JPH072915B2 - Coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention is characterized by containing a fluorine-based compound,
Polymerized by energy rays such as ultraviolet rays or electron rays, the surface is smooth, friction-reducing, and water / oil repellent,
The present invention relates to a coating composition that forms a coating excellent in rust prevention and the like.

<Prior art> As a method for protectively coating the surface of metal, plastic, porcelain, glass, etc., a curable resin material such as a polymerizable monomer or a prepolymer of these is applied to the surface and then cured by irradiation with energy rays. A method is known in which a strong resin material is polymerized to form a strong cured resin film on the surface.

In this method, it has recently been noted that the surface formed from the aggregate of fluorinated alkyl groups has a low surface energy, and a fluorinated alkyl group-containing monomer is used as one component of the curable resin composition to improve solvent resistance. Resistance, wear resistance,
Motivation to form a film with excellent friction reduction properties has increased, and it is applied not only to the protective coating of various molded products but also to the surface coating of electrophotographic image carrier and magnetic tape, magnetic disk, etc. It became so. For example, U.S. Pat.Nos. 2,803,615, 2,642,416, 3,384,
No. 627, No. 3,419,602, No. 3,719,698, No. 3,981,928
No. 3,102,103, 3,171,861, 3,818,074,
Compounds containing one perfluoroalkyl group and one vinyl group in one molecule described in the specification of No. 3,814,741 or the like, or fluorocarbons such as -OCH ₂ CF ₂ OCF ₂ CF ₂ OpCF ₂ OqC ₂ CF ₂ O- A technique in which a compound in which vinyl groups are linked to both ends of an oxyalkylene group through a divalent linking group is added to a curable resin composition to perform coating with high solvent resistance (JP-A-57-16067).
Issue).

A technique for coating the above-mentioned fluorine-containing vinyl monomer on the magnetic surface side of a magnetic recording medium and curing with an energy ray to obtain a magnetic surface protective layer excellent in abrasion resistance and friction reduction property (JP-A-59- 28244 publication).

Fluorine-containing vinyl monomer such as 1,1,1,3,3,3-hexafluoropropyl (meth) acrylate or perfluoroethoxy-1,1-dihydroperfluoropropyl (meth) acrylate in the energy ray-curable composition Is added to the surface of a plastic or metal and cured to form a coating having excellent smoothness and abrasion resistance (Japanese Patent Laid-Open No. 52-105936).

<Problems to be Solved by the Invention> However, these conventionally used perfluoroalkyl group- or perfluoroalkylene group-containing vinyl monomers have poor compatibility with non-fluorine-based components and are cured by energy rays. The obtained cured coating film does not have sufficient friction reducing property, homogeneity and smoothness, and does not satisfy the surface characteristics required for the magnetic tape or the magnetic disk. On the other hand, 1,1,1,3,
Attempts have been made to increase compatibility with non-fluorine-containing components by using vinyl monomers containing partially fluorinated alkyl groups such as 3,3-hexafluoropropyl (meth) acrylate. Since the surface energy of the film cannot be lowered sufficiently, the friction reducing property, the homogeneity and the smoothness are insufficient, and the required surface characteristics of the recording material cannot be satisfied at present.

<Means for Solving Problems> The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, have two perfluoroalkyl groups in one molecule,
A perfluoroalkyl group and an acryloyl group, or a fluorine-containing compound in a form in which it is linked by a divalent linking group having a specific structure has good compatibility with a non-fluorine-containing component, and after curing with energy rays, the conventional compound Much better surface properties than fluorinated vinyl monomers or fluorinated surfactants, namely friction reduction, homogeneity, smoothness, scratch resistance, rust resistance, moisture resistance, solvent resistance, water and oil repellency. The present invention has been completed by finding that it can be used as a surface modifier exhibiting the above.

One of the objects of the present invention is to provide an energy ray-polymerizable and curable coating composition comprising a novel fluorine-containing compound having excellent compatibility and surface characteristics such as the general formula [I]. It is in.

The novel reactive fluorine-containing surface modifier according to the present invention has the general formula [I] [In the formula, Rf and Rf ′ are perfluoroalkyl groups having 3 to 20 carbon atoms and may be the same or different.

Z ₁ and Z ₂ are (Wherein R ₁ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), or a divalent linking group selected from CH ₂ n (where n is an integer of 1 to 6). Yes, they may be the same or different.

Z ₃ is CH ₂ m (however, m is an integer of 2 to 6).
Or Is.

R is a hydrogen atom, a methyl group, or a halogen atom.

X ₁ , X ₂ , and X ₃ are (However, R ₂ is a hydrogen atom, or an alkyl group or an alkenyl group having 1 to 36 carbon atoms.) Or It is a divalent linking group selected from and may be the same or different.

A is (However, R ₃ is a hydrogen atom, a hydroxymethyl group, a methyl group, an ethyl group, or a nitro group.), Or Is a trivalent linking group represented by. ] It is a compound represented by.

In the fluorine-based compound according to the present invention, Rf has 3 to 3 carbon atoms.
20 is a perfluoroalkyl group or a perfluoroalkenyl group, which may be linear, branched, cyclic or a combination thereof, and in which an oxygen atom intervenes in the main chain, for example, And so on.

Specific examples of the reactive fluorine-containing surface modifier according to the present invention include the following, but it goes without saying that the present invention is not limited to the following compounds.

The method for producing the fluorine-based compound according to the present invention is not particularly limited, but for example, a fluorine-containing alcohol Rf-Z ₁ -OH [II] Rf'-Z ₂ -OH [II '] hydroxyl group-containing (meth) acrylate compound Dicarboxylic acid anhydride Compound containing 3 epoxy groups in the molecule [However, Rf, Rf ′, Z ₁ , Z ₂ , Z ₃ , R, R ₂ and R ₃ are as described above. ], It is easily produced in good yield.

That is, a fluorine-containing alcohol [II] and / or [II '] and a dicarboxylic acid anhydride [IV] and / or [IV'], and a hydroxyl group-containing (meth) acrylate compound [III] and a dicarboxylic acid anhydride [IV] Or [IV ′] and a molar ratio of 0.7: 1 to 1: 1.3, preferably 0.9: 1 to 1: 1.1, at a reaction temperature of 0.
~ 180 ℃, preferably at 50 ~ 130 ℃, And To manufacture. Then, the compounds [VI] and [VII], and the compound [V] containing three epoxy groups in the molecule,
The molar ratio of [V ′] or [V ″] is 2: 1: 0.8 to 2: 1: 1.
2, preferably 2: 1: 0.9 to 2: 1: 1.1, reaction temperature 0 to 180 ° C,
The reaction is preferably carried out at 50 to 130 ° C. to produce the intended reactive fluorine-containing surface modifier [I] according to the present invention.

The above reaction can be carried out without a solvent, but a solvent can be used if necessary. As the solvent, dicarboxylic acid anhydrides [IV], [IV '] or epoxy compounds [V],
There is no particular limitation as long as it does not react with [V ′] and [V ″]. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, dimethylformamide, dimethylsulfoxide, ethyl acetate, butyl acetate, tetrahydrofuran, benzotrifloryl. Do and the like.

In the reaction of the compounds [VI] and [VII] with the epoxy group-containing compound [V], [V ″], or [V ″], if necessary, a tertiary amine compound or a quaternary ammonium salt compound, etc. A catalyst can be used.

In the above production method, the compound [VI] 1 containing a compound [V], [V '] or [V "] containing 3 epoxy groups in the molecule is added to the compound [VI] 1
And by addition of two compounds [VII], and further by addition of three compounds [VII] are by-produced. Even if these are mixed in the compound [I], the surface referred to in the present invention It does not have a great adverse effect on the characteristics. If necessary, it may be purified by fractionation by gel permeation chromatography.

The coating composition according to the present invention is a non-fluorine-based component, that is, a hydrocarbon-based component referred to below, from the viewpoint of economical strength or technical strength of the coating film and adhesion of the coating film to various materials. Although it is used in combination with the monomer (B), (C), or (D), it can also be used in combination with the photopolymerization initiator (E) described later.

The hydrocarbon-based monomer referred to in the present invention is one having one (meth) acryloyl group in the molecule (B), (meth).
Those having two or more acryloyl groups (C) and those having a vinyl group (D).

The hydrocarbon-based monomer (B) having one (meth) acryloyl group in the molecule includes those generally referred to in the art as a diluting monomer, and specifically, B-1 (meth) acrylic acid 〃 2 Alkyl (meth) acrylate (C ₁ -C ₁₈ ) 〃3 Phenoxyethyl (meth) acrylate 〃4 Ethoxyethyl (meth) acrylate 〃5 Methoxyethyl (meth) acrylate 〃6 Butoxyethyl (meth) acrylate 〃7 N, N-diethylaminoethyl (meth) acrylate 〃 8 N, N-dimethylaminoethyl (meth) acrylate 〃 9 glycidyl (meth) acrylate 〃 10 allyl (meth) acrylate 〃 11 2-hydroxyethyl (meth) acrylate 〃 12 2-hydroxy Propyl (meth) acrylate 〃 13 2-Methoxyethoxyethyl (meth) acrylate 〃 14 2-D X-ethoxyethyl (meth) acrylate B-15 Benzyl (meth) acrylate 〃 16 Cyclohexyl (meth) acrylate 〃 17 Dicyclopentenyl (meth) acrylate 〃 18 Dicyclopentenyloxyethyl (meth) acrylate 〃 19 2-Hydroxyethyl (meth) ) Acryloyl phosphate 〃 20 Tetrahydrofurfuryl (meth) acrylate 〃 21 Dicyclopentadienyl (meth) acrylate 〃 22 Dicyclopentadiene ethoxy (meth) acrylate 〃 23 P-benzylphenoxyethyl (meth) acrylate 〃 24 1,6- Hexanediol Mono (meth) acrylate 〃 25 Neopentyl glycol mono (meth) acrylate 〃 26 Glycerin mono (meth) acrylate 〃 27 Trimethylolpropane mono (meth) acrylate 〃 28 Pentaerythritol Rumono (meth) acrylate 〃 29 2-Hydroxy-3-phenyloxypropyl (meth) acrylate 〃 30 2-Hydroxy-3-octyloxypropyl (meth) acrylate 〃 31 Diethylene glycol mono (meth) acrylate 〃 32 Polyethylene glycol (400) Mono (meth) acrylate 〃 33 2- (Perfluorooctyl) ethyl (meth) acrylate The hydrocarbon-based monomer (C) having two or more (meth) acryloyl groups is one generally referred to in the art as a polyfunctional (meth) acrylate or a special (meth) acrylate, a prepolymer, a base resin, an oligomer. In addition, the following are specifically exemplified, including those referred to as acrylic oligomers.

(I) A polyvalent (meth) acrylate in which two or more (meth) acrylic acids are bonded to a polyhydric alcohol.

(Ii) A polyester acrylate in which two or more (meth) acrylic acids are bonded to a polyester polyol obtained by the reaction of a polyhydric alcohol and a polybasic acid.

Examples of the polyhydric alcohol in the above (i) and (ii) include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, trimethylolpropane, dipropylene glycol, polyethylene glycol, polypropylene glycol and penta. Examples thereof include erythritol and dipentaerythritol. Examples of polybasic acids include phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid, succinic acid, terephthalic acid and alkenylsuccinic acid.

(Iii) An epoxy acrylate in which an epoxy group of an epoxy resin is esterified with (meth) acrylic acid to form a (meth) acryloyl group as a functional group.

Examples of the epoxy resin include bisphenol A-epichlorohydrin type, phenol novolac-epichlorohydrin type, and alicyclic resins.

(Iv) A polyurethane acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate with a polyvalent isocyanate compound.

Examples of the polyvalent isocyanate compound include those having a structure of polyester, polyether, polyurethane or the like in the central part of the molecule and having isocyanate groups at both ends.

(V) Other examples include polyether (meth) acrylate, melamine (meth) acrylate, alkyd (meth) acrylate, isocyanurate (meth) acrylate, and silicon (meth) acrylate.

The following are mentioned as an example of these more concrete compounds.

C-1 1,3-Butanediol di (meth) acrylate 〃 2 1,4-Butanediol di (meth) acrylate 〃 3 1,6-Hexanediol di (meth) acrylate 〃 4 Diethylene glycol di (meth) acrylate 〃 5 Neopentyl glycol di (meth) acrylate 〃 6 Polyethylene glycol 400 di (meth) acrylate 〃 7 Hydroxypipalinate neopentyl glycol di (meth) acrylate 〃 8 Tripropylene glycol di (meth) acrylate 〃 9 1,3-bis (3 "-acryloxyethoxy-2 '
-Hydroxypropyl) 5,5-dimethylhydantoin 〃 10 Hydroxypipalinate neopentyl glycol di (meth) acrylate 〃 11 Trimethylolpropane tri (meth) acrylate 〃 12 Pentaerythritol tri (meth) acrylate 〃 13 Dipentaerythritol hexa (Meth) acrylate 〃 14 pentaerythritol tetra (meth) acrylate 〃 15 trimethylolpropane di (meth) acrylate 〃 16 Bisphenol A di (meth) acrylate C-17 dipentaerythritol monohydroxypenta (meth) acrylate 〃 18 Hitachi Chemical ( Products FA-731A Etc.

The hydrocarbon group-containing monomer (D) referred to in the present invention is D-1 styrene 〃 2 P-chlorostyrene 〃 3 P-methoxystyrene 〃 4 divinylbenzene 〃 5 N-vinylpyrrolidone 〃 6 N-vinylcaprolactam 〃 7 Acrylonitrile and the like.

The fluorine-based compound [I] according to the present invention is used in combination with the above-mentioned hydrocarbon monomers (B), (C) and (D). In that case, in order to sufficiently exhibit the surface characteristics shown in the present invention, that is, the friction reducing property, the homogeneity, the smoothness, the scratch resistance, the rustproof property, the moistureproof property, the solvent resistance, the water and oil repellency, etc. , (B) + (C)
The mixing ratio of the fluorine-based compound [I] to + (D) is
The film forming composition according to the present invention, which has a weight ratio of 0.05: 15 to 15: 2.0, is applied or impregnated on a substrate, and then polymerized and cured by applying heat, light, an electron beam, or radiation energy to obtain a desired composition. Can be formed. When heat is used as the polymerization initiation energy, a catalyst-free or azobisisobutyronitrile, a benzoyl peroxide, a polymerization initiator such as methyl ethyl ketone peroxide-cobalt naphthenate, or a light such as ultraviolet light is used, A so-called photopolymerization initiator known in the art,
For example, E-1: benzophenone, E-2: acetone phenone, E-
3: benzoin, E-4: benzoin ethyl ether, E-5: benzoin isobutyl ether, E-6: benzyl methyl ketal, E-7: azobisisobutyronitrile, E-8: 1-hydroxycyclohexyl phenyl ketone, E-9: 2-hydroxy-2-methyl-1-phenyl-1-one and the like and, if necessary, a photosensitizer such as an amine compound or a phosphorus compound can be added to accelerate the polymerization. it can. When polymerizing and curing with an electron beam or radiation, it is not necessary to add a polymerization initiator or the like.

In the coating composition of the present invention, in addition to the above-mentioned polymerization initiator and the like, various additives such as a solvent, a light resistance stabilizer, a coupling agent, a defoaming agent, a leveling agent, and a surfactant may be added. it can.

The solvent can be added in order to control the viscosity, coatability, and film thickness of the coating composition of the present invention. Such a solvent is not particularly limited as long as it does not adversely affect the polymerization reactivity of the composition of the present invention, but methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate. , Chloroform, dichloroethane, carbon tetrachloride, and 1-fluoro-1-dichloro-2-difluoro-2-chloroethane low boiling point solvents are preferable from the viewpoint of workability.

When the composition of the present invention is applied to or impregnated into a substrate as a solution dissolved in a solvent, a step of removing the solvent at room temperature, or if necessary by heating or depressurizing is required before starting the polymerization and curing. Become. When the solvent is removed by heating, it is preferable to carry out the heating at 80 ° C. or lower in order to prevent the heat polymerization of the monomers and the like.

As a method of applying the coating composition according to the present invention to a substrate, various methods known in the art, for example, a brush coating, an applicator, a bar coater, a roller brush, a roll coater or the like coating method, air spray or air. A spray coating method using a less spray coating machine, a flow coating method using a Java coater or a curtain flow coater, a dipping method, a casting method, and a spinner coating method can be used. It is desirable to use them properly according to the application.

When the composition of the present invention is polymerized and cured by irradiation with energy rays, known in the art, germicidal lamp, fluorescent lamp for ultraviolet rays, carbon arc, xenon lamp, high pressure mercury lamp for copying, medium or high pressure mercury lamp, ultra high pressure mercury lamp, Electrodeless lamps, metal halide lamps, ultraviolet rays using natural light as a light source, or electron beams by scanning type or curtain type electron beam accelerating paths can be used. In the case of ultraviolet curing of a coating layer having a thickness of 5 μm or less, polymerization is performed. From the viewpoint of improving efficiency, it is preferable to irradiate in an atmosphere of an inert gas such as nitrogen gas.

<Operation> As mentioned above, there is a proposal to add a fluorine-containing vinyl monomer to a non-fluorine-based component to improve the surface characteristics of the cured coating film. However, according to the findings of the present inventors,
Perfluoroalkyl group or perfluoroalkylene group-containing vinyl monomer, which has been proposed in the past, causes phase separation due to poor compatibility with the non-fluorine-based component, and significantly impairs the homogeneity of the coating film. Does not exhibit friction reduction, rust prevention, scratch resistance, etc. On the other hand, there is also an example in which a fluorine-containing vinyl monomer containing a partially fluorinated alkyl group is used to improve the compatibility, but in such a system, the surface migration of the fluorinated alkyl group is poor, The reality is that they do not exhibit sufficient surface properties.

On the other hand, the fluorine-containing compound according to the present invention does not reduce the compatibility with the non-fluorine-containing component because it has an appropriate lipophilic group, and contains two perfluoroalkyl groups in one molecule. It is considered that the surface transferability is not impaired. For this reason, a microscopically dense aggregate of perfluoroalkyl groups is formed on the surface of the coating film, which is homogeneous and has a friction reducing property, a smoothness,
It is presumed that a surface excellent in scratch resistance, rust resistance, moisture resistance, solvent resistance, water and oil repellency, etc. can be obtained. It should be noted that the above speculation is for helping to understand the present invention, and it goes without saying that the present invention is not limited at all.

<Effects of the Invention> As described above, the coating composition according to the present invention can be used as a protective coating layer for various solid surfaces such as a moisture-proof rust preventive agent, an antifouling agent, a lubricant, an antifriction agent, a release agent, a release agent, Although it can be used as a sealant for electronic parts and the like, it is particularly preferably used for coating a magnetic layer of a magnetic recording product in the field of recording materials by taking advantage of thinness, smoothness and moisture resistance of the coating.

For example, copper, aluminum, non-magnetic metals such as zinc, polyethylene terephthalate, polyesters such as polyethylene-2,6-naphthalate, polyolefins such as polypropylene, plastics such as cellulose derivative polycarbonate such as cellulose acetate, and, depending on the case, Ferromagnetic alloy deposited on ceramics such as glass, paper, wood, fibers, porcelain and pottery (iron, cobalt and / or nickel as the main component with a small amount of aluminum,
(Including silicon, chromium, manganese, molybdenum, titanium, various heavy metals, rare earth metals, etc.) or a small amount of oxygen, magnetic tape obtained by vapor deposition of a magnetic material such as iron, cobalt, chromium on a plastic film such as polyester, or It is also suitable as a protective coating for the magnetic layer of a magnetic disk, and as a surface and back surface treatment agent for magnetic recording media such as magnetic tapes and floppy disks, which are particularly required to have antifriction properties.

On the other hand, since the coating composition of the present invention can form a transparent and smooth thin film on the glass surface, it is also used in applications requiring oil resistance and wiping resistance as an oil stain preventive agent for various optical devices. can do.

Furthermore, a protective film for solar cells, which is particularly required to have moisture resistance,
It is also suitable as a protective coating agent for optical fibers, optical fiber cables, optical disks, magneto-optical disks and the like. Further, since it is excellent in scratch resistance, antifouling property, and moisture resistance, it can be used as surface protection for medical devices and instruments, surface protection for teeth and dentures, tooth cavities and molds.

Further, since the coating composition of the present invention can form a coating having excellent scratch resistance, it can be used as a hard coating agent for various molded articles or films, sheets and the like.

Furthermore, a pigment and a dispersant are mixed in the composition of the present invention,
A paint or ink excellent in antifouling property or non-adhesiveness can be formed.

Next, specific synthesis examples and examples of the present invention will be described, but it goes without saying that the present invention is not limited to these explanations. In the text, "part" and "%" are based on weight.

Synthesis example 1 Synthesis of A-19 In a 300 ml four-neck round bottom flask equipped with a stirrer, thermometer, condenser, 35.1 g (0.06 mol), C ₈ F ₁₇ CH ₂ CH ₂ OH 27.9 g (0.06 mol), 2-hydroxyethyl acrylate 7.1 g (0.06 mol), hydroquinone 0.5 g, and succinic anhydride 18.0 g
(0.18 mol) was weighed and reacted at 95 to 100 ° C. for 1 hour in a dry oxygen atmosphere. After lowering the temperature in the system to 70-75 ℃, 18.1 g (0.06 mol) and then 0.9 g of N, N-dimethylbenzylamine were added, and the mixture was reacted at 95 to 100 ° C for 3 hours. As a result, 107.6 g of a pale yellow paste was obtained. As a result of titrating the amount of residual carboxyl groups with a 0.1 (N) sodium hydroxide aqueous solution, the reaction rate was 98.7%. This crude product can be directly used as a coating agent, but if necessary, it can be purified as follows.

Tetrahydrofuran solution of the crude product is GPC (column: Hitachi, Gelco GL-A130, 8 mmφ x 500 mm, eluent:
When subjected to tetrahydrofuran, detection: ultraviolet absorption meter, 254 nm), several small peaks were obtained before and after the main peak. The ratio of main peak area to total peak area is 70
%Met.

When the main peak was collected and subjected to ¹ H-NMR measurement, IR measurement, and elemental analysis, it was confirmed to be the target fluorine-based compound.

Synthesis example 2 Synthesis of A-1 All the fluorine-containing alcohols of Synthesis Example 1, succinic anhydride,
Then, 2-hydroxyethyl acrylate was added to C ₈
F ₁₇ CH ₂ CH ₂ OH55.8g (0.12mol), Substituting 37.8 g (0.18 mol) and 7.8 g (0.06 mol) of 2-hydroxyethyl methacrylate, the same reaction was performed and purification was performed. The yield of the crude product was 120.9 g, and the reaction rate with a 0.1 (N) sodium hydroxide aqueous solution was 9.90%. GP
The ratio of the main peak area in C analysis was 78%, and the main peak was collected and subjected to ¹ H-NMR measurement, IR measurement, and elemental analysis, whereupon it was confirmed to be the target compound.

Examples 1 to 12 and Comparative Examples 1 to 8 A copper plate (JIS G3141), an aluminum plate (JIS H4000), and a glass plate were coated with the coating composition of the present invention shown in Table-1, and the solvent was evaporated at room temperature. After that, the coating layer was cured by ultraviolet electron beam heat under the following conditions, and various characteristics of the coating film were examined. The results are shown in Table-1.

Equipment: UV curing uses a high pressure mercury lamp (80w / cm),
The irradiation distance was 10 cm, the irradiation time was 60 seconds, and the irradiation was performed at 33 ° C. in a nitrogen atmosphere. Curing with an electron beam was performed with a curtain type electron beam accelerator (200 kV) at a dose of 10 Mrad.

Heat curing conditions: Heat curing was performed in a heating oven under heating conditions of 150 ° C. for 10 minutes.

Coating method: A composition comprising the fluorine-based compound (A), the hydrocarbon-based monomers (B), (C) and (D) according to the present invention, and other compounds is diluted to 5% with ethyl acetate, and a bar coater is used. To form a coating layer having a nonvolatile content of 1.0 μm.

Coating method: The composition comprising the reactive fluorine-containing surface modifier (A), the hydrocarbon-based acrylates (B) and (C), and the photopolymerization initiator (D) according to the present invention was made 5% with ethyl acetate. It was diluted and coated with a bar coater to form a coating layer having a nonvolatile content of 0.5 μm.

Surface smoothness: The smoothness of the surface coating film is observed with an optical microscope at a magnification of 160 times for the presence or absence of spots on the coating film, and there are 5 stages (5: no spots at all, 4: only slight spots at the edges, 3: The surface had only a few spots, 2: the surface had a few spots, 1: all the spots were larger.

Surface dryness: ◎ By finger touch ⊙ No stickiness at all ∘ Marked stickiness is slightly felt △ Mark There is some stickiness × Sign There is stickiness Surface hardness: It was carried out based on the method of JIS 5400.

Contact angle: n-dodecane or water was dropped onto a measuring surface of 6μ and contact angle was measured using an Elma goniometer-type contact angle measuring device.
It was measured at ° C.

Rust resistance: The test piece is dipped in a 20% sodium chloride aqueous solution, and the time until rust is generated in the coating film is observed, and 5 stages (5: 200 hours or more, 4: 150-200 hours, 3: 100- 150 hours, 2:50 to 100 hours, 1: 0 to 50 hours).

Cross-cut test: 1 cm square is cut by 1 mm and cut vertically and horizontally with a cutter to make 100 squares. Then, cellophane tape (Sekisui Chemical S-832) is adhered, and peeled off at a stretch to find out the number of remaining squares. Represented.

The UV indications in the columns of Examples and Comparative Examples No. indicate the formation of a polymer film by ultraviolet curing, EB indications indicate electron beam curing, and HEATs indicate heat curing. Further, (A), (B), (C), (D), and (E) in the table represent the compounds in the main component.

As in Examples 1 to 12, the inventive examples were found to have excellent properties in surface smoothness, surface dryness, surface hardness, contact angle, salt water resistance, and cross-cut test. On the other hand, as in Comparative Examples 1 to 8, when the fluorine-based compound according to the present invention is absent or a reactive fluorine-containing compound of another type is added instead of the fluorine-based compound, it is extremely poor as compared with the Examples. It turns out that only performance can be obtained.

Examples 13 to 19 and Comparative Systems 9 to 16 Next, a coating film was formed on the polyester film with the same composition as that of the example shown in Table 1 to form a coating film thickness of 5 μm. The contact angle and sliding angle of n-dodecane, friction resistance reduction, solvent resistance to acetone and chlorothene, light resistance, and humidity resistance were investigated. Table of the results
2 shows.

In addition, the measurement of the dynamic friction coefficient is based on the American Sample Testing Association Standard D-1894.
Was performed using a friction test jig manufactured by Toyo Baldwin Co., Ltd. (weight weight: 236 g, tensile strength: 100 mm /
mm).

The solvent resistance was evaluated by a multi-view and cross-cut test by immersing the polyester film having the coating film of the present invention in acetone and chlorothene at 50 ° C. for 1 hour and then pulling it up.

The light resistance was evaluated by visually observing the appearance of the coating film after exposure for 1000 hours using a fade meter.

Moisture resistance was evaluated by a cross-cut test for the appearance and adhesion of the coating film after the lapse of 150 hours at 80 ° C and 90% RH.

From Table-2, clear differences between the examples of the present invention and the comparative examples are recognized in terms of surface smoothness, surface dryness, contact angle, coefficient of dynamic friction, solvent resistance, light resistance and humidity resistance. The sex was confirmed.

Claims (1)

[Claims] 1. A general formula [Wherein Rf and Rf ′ are perfluoroalkyl groups having 3 to 20 carbon atoms, and Z ₁ and Z ₂ are (Wherein R ₁ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), or a divalent linking group selected from CH ₂ n (where n is an integer of 1 to 6). And Z ₃ is CH ₂ m (however, m is an integer of 2 to 6).
Or And R is a hydrogen atom, a methyl group, or a halogen atom, and X ₁ , X ₂ , and X ₃ are (However, R ₂ is a hydrogen atom, or an alkyl group or an alkenyl group having 1 to 36 carbon atoms.) Or Is a divalent linking group selected from (However, R ₃ is a hydrogen atom, a hydroxymethyl group, a methyl group, an ethyl group, or a nitro group.), Or Is a trivalent linking group represented by. ] A fluorine-based compound represented by and a hydrocarbon-based monomer having a (meth) acryloyl group or vinyl group in the molecule, and the weight ratio of the former to the latter is 0.05: 15 to 15: 2.0. A coating composition capable of being polymerized by irradiation with an energy ray, characterized in that