paint, which is a baking type polyester paint, was obtained. The obtained test coating material was immediately coated on an aluminum base material with a # 42 bar coater, and immediately baked at 245 ° C. × 60 seconds (PMT: 225 ° C.) and cured to form a cured film.

For comparison, a cured film prepared from the test coating material obtained by using the surface conditioner of Comparative Example 6 was immersed in a 1% sulfuric acid aqueous solution for 24 hours to promote hydrolysis, and a cured film obtained was used as a comparative example. As No. 7, a cured film for comparison of hydrophilicity was used.

(Evaluation of armpits generated on the cured film)
The number of armpits generated per 10 cm ^{2 of the} cured film was visually counted, and the results of evaluation in 5 stages according to the following evaluation criteria are shown in Table 4 below.
Evaluation Criteria for Armpit Occurrence No Armpit Occurrence: ◎
Approximately 3 places or less: ○
Approximately 7 locations or less: ○ ~ △
10 or more locations: △
Armpits occur on the entire surface: ×

(Evaluation of leveling property of cured film surface)
The skin condition of the painted surface after curing was visually observed, and the results of evaluation in four stages according to the following evaluation criteria are shown in Table 4 below.
Evaluation criteria for leveling property Good; ○
A few paint streaks on the bar coater remain: ○ ~ △
Bar coater paint streaks remain noticeable: △
Hajiki occurs: ×

(Measurement of water contact angle of cured film)
0.02 μL of water droplets were dropped on the surface of the cured film immediately after curing, and the initial water contact angle was measured using a contact angle measuring meter (manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Table 4 below. The water contact angle of the cured film of Comparative Example 7 was measured for comparison of hydrophilicity.
Evaluation criteria for water contact angle Less than 30 °: ◎
30 ° or more and less than 40 ° C: ○
40 ° or more and less than 50 °: ○ ~ △
50 ° or more and less than 60 °: △
60 ° or more: ×

(Actual exposure evaluation of cured film)
A coated plate having a cured film formed on its surface was bent at 45 ° and erected vertically, exposed to the south surface outdoors for 2 months, and the degree of contamination was visually evaluated on a 4-point scale according to the following evaluation criteria. The results are also shown in Table 4 below.
Evaluation criteria for pollution Good with almost no pollution: ○
Slightly contaminated: ○ ~ △
Contaminated: △
Heavy pollution: ×

As is clear from Table 4, the cured coatings of Examples 1 to 18 using the test coating material 1 have a smaller amount of armpit generation and better leveling property than the cured coatings of Comparative Examples 1 to 6. , The coating surface is smooth. Further, the water contact angle of the cured coatings of Examples 1 to 17 and the stains in the actual exposure test were similar to those of the cured coatings of Comparative Example 7 for comparison of hydrophilicity, and had good hydrophilicity and antifouling properties. Is presented.

(Adjustment of test paint 2 and preparation of film)
The obtained preparatory paint 2 contains 0.5% of an antifoaming agent (Floren AC-300, manufactured by Kyoeisha Chemical Co., Ltd.) and the surface adjustments obtained in Examples 1 to 18 and Comparative Examples 1 to 6 as solid contents. A cured film was formed and the performance was evaluated in the same manner as in Test Paint 1, except that 1.5% of the agent was added. The results of the performance evaluation are shown in Table 5 below.

As is clear from Table 5, the cured coatings of Examples 1 to 18 using the test coating material 2 have a smaller amount of armpit generation and better leveling property than the cured coatings of Comparative Examples 1 to 6. , The coating surface is smooth. Further, the water contact angle of the cured coatings of Examples 1 to 18 and the stains in the actual exposure test were similar to those of the cured coatings of Comparative Example 7 for comparison of hydrophilicity, and had good hydrophilicity and antifouling properties. Is presented. On the other hand, the cured coatings of Comparative Examples 1 to 7 had a high water contact angle or had an armpit, and had insufficient surface characteristics.

(Evaluation of stability of test paint over time)
For Examples 1 to 18 and Comparative Examples 1 to 6 of the prepared test paint 1, the viscosities (B-type viscometer) after initial storage at 40 ° C. for 1 month and 2 months were measured, and the results are shown in the table below. 6 is described. Further, for each of the initial stage and after storage at 40 ° C. for 1 month, a cured film was prepared by the above-mentioned film forming method, and the water contact angle was evaluated by the above-mentioned water contact angle measuring method, and the results are shown in the table below. It is also described in 6. In Table 6 below, the water contact angle shown in Table 4 is also shown as the initial water contact angle.

The surface conditioner for coating agents of the present invention is used for exterior materials, daily necessities, and building materials for home appliances, automobiles, and automobiles made of plastic, rubber, paper, wood, glass, metal, stone, cement, mortar, and ceramic materials. It can be blended in a coating agent such as a paint applied to the surface. Further, even when the coating agent contains a silicone-based surface conditioner typified by a leveling agent or a fluororesin having a low surface tension, hydrophilicity can be exhibited.

The cured film formed on the base material by the coating agent containing the surface conditioner and the film-forming component is provided with antifouling property because it exhibits hydrophilicity on the surface of the film, and is coated on various base materials. Useful as a coating.

Claims (5)

At least one N, N-di-substituted (meth) acrylamide monomer selected from N, N-dialkyl (meth) acrylamides, and / or at least one unsaturated group-containing morpholinamide selected from unsaturated group-containing morpholinamides. Monomer 65.00 to 99.99 parts by mass and the following chemical formula (1)
CH ₂ = C (R ¹ ) -CO-O-R ^2- R ^F ... (1)
(In the formula (1), ^{R 1} represents a hydrogen atom or a methyl group, ^{R 2} is an alkylene group of 0-12 carbon atoms, ^{R F} is a perfluoroalkyl group having 1 to 12 carbon atoms, and / or perfluoropolyether group ), 35.00 to 0.01 parts by mass of the fluorine-containing (meth) acrylate monomer , the N, N-di-substituted (meth) acrylamide monomer and / or the unsaturated group-containing morpholinamide monomer and the fluorine-containing (. Meta) acrylate monomers and unsaturated copolymers, which are alkyl (meth) acrylates, (meth) acrylamides, and / or vinyl group-containing compounds, up to 30 parts by mass with respect to 100 parts of the total mass of those monomers. It is a copolymer of a comonomer composed of, and is composed of a copolymer having a weight average molecular weight of 1500 to 50,000 .
A coating agent containing a silicone-based resin or a fluorine-based resin, and / or a coating agent containing a surface-oriented additive that is a silicone-based leveling agent, and 0.1 to 10 in terms of solid content with respect to the total amount of the coating agent. a hydrophilic surface of the coating which is added a small amount is Gana formed by the coating agent is a mass%, the antifouling property and / or leveling properties, intended to impart a popping property during the formation of the film A surface conditioner for a coating agent, which is characterized by being. The N, N-di-substituted (meth) acrylamide monomer and / or the unsaturated group-containing morpholinamide monomer and the fluorine-containing (meth) acrylate monomer, and a maximum of 10 parts by mass ratio with respect to the total mass of 100 parts of these monomers. At least one functional group-containing comonomer selected from a (meth) acrylate monomer having a blocked isocyanate, a (meth) acrylate monomer having an alkoxy group, a (meth) acrylate monomer having a hydroxyl group, and a (meth) acrylamide containing a hydroxyl group. The surface conditioner for a coating agent according to claim 1 , wherein the copolymer contains the copolymer of and. A coating agent containing the surface conditioner for a coating agent according to any one of claims 1 to 2 and a film-forming component. A cured film formed on a substrate by the coating agent according to claim 3. In the coating agent surface conditioner by the coating surface, wherein the hydrophilic, and a said antifouling and / or the leveling property, with the popping of a time the formation of the film The cured coating according to claim 4.