JPH0510393B2 - - Google Patents

Description

[Detailed description of the invention]

<Field of Industrial Application> The present invention relates to a film-forming composition capable of forming a film with excellent smoothness, antifriction, rust prevention, scratch resistance, homogeneity, and durability, and a method for forming the film. More specifically, it relates to a fluorine-containing coating composition that forms a coating film with the above properties on solid surfaces such as metal, porcelain, glass, plastic, etc., and a method for forming a coating using the composition. . <Prior art> Various paints and coating materials have been used for the purpose of protecting metals, porcelain, glass, plastics, etc., but especially when surface smoothness is required, coating materials This is accomplished by containing additives such as higher fatty acids, higher fatty acid esters, paraffinic hydrocarbons, silicone oils, such as dimethylpolysiloxane, diphenylpolysiloxane, and the like. Furthermore, recently, attention has been paid to the fact that surfaces formed from aggregates of perfluoroalkyl groups have low surface energy, and fluorine-containing polymers have been utilized as surface coating agents by various methods. For example, by adding a fluorine-containing polymer to a coating material,
Method of forming a film by heat curing (Japanese Patent Application Laid-Open No. 1983
−126220). A method in which a fluoropolymer in which a fluoropolymer such as polytetrafluoroethylene is dispersed is applied in solution and a film is formed by curing at room temperature (Japanese Patent Publication No. 58-49580). A method of coating a fluororesin solution dispersion such as polytetrafluoroethylene and forming a film by heat treatment (300℃ or higher) (Japanese Patent Publication No. 47-37261)
Publication No. 58-33266, Special Publication No. 58-33266
Publication No. 33267). A method in which a monomolecular film consisting of a structurally unique fluorine-containing olefin having unsaturated bonds in the molecular chain is formed by the Langmuir-Blodgett method, and a film is formed by ultraviolet curing.
Publication No. 36172). A method of applying an organic solvent solution of perfluoroalkyl group-containing resin and removing the solvent to form a film. A method in which a film is formed by applying an emulsion of a perfluoroalkyl group-containing resin and heating it to form a film. etc., are usually used for water- and oil-repellent treatment of fibers, and there are also types that are cured at room temperature or by heating in the presence of a crosslinking agent, etc. These methods have a fatal flaw in that they cannot be applied to heat-sensitive materials because they require heat treatment. Mataya's method does not require heat treatment, but the coating hardness is 2H or less in terms of pencil hardness, as in the case of .
Does not withstand high levels of scratches and friction. In the method of
Although an ultra-thin film is formed, according to the findings of the present inventors, water tends to adhere when forming a monomolecular film,
Furthermore, even if UV curing is performed after sufficient moisture has been removed, rust prevention properties are insufficient when metal is used as the material. On the other hand, recent advances in recording materials have been remarkable, especially in the field of magnetic tapes and magnetic disks, where recording density has increased and recording wavelengths have become shorter, less than 2 μm, and there is a particular demand for lower noise levels and increased signal output. In addition to improving the characteristics of the magnetic layer, there is a particular demand for smoothing the surface of the magnetic layer and reducing friction. In addition, in order to improve the running performance of tapes and to reproduce still images clearly and over long periods of time in video tapes, the coating film used to protect the magnetic layer has been improved by smoothing, reducing friction, and improving durability. However, on the other hand, it is desired that the coating film be made thinner due to the need to express magnetic properties more sharply. Furthermore, since ferromagnetic metals are generally prone to corrosion in high humidity, it is required to form a coating film that also has rust prevention properties. <Problems to be Solved by the Invention> However, the various paints and coating materials to which the various smoothness improvers mentioned above are added, as well as the coatings made of the fluorine-containing polymers, cannot be used in high humidity. It shows almost no rust prevention effect regarding the corrosion resistance of the base metal, and because the scratch resistance is not sufficient, the coating film surface is easily scratched, and when the coating film is made thin (for example, 1 μm or less), the homogeneity, smoothness, and It has the disadvantage that durability is significantly reduced. Furthermore, a technique relating to a radiation-curable coating film containing a fluorine-containing acrylate is disclosed in Japanese Patent Application Laid-Open No. 16067/1983, and it is said that this technique provides a solvent-resistant adhesive coating material. However, according to the findings of the present inventors, when based on such known techniques, fluorine-containing acrylates do not have sufficient compatibility with non-fluorine components, and the uniformity of the cured coating film obtained by radiation curing is poor. It has been found that this results in significant defects in features such as smoothness. Furthermore, even if the mixtures are in a compatible state before curing, radiation curing causes the fluorine-containing segment portion mainly composed of fluorine-containing acrylate to bleed from the bulk resin layer, resulting in a uniformity of the cured coating film. It was observed that functions such as hardness, smoothness, durability, and scratch resistance were not fully expressed. On the other hand, in Tokukoho No. 59-30170,
A technique related to a radiation-cured coating film containing a nonionic fluorine surfactant or a fluorine-containing vinyl monomer is disclosed, and it is said that a coating film with excellent abrasion resistance can be formed by such a technique. However, according to the knowledge of the present inventors, when adding a lower fluoroalkyl group-containing vinyl monomer or a nonionic fluorosurfactant as disclosed in the publication, the coating film has a high-grade surface as shown in the present invention. Smoothness, contact angle, and friction reduction effects were not exhibited. <Means for Solving the Problems, Part 1> As a result of intensive research to solve the problems of conventional protective coating films, the present inventors have found that, as a result of applying fluorine-containing polymers as in the past, Instead, a composition consisting of a specific ratio of an oil-soluble fluorine-containing surfactant (C) to a fluorine-containing acrylate (A), a hydrocarbon acrylate (B), and an oil-soluble fluorine-containing surfactant (C) was applied to the substrate, and the solvent was allowed to evaporate. By subsequently polymerizing with ultraviolet or electron beam irradiation, it was possible to form a protective coating film with superior smoothness, friction reduction, rust prevention, scratch resistance, homogeneity, and durability compared to conventional methods. I found it. Furthermore, compared to the conventional method of applying a fluorine-containing polymer, according to this method, even if the amount of fluorine-containing acrylate used, which is relatively expensive compared to hydrocarbon-based acrylate, is reduced,
They also discovered the economical advantage of being able to obtain sufficient performance, leading to the completion of the present invention. As mentioned above, Japanese Patent Publication No. 54-36172 discloses a method of forming a monomolecular film of fluorine-containing olefin and then curing it with ultraviolet rays to form a coating. Due to the need to form a monomolecular film, fluorine olefins are so-called olefins in which one end of the molecular chain consists of a hydrophobic perfluoroalkyl group and a hydrophilic carboxyl group, and a polymerizable unsaturated bonding group is incorporated between them. It has an inner olefin structure. Moreover, since the manufacturing process is complicated, it lacks industrial versatility. On the other hand, the fluorine-based polymerizable monomer according to the present invention is a versatile fluorine-containing acrylate having no hydrophilic group, and the two can be clearly distinguished chemically. On the other hand, if we turn to the method of film formation,
In order to obtain a homogeneous coating layer by forming a monomolecular film as described in Publication No. 36172,
Langmuir-Blodgett method (New Experimental Chemistry Course, 18 ,
Interfaces and Colloids, pp. 439-476, Maruzen, 1977) or
According to the knowledge of the present inventors, vacuum deposition is the only other method. However, these methods are industrially and economically unsuitable because the process is complicated, such as transferring the monomolecular film once formed to the target substrate and requiring large-scale equipment to form the monomolecular film. Undesirable. In contrast, according to the method of the present invention, the film-forming composition can be coated using methods known in the art, such as brush coating,
Coating method using an applicator, bar coater, roller brush, or roll coater, spray coating method using an air spray or airless spray coating machine, flow coating method using a shower coater or curtain flow coater, dipping method, coating method using a shower coater, curtain flow coater, etc. It can be applied to a substrate by a general-purpose method such as a staining method or a spinner coating method to obtain a homogeneous coating layer. The present invention is based on the general formula () R _f (-A) _a --QCOC (R ₁ ) ₌ CH ₂ () [wherein, R _f is a perfluoroalkyl group having 4 to 20 carbon atoms, and A is 2 A valent linking group,

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[expression] or

[Formula] (wherein, R is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms or an alkyl group containing ether oxygen), a is 0 or 1, preferably 1, and Q is (—CH ₂ ) _o — (where n is an integer of 2 to 4), and R ₁ is a hydrogen atom, a methyl group, or a halogen atom. ] Fluorine-containing acrylate represented by
A composition consisting of (A), a hydrocarbon acrylate (B), and an oil-soluble fluorine-containing surfactant (C), in which the weight ratio of components (A) and (B) is 1:4 to 1:4. 1:10000, and the amount of component (C) in the composition is 0.005 to 5% by weight.
A film-forming composition that can be polymerized by ultraviolet rays or electron beams and provides a polymer film with excellent smoothness, homogeneity, and scratch resistance, which is an oil-soluble fluorinated surfactant (C). The present invention provides a film-forming composition characterized by using a copolymer of a fluorine-containing acrylate and a hydrocarbon vinyl monomer. The fluorine-containing acrylate (A) of the present invention is a compound represented by the above general formula (). The R _f group is a perfluoroalkyl group or perfluoroalkenyl group having 4 to 20 carbon atoms, and may be linear, branched, cyclic, or a combination thereof, and further has an oxygen atom intervening in the main chain. For example, (CF ₃ ) ₂ CFOCF ₂ CF ₂ − etc. may be used. Specific examples of the fluorine-containing acrylate A include the following, but it goes without saying that the present invention is not limited to the following compounds. As the hydrocarbon acrylate (B) according to the present invention, those known in the art (for example, "Introduction to UV Curing Technology" by Kiyomi Kato and Shoji Nakahara, published by Kobunshi Publishing Co., Ltd.,
1984, [hereinafter referred to as the book], pages 34 and 35, table
10, Table 16 on pages 46 to 48, Table 20 on page 57, Table 60 on pages 170 to 172, etc.), such as the following (D) and (E). It is. Compound (D) containing one acryloyl group D-1 CH ₂ =C(R ₂ )COOR ₃ (R ₃ is an alkyl group having 1 to 20 carbon atoms) D-2 CH ₂ =C(R ₂ )COOCH _{2 CH2OH} (However, it is R2 _- H or _-CH3 .) etc. Compound containing two or more acryloyl groups (E) E-1 CH ₂ =C(R ₂ )COO(-CH ₂ ) _o --OOCC
(R ₂ )=CH ₂ (n is an integer from 1 to 10) E−2 CH ₂ =C(R ₂ )COO(—CH ₂ CH ₂ O) _o —COC(R ₂
)=CH ₂ (n is an integer from 1 to 10) E-13 (CH ₂ = C(R ₂ )COOCH ₂ ) ₃ --CCH ₂ OH E-14 (CH ₂ =C(R ₂ )COOCH ₂ ) ₃ --
CCH ₂ CH ₃ E−15 (CH ₂ = C(R ₂ )COOCH ₂ CH ₂ O) ₃ --P
=O E-17 (CH ₂ =C(R ₂ )COOCH ₂ ) ₄ --C (wherein R ₂ is -H or -CH ₃ ), and the like. In addition, as the photopolymerization initiator (F), those known in the art (for example, Table 22 on page 62 and Table 22 on page 71 of the above-mentioned book)
F-1: benzophenone, F-1: benzophenone,
-2: Acetophenone, F-3: Benzoin, F
-4: benzoin ethyl ether, F-5: benzoin isobutyl ether, F-6: benzyl methyl ketal, F-7: azobisisobutyronitrile, F-8: 1-hydroxycyclohexyl phenyl ketone, F-9: 2-hydroxy-2-methyl-1-phenyl-1-one and the like. The oil-soluble fluorine-containing surfactant (C) of the present invention is one that is soluble in aliphatic or aromatic hydrocarbon solvents such as alcohols, ketones, esters, or halogen organic solvents. It exhibits a surfactant effect and is a polymer having a molecular weight of 3,000 to 100,000 obtained by polymerizing the fluorine-containing acrylate of component (A) represented by the above general formula () and a hydrocarbon vinyl monomer. A hydrocarbon vinyl monomer is, for example, CH ₂ =
C(R ₄ )COOR ₅ , CH ₂ =C(R ₄ )CO(-OCH ₂ CH ₂
) _o --OR ₅ ,

[Formula] (R ₄ is a hydrogen atom, a chlorine atom, or an alkyl group having 1 to 3 carbon atoms, R ₅ is an alkyl group having 1 to 20 carbon atoms,
or an aromatic group, a group containing an aromatic group such as a benzyl group, and n is an integer of 1 to 30. ),styrene,
Hydroxyethyl methacrylate and the like. Specific examples of these include CH ₂ =C(CH ₃ )
COOCH ₃ , CH ₂ = C (CH ₃ ) COOiSt (iSt: isostearyl), CH ₂ = C (CH ₃ ) CO (-OCH ₂ CH ₂
) ₂₃ --OCH ₃ ,

Examples include [Formula]. The oil-soluble fluorine-containing surfactant (C) can be obtained by random copolymerization or block copolymerization based on a macromonomer method based on radical polymerization, anionic polymerization mechanism, etc. of these monomers. Other readily available products such as Florinade
FC-430 (3M product), Aron GF-150,
GF-300 (Toagosei product), Modeiper F-100,
Commercially available products such as F-110, F-200, F-210 (products of NOF Corporation) can be used. In the coating forming composition of the present invention, the mixing ratio of the fluorine-containing acrylate (A) and the hydrocarbon acrylate (B) is determined in terms of weight ratio from the viewpoint of compatibility, economical efficiency, and performance of the obtained coating. The ratio is preferably 1:4 to 1:10,000, more preferably 1:10 to 1:5,000. The proportion of component (C) in a composition characterized by containing a fluorine-containing acrylate (A), a hydrocarbon acrylate (B), and an oil-soluble fluorine-containing surfactant (C) is )+(B)+(C) from 0.005 to 5% by weight. If the amount of component (C) is less than this range or too much, the effect of improving the surface properties of the effect coating will not be sufficiently expressed. Furthermore, for the composition of the present invention, so-called photopolymerization initiators and photosensitizers known in the art (for example, the above-mentioned books,
Compounds listed in Table 28 on page 72 and Table 29 on page 73), solvents,
And various additives can be added. The solvent is not particularly limited as long as it does not adversely affect the reactivity of the acrylate monomer, but methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, chloroform, dichloroethane, carbon tetrachloride, 1-fluoro- 1-dichloro-2-difluoro-
2-chloroethane-based low boiling point solvents are preferred. Examples of additives include leveling agents and antifoaming agents. When the film formation according to the present invention is carried out using ultraviolet rays, the fluorine-containing acrylate (A) and the hydrocarbon-based acrylate (B) are α carbon-unsubstituted (i.e., in the general formula and specific compound, R ₁ , R ₂ co-hydrogen atoms) are preferred. As a method for applying the film-forming composition according to the present invention to a substrate, various methods known in the art such as those described above can be used, and it is desirable to use appropriate methods depending on the material, shape, or purpose of the substrate. . The composition can be applied as is, or in cases where the viscosity is too high or when controlling the film thickness, the composition can be applied as a solution dissolved in a solvent. can do.
In the case of this solution, before irradiation with ultraviolet rays or electron beams, it is necessary to carry out a step of removing the solvent at room temperature or, if necessary, by heating or reducing pressure. When removing the solvent by heating, it is preferable to remove the solvent at a temperature of 80° C. or lower to avoid thermal polymerization of monomers, etc. The fluorine-containing protective coating according to the present invention is applied to a coating layer formed on a substrate by the above method, using a germicidal lamp, an ultraviolet fluorescent lamp, a carbon arc, a xenon lamp, a high-pressure copying lamp, etc., which are known in the art. Formed by irradiation with ultraviolet rays from mercury lamps, medium- or high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light, or electron beams from scanning or curtain-type electron beam acceleration paths. . Thickness is 5μ
In the case of ultraviolet curing of a coating layer of m or less, it is preferable to perform the irradiation under an inert gas atmosphere such as nitrogen gas in order to improve polymerization efficiency. <Function> According to the findings of the present inventors, when the proportion of fluorine-containing acrylate (A) exceeds the above range and is present in a large amount, the compatibility improving effect based on component (C) cannot function sufficiently. Phase separation occurs due to poor compatibility between components (A) and (B), which significantly impairs the homogeneity of the coating, resulting in poor adhesion to the substrate as well as antifriction, rust prevention, and scratch resistance. It was found that the surface properties such as surface properties were significantly deteriorated. In addition, when the proportion of fluorine-containing acrylate A is lower than the lower limit of the above range, the perfluoroalkyl group improves coating functions such as smoothness, antifriction, rust prevention, scratch resistance, homogeneity, and durability. It was also found that the effect was not sufficient and the object of the present invention could not be achieved. Further, according to the studies of the present inventors, regarding the fluorine-containing acrylate (A) (general formula) according to the present invention, when a is 1, the compatibility with component (B) is better than when a is 0. In this sense, fluorine-containing acrylates in which a is 1 are more preferred. Techniques for adding oil-soluble fluorine-containing surfactants as wear resistance improvers to UV-cured coatings are well known in the art. However, the surface properties of the film obtained by adding an oil-soluble fluorine-containing surfactant to a known UV-curable hydrocarbon acrylate that does not contain fluorine-containing acrylate and UV-curing it are certainly smooth and friction-reducing. Although some improvement effect can be seen, the actual situation is that the level required by users cannot be reached and furthermore, the effect of improving rust prevention and scratch resistance is hardly recognized. On the other hand, the surface properties of the coating obtained by curing the composition of the present invention by irradiation with radiation not only significantly improves smoothness and friction reduction functions, but also particularly improves rust prevention and scratch resistance. The improvement effect has reached a level that far exceeds expectations. Although the mechanism by which such functions are expressed is not clear, (A), (B),
(C) It is presumed to be based on the synergistic effect of the three components. <Effects of the Invention> As mentioned above, the film-forming composition of the present invention can be used as a protective coating layer on various solid surfaces, such as as a moisture and rust preventive agent, an antifouling agent, an antifriction agent, a stripping agent, a mold release agent, etc. However, taking advantage of the thinness and smoothness of the coating,
It is suitably used for coating the magnetic layer of magnetic recording products in the field of recording materials. For example, non-magnetic metals such as copper, aluminum and zinc, polyesters such as polyethylene terephthalate and polyethylene-2,6-naphthalate,
Ferromagnetic alloys deposited on plastics such as polyolefins such as polypropylene, cellulose derivatives such as cellulose acetate, polycarbonates, and, in some cases, ceramics such as glass, paper, wood, fibers, porcelain and earthenware. (Main components of iron, cobalt and/or nickel, with small amounts of aluminum, silicon, chromium, manganese, molybdenum, titanium, various heavy metals, rare earth metals, etc.) or iron, cobalt, chromium in the presence of trace amounts of oxygen. It is also suitable for use as a protective coating for magnetic tapes, such as magnetic materials deposited on plastic films such as polyester, or magnetic layers of magnetic disks, and as a backing agent for magnetic tapes that particularly require anti-friction properties. On the other hand, the film-forming composition of the present invention can form a transparent, smooth, and thin film even on glass surfaces.
It can also be used in applications that require oil resistance and extraction resistance, such as as an oil stain preventive agent for various optical equipment. Furthermore, it is suitable as a protective coating for optical fibers and optical fiber cables which particularly require moisture resistance. Next, specific examples of the present invention will be described, but it goes without saying that the present invention is not limited by such explanations. ``part'' in the sentence
"%" shall be based on weight. <Example> Examples 1 to 11 Steel plate (JIS G3141) or aluminum plate (JIS G3141)
The film-forming composition of the present invention was coated on H4000), the solvent was evaporated at room temperature, and then the coated layer was cured with ultraviolet rays or electron beams under the following conditions, and various properties of the coated film were examined. . The results are shown in Table-1. Equipment: For curing with ultraviolet rays, use a high-pressure mercury lamp (80w/
cm), irradiation distance 10cm, irradiation time 60 seconds,
It was carried out at 33°C under a nitrogen atmosphere. Curing with electron beams was performed using a curtain-type electron beam accelerator (200 kV) at a dose of 10 Mrad. Coating method: A composition consisting of a fluorine-containing acrylate (A), a hydrocarbon acrylate (B), an oil-soluble fluorine-containing activator (C), and a photopolymerization initiator (F) is mixed with 5% ethyl acetate. The solution was diluted to 100% and coated using a bar coater to form a coating layer with a nonvolatile content of 0.5 μm. Surface smoothness: The smoothness of the surface coating film is determined by observing the presence or absence of bumps on the coating surface using an optical microscope with a magnification of 160x, and grading it into 5 grades (5: No bumps at all, 4: Slight bumps on the edges, Evaluation was made as follows: 3: Slight bumps on the surface, 2: Slight bumps on the surface, 1: Slight bumps on the entire surface.The higher the value, the better. Surface drying property: ◎ mark by finger touch ○ mark with no stickiness at all △ mark with a slight sense of stickiness × mark with some stickiness Surface hardness: Conducted based on the method of JIS5400. Contact angle: The contact angle was measured at 25° C. by dropping n-dodecane onto the measurement surface at 6 μm using a goniometer type contact angle measuring device manufactured by Elma. Rust prevention: Immerse the test piece in a 20% sodium chloride aqueous solution, observe the time until rust appears on the coating, and rate it in 5 stages (5: 200 hours or more, 4: 150-200 hours)
Time, 3:100-150 hours, 2:50-100 hours,
1:0 to 50 hours). Grid test: Cut a 1cm square vertically and horizontally at 1mm intervals using a cutter.
We made 100 squares, covered them with cellophane tape (Sekisui Chemical S-832), and then peeled them off all at once to indicate the number of squares remaining. In addition, "UV" in the column of Examples and Comparative Example No. indicates the formation of a polymer film by ultraviolet curing, and "EB"
The display shows that of electron beam curing. In addition, the "S" designation in the Comparative Example No. column is obtained by copolymerizing the acrylate monomer shown in the composition column in ethyl acetate using azobisisobutyronitrile as an initiator (average degree of polymerization 30).
It is then coated on the material together with an oil-soluble fluorine-containing surfactant to give a film thickness of 0.5 μm. Furthermore, A, C, D, E, F, and G in the table represent the symbols of the compounds described in the text. Furthermore, the oil-soluble fluorine-containing surfactant (C) is a fluorine-containing acrylate (A) selected from the above-mentioned A-1 to A-33 and the following hydrocarbon vinyl monomer G.
-1 to G-5 were obtained by radical copolymerization. In addition, the values in parentheses in the table are the weight ratios of the preparations. G-1 _CH2 =C( _CH3 ) _COOCH3 G-2 _CH2 =C( _CH3 )COOist G-3 _CH2 =C( _CH3 )CO( _{-OCH2CH2 ) 23} ---
OCH ₃

【table】

【table】

[Table] Comparative Example 7 A-31, E-16 (R ₂ = H), and methyl methacrylate-ethyl acrylate-acrylic acid copolymer "Carboset" 525 (weight ratio 1/
A tetrahydrofuran solution (10%) of 4/) was prepared, and a coating film with a thickness of 1 μm was obtained on a steel plate by the same method as described above (EB curing). Various properties of the coating film are shown in Table 2.
From this result, JP-A-57-16067
It has been found that the method disclosed in the present invention cannot provide a coating film with excellent smoothness, scratch resistance, etc., which is the objective of the present invention.

[Table] Examples 12 to 15 Next, coatings were formed on polyester films under the same conditions as in Examples 1 to 11, and their surface smoothness, surface drying properties, contact angle, and friction reduction properties were examined.
The results are shown in Table-3. The coefficient of dynamic friction was measured using a friction test jig manufactured by Toyo Baldwin in accordance with the American Society for Testing and Materials standard D-1894 (weight: 236 g, tensile strength: 100 mm/min). .

【table】

【table】

[Table] Comparative Examples 11 to 16 Thermosetting paint “Acrose #6000” (product name:
Using white paint manufactured by Dainippon Toyo Co., Ltd. (containing TiQ ₂ ),
Steel plate (JIS G3141) or aluminum plate (JISH4000)
A coating film with a thickness of 0.5 μm was formed under curing conditions of 150° C. for 30 minutes. Table 4 shows various properties of the coating film.

[Table] As is clear from Table 4, the coating film obtained from the composition containing the fluorine-containing polymer has better hardness (scratch resistance) and rust prevention than the coating film obtained from the composition of the present invention. It was inferior in that respect. Comparative Examples 17 to 24 Using the hydrocarbon acrylates (B) of Examples 1 to 11 (sample Nos. 1 to 11), the fluorine-containing acrylate (A) of the present invention and the oil-soluble fluorine-containing surfactant ( In place of C), lower fluoroalkyl group-containing vinyl monomers and nonionic fluorine-containing surfactants shown in Table 5 were used to form coatings, and their surface smoothness, contact angle, and friction reduction properties were examined.

[Table] As is clear from Table 4, the coating using a lower fluoroalkyl group-containing vinyl monomer and a nonionic fluorine-containing surfactant has better friction reduction properties, contact angle, and surface smoothness than the coating of the present invention. It was inferior in some respects.

Claims (1)

[Claims] 1 R _f (-A) _a --Q-OCOC(R ₁ ) ₌ CH ₂ [In the formula, R _f is a perfluoroalkyl group having 4 to 20 carbon atoms, and A is a divalent [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] [Formula] or [Formula] (where R is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms or an alkyl group containing ether oxygen), a is 0 or 1, Q is (-CH ₂ ) _o -- (however, n is an integer from 2 to 4), R ₁ is a hydrogen atom, a methyl group, or a halogen atom] Fluorine-containing acrylate (A)
, a hydrocarbon-based acrylate (B), and an oil-soluble fluorine-containing surfactant (C), and the weight ratio of the (A) component and (B) component is 1:4 to 1:10000. and the amount of component (C) in the composition is from 0.005 to 5% by weight, the composition being polymerizable by ultraviolet rays or electron beams, and comprising an oil-soluble fluorine-containing surfactant ( A film-forming composition characterized in that C) is a copolymer of a fluorine-containing acrylate and a hydrocarbon vinyl monomer. 2. The film-forming composition according to claim 1, wherein a of the fluorine-containing acrylate (A) is 1.