JPH0751694B2 - Coating film forming composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention has good surface smoothness, friction resistance reduction property, water repellency, oil repellency, antifouling property, weather resistance, light resistance and adhesion to a substrate. The present invention relates to a coating film-forming composition having excellent surface protection capable of forming a cured film.

<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 an energy ray is irradiated. A method is known in which a curable resin material is polymerized by a method to form a strong cured resin film on the surface.

In this method, in recent years, it has been noticed that the surface formed from a polymer of a fluorinated alkyl group has a low surface energy, and a fluorinated alkyl group-containing monomer is used as one component of a curable resin composition to produce a solvent resistant composition. Resistance, wear resistance,
Motivation to form a film with excellent friction reduction properties has increased, and it is applied not only to the protective film 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, as described in the specification such as 3,814,741
Or at both ends of the _{-OCH 2 CF 2 OCF 2 CF 2} O p CF 2 O q CF 2 CH 2 O- in such fluoroalkyl oxyalkylene group, curing compounds vinyl group is linked via a divalent linking group Of adding a solvent-resistant resin composition to form a coating with high solvent resistance (JP-A-57
-16067).

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 reducing property (JP-A-59-59). 28244 publication).

The energy ray-curable composition contains 1,1,1,3,3,3-hexafluoropropyl (meth) acrylate or perfluoroethoxy 1,1-dihydroperfluoropropyl (mer)
Add a fluorine-containing vinyl monomer such as acrylate,
A technique of applying such a composition to the surface of a plastic or a metal and curing it to form a film having excellent smoothness and abrasion resistance (JP-A-52-105936).

A technology that forms a coating film with excellent wear resistance and smoothness by applying a composition obtained by adding a fluorosurfactant to a crosslinkable polymerizable compound to the surface of a plastic and curing it.

There is a suggestion such as.

<Problems to be Solved by the Invention> These conventionally used perfluoroalkyl group- or perfluoroalkylene group-containing vinyl monomers have poor compatibility with non-fluorine-based components and are obtained by curing with energy rays. The cured coating does not have sufficient friction reduction property, homogeneity and smoothness, and does not satisfy the surface characteristics required for magnetic tapes or magnetic disks. On the other hand, a vinyl monomer containing a partially fluorinated alkyl group such as 1,1,1,3,3,3-hexafluoropropyl (meth) acrylate is used as the fluorinated vinyl monomer, and Attempts have been made to increase the compatibility, but since the surface energy of the cured film cannot be sufficiently reduced by such a method, the friction reducing property, the homogeneity, and the smoothness are insufficient. The current situation is that the characteristics cannot be satisfied again. Further, although the cured film obtained from the composition obtained by adding a fluorosurfactant to the curable composition shows an improvement in smoothness and homogeneity, it has reduced frictional resistance, hardness, water repellency, oil repellency, Antifouling property, moisture resistance,
Impact resistance, weather resistance, light resistance, etc. are not sufficient, and they are still unsatisfactory for use in fields where these characteristics are highly required.

<Means for Solving Problems> The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, have found that the average molecular weight is substantially water-insoluble and soluble in an organic solvent.
The cured surface protective coating of the composition obtained by adding and blending 2,000 or more polyfluoroalkyl group-containing polymers into the polymerization curable monomer is far superior to the coating obtained from the prior art. Surface properties, that is, friction reduction, homogeneity, smoothness, scratch resistance, rust resistance, moisture resistance, solvent resistance, water and oil repellency, weather resistance, light resistance, etc. are highly expressed. The present invention has been completed and the present invention has been completed.

That is, the present invention is a substantially water-insoluble organic solvent-soluble polymer having an average molecular weight of 2,000 or more and a perfluoroalkyl group-containing polymer and a polymerization-curable polyfunctional monomer having two or more (meth) acryloyl groups in the molecule. And / or a polymerization-curable coating film-forming composition based on a multifunctional oligomer.

As the polymer which is a constituent component of the composition of the present invention, a polymer which is substantially insoluble in water, preferably having a solubility of 0.001% by weight or less and soluble in an organic solvent and not having a mean molecular weight of 2,000 or more is used. Solubility in organic solvent is 25 ℃
In the above, those having a solubility of 0.1% by weight or more are preferable. As the organic solvent, alcohols (methanol, isopropyl alcohol), ketones (acetone, methyl isobutyl ketone), ethers (ethyl ether, tetrahydrofuran), esters (ethyl acetate, isobutyl acetate), hydrocarbons (n-hexane) ,toluene),
Halogenated hydrocarbons (chloroform, Freon-113)
25 ° C against any of these solvents
Those having a solubility of 0.1% by weight or more are preferred. The average molecular weight is 2,000 or more, and from the viewpoint of solubility, the average molecular weight of 500,000 or less is easy to use. The fluorine atom in the polymer is one that is covalently linked to a carbon atom, and the fluorine atom content is preferably 0.01% by weight to 76% by weight, more preferably 0.1% by weight to 50% by weight. The above-mentioned ones are easy to use and effective in terms of performance.

The fluorine atom is preferably contained as a polyfluoroalkyl group having 1 to 16 carbon atoms and introduced as a side chain of the polymer skeleton. Some of such polymers can be obtained from commercial products. For example, the solvent-type water and oil repellents Dick Card F-320 and F-327 manufactured by Dainippon Ink and Chemicals, Inc. are particularly preferable examples. In addition, it can also be obtained by synthesizing polymers having various molecular structures depending on the required characteristic level. The following can be mentioned as an example of such a thing.

B-1 And methyl methacrylate in a molar ratio of 1: 5 (average molecular weight 20,000) B-2 C _n F _{2n + 1} CH ₂ CH ₂ OCOCH = CH ₂ (n: 1 to 16 mixture,
Copolymer having an average molecular weight of 520) and a methyl methacrylate macromer having an average molecular weight of about 5,000 in a molar ratio of 3: 1 (average molecular weight 40,000) B-3 C ₁₀ F ₂₁ CH ₂ CH ₂ OH, PPG-5000, and tolylene diisocyanate molar ratio of 2: 1: 2 of polyurethane (average molecular weight _{5,900) B-4 C 8 F} 17 SO 2 N (CH 2 CH 2 OH) 2, the molar ratio of polyethylene glycol and adipic acid of 1: 3: 4 Polyester (Average Molecular Weight 4,700) All of the above-exemplified polymers B-1 to B-4 have a solubility of 0.1% or more in the organic solvent methyl isobutyl ketone, and are substantially insoluble in water.

The polymer relating to the present invention must be contained in the coating film forming composition of the present invention in an amount of 0.01% by weight or more, preferably 0.1% by weight or more. When the amount added is 0.01% by weight or less, various properties attributed to the fluorine compound are not sufficiently expressed, and the effects of the present invention cannot be exhibited.

It is as described above that the polymer relating to the present invention remarkably improves the function of the surface protective coating film by adding and blending the polymerization curable monomer and / or oligomer.
In addition to this, it has an important effect newly discovered by the present inventors. That is, originally a polymerizable curable monomer, poor compatibility with oligomers, perfluoroalkyl group-containing monomer that could not be used as a mixture, in the coexistence of the polymer according to the present invention, a polymerizable curable monomer,
It is compatible with oligomers and can be used for fitting. Therefore, not only the homogeneity of the cured protective coating film but also the surface properties of the cured protective coating film have a remarkable synergistic effect. This is also one of the important effects of the present invention.

The other component of the composition of the present invention, which is a polymerization-curable monomer or oligomer, is one having two or more (meth) acryloyl groups in the molecule. For example, UV or electron beams which are usually commercially available. A curable paint or ink can be used. Examples of such products are UV curable paints (trade name: Unidick series), UV curable inks (trade name: Dicure series) manufactured by Dainippon Ink and Chemicals, Inc., Soma Examples include the coat series and the Seika Beam series manufactured by Dainichi Seika Kogyo Co., Ltd.

In addition, various other polymerization-curable monomers and / or oligomers may be blended with the above-mentioned commercially available product according to the required characteristic level to form a new blending system. Other polymerization-curable monomers and / or oligomers to be added to the new compounding system in this case have two or more (meth) acryloyl groups in the molecule, and as an essential component, for example, in the molecule. The studies made by the present inventors have revealed that it is preferable to contain a polyfunctional monomer or a polyfunctional oligomer having two or more (meth) acryloyl groups. That is, the presence of a polyfunctional monomer or a polyfunctional oligomer having two or more (meth) acryloyl groups in the molecule is preferable in addition to the above-mentioned polymer in the present invention. Examples of such polyfunctional monomers or polyfunctional oligomers include the following.

(I) Polyhydric acrylate in which two or more (meth) acrylic acids are added to polyhydric alcohol.

Examples of the polyhydric alcohol include ethylene glycol, 1,6-hexanediol, trimethylolpropane, pentaerythritol and dipentaerythritol.

(Ii) A polyester acrylate obtained by adding two or more (meth) acrylic acids to a polyester polyol obtained from a polyhydric alcohol and a polybasic acid.

Examples of polyhydric alcohols include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, trimethylolpropane, dipropylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, and dipentaerythritol. Is phthalic acid, adipic acid, maleic acid,
Examples thereof include trimellitic acid, itaconic acid, succinic acid, terephthalic acid and alkenylsuccinic acid.

(Iii) Epoxy acrylate in which the epoxy group of the epoxy resin is esterified with (meth) acrylic acid and the functional group is an acryloyl group. Examples of the epoxy resin include bisphenol A-epichlorohydrin type, phenol novolac-epichlorohydrin type, and alicyclic resin. .

(IV) Polyurethane acrylate obtained by reacting polyvalent isocyanate with hydroxy (meth) acrylate Polyvalent isocyanate includes those having a structure such as polyester or polyether at the center of the molecule and having isocyanate groups at both ends. .

(V) Others, such as polyether acrylate, melamine acrylate, alkyd acrylate, isocyanurate acrylate,
Silicon acrylate etc.

Of these, when specific compounds are exemplified,
The following are listed.

_{A-1 CH 2 = C (} R 3) COOCH 2 n OOCC (R 3) = CH
₂ (n is an integer of from 1 to _{10) A-2 CH 2 = C} (R 3) COOCH 2 CH 2 O n COC (R 3) = CH 2
(N is an integer from 1 to 10) _{A-13 (CH 2 = C} (R 3) COOCH 2 3 CCH 2 OH A-14 (CH 2 = C (R 3) COOCH 2 3 CCH 2 CH 3 A-15 (CH 2 = C (R 3) COOCH ₂ CH ₂ O ₃ P = O _{A-17 (CH 2 = C} (R 3) COOCH 2 4 C ( where, R ₃ is -H or -CH _3.) And the like.

Polyfunctional monomers or oligomers having two or more (meth) acryloyl groups in these molecules are
The coating material of the present invention must be contained in an amount of preferably 1% by weight or more, more preferably 5% by weight or more. A cured coating obtained by applying a composition having a content of less than 1% by weight to a substrate and curing it has not only a very low hardness but also a poor antifriction property. According to the knowledge of the present inventors, from the viewpoint of the surface hardness, weather resistance and light resistance of the cured protective coating film, not only the bifunctional monomer but also the trifunctional monomer or the tetrafunctional monomer coexists. Preferably
It has been found that it is more preferable that the polymerization-curable monomer is a mixed system of these 2 to 4 functional polyfunctional monomers or polyfunctional oligomers. This is also one of the remarkable effects of the present invention.

The coating film forming composition of the present invention is applied to the surface of a protected substrate or impregnated into the substrate, and then subjected to crosslinking, polymerization and curing by applying energy such as heat, light or electron beam to obtain a desired protective coating. A film can be formed. When heat is used as the polymerization initiation energy, thermal polymerization initiators such as azobisisobutyronitrile and benzoyl peroxide, and when light such as ultraviolet rays is used, photoinitiators such as benzophenone and benzyl dimethyl ketal. In some cases, photosensitizers such as amines and phosphorus compounds can be added to accelerate the cross-linking polymerization and improve the efficiency. In the case of curing with an electron beam, it is not necessary to add an initiator.

In addition to the above-mentioned polymerization initiator, a reactive diluent monomer, a solvent and various additives can be added to the coating film forming composition of the present invention.

The reactive diluent monomer may be added not only to adjust the viscosity of the composition of the present invention but also to improve the coatability and adhesion of the surface protective coating film to the substrate to be coated. is there. If the amount of the reactive diluent monomer to be added increases, the hardness of the cured film will decrease, so it is not preferable to add a too large amount. The mixing ratio of the reactive diluent monomer to the polyfunctional monomer or polyfunctional oligomer is 1/100 to 5/1, preferably 1/10 to 2/1 by weight.

Such a reactive diluting monomer is a monomer having one vinyl group as a reactive group and is a solvent, and examples thereof include the following, but are not limited thereto.

C-1 methoxyethyl acrylate, C-2 butoxyethyl acrylate, C-3 ethoxydiethylene glycol acrylate, C-4 butoxytriethylene glycol acrylate, C-5 methoxypropylene glycol acrylate, C-6 phenoxyethyl acrylate, C-7 2- Hydroxyethyl acrylate, C-8 2-hydroxy-3-phenyloxypropyl acrylate, C-9 nonylphenol EO adduct acrylate, C-10 benzyl acrylate, C-11 cyclohexyl acrylate, C-12 tetrahydrofurfuryl acrylate, C-13 Monoacryloxyethyl phosphate, C-14 cyclopentenyl acrylate, C-15 dicyclopentenyloxyethyl acrylate C-16 N-vinyl-2-pi Ridone, C-17 2- (perfluorooctyl) ethyl acrylate, C-18 styrene, C-19 N-vinylpyrrolidone, C-20 N-vinylcaprolactone, C-21 2-acrylamido-2-methylpropanesulfonic acid, The C-22 (meth) acrylic acid solvent can be added in order to improve the viscosity, coatability or controllability of the film thickness of the coating film forming composition of the present invention.

Such a solvent is not particularly limited as long as it does not adversely affect the cross-linking polymerization property of the composition of the present invention, but is, for example, methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, chloroform. , A low boiling point solvent such as dichloroethane, carbon tetrachloride, and Freon-113 is preferable from the viewpoint of workability.

When the composition of the present invention is applied as a solution dissolved in such a solvent, a step of removing the solvent at room temperature or, if necessary, by heating or depressurization is required before starting the cross-linking polymerization. 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.

When the composition of the present invention is cross-linked and cured by irradiation with energy rays, known in the art, germicidal lamp, ultraviolet fluorescent lamp, carbon arc, xenon lamp, high pressure mercury lamp for copying, medium or high pressure mercury lamp, ultra high pressure mercury lamp, no electrode It is possible to use a lamp, a metal halide lamp, ultraviolet rays having a light source such as natural light, or an electron beam from a scanning type or curtain type electron beam accelerating path. Further, in the case of ultraviolet curing of the coating layer having a thickness of 5 μm or less, it is preferable to irradiate under an inert gas atmosphere such as nitrogen gas from the viewpoint of efficient polymerization.

Examples of the base material used in the composition of the present invention include metals and alloys such as iron, aluminum, copper, tin, lead, zinc, nickel, cobalt, chromium, gold and silver, glass, pottery, porcelain, ceramics and wood. Objects, fibers (glass fiber, carbon fiber), papers, molded articles of plastics, sheets, films (polyolefins, urethanes, polyesters,
Polyamide type, phenol type, epoxy type, acrylic type, vinyl chloride type, vinyl acetate type, etc.) and the like.

<Function> As described 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 film. However, according to the findings of the present inventors,
Conventionally proposed perfluoroalkyl group- or perfluoroalkylene group-containing vinyl monomers cause phase separation due to poor compatibility with non-fluorine-based components, and significantly impair the homogeneity of the coating film, so that sufficient friction Does not exhibit reduction properties, rust resistance, scratch resistance, etc. Also, as the fluorinated vinyl monomer, one containing a partially fluorinated alkyl group is used,
Although there is an example in which the compatibility is improved, in such a system, the surface transfer property of the fluorinated alkyl group is poor, so that it is the actual situation that sufficient surface properties are not exhibited.

On the other hand, there is also a proposal to improve the homogeneity of the cured coating film by blending a fluorine-based surfactant in the UV-curable monomer composition. Functions such as dirt resistance, moisture resistance, and impact resistance are not sufficient.

On the other hand, in the present invention, a substantially water-insoluble organic solvent-soluble polymer is used as an essential component,
The various problems mentioned above are solved, and the physical properties of the cured coating film,
It was confirmed that the function was significantly improved.

Since the polymer of the present invention has good compatibility with the crosslinkable polymerizable monomers, no phase separation phenomenon is observed. In addition, it is presumed that intermolecular entanglement between the polymer and the cross-linked polymerization-cured resin has occurred. Therefore, in terms of the durability of surface characteristics, durability, weather resistance and light resistance, a fluorine-based surfactant is added. It was also confirmed that it was significantly improved compared to what was done.
Further, since the polymer is substantially water-insoluble, the moisture resistance and water resistance of the obtained cured coating are significantly improved as compared with the coating containing a fluorosurfactant.

It should be noted that the above-mentioned rubbing 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 surface protective coating film forming composition of the present invention can be used as a protective coating layer for various solid surfaces such as a moisture-proof anticorrosive agent, an antifouling agent, a lubricant, an antifriction agent, a release agent, and Although it can be used as a release agent, a sealant for electronic parts, etc., it is particularly preferably used for coating the magnetic layer of a magnetic recording product in the field of recording materials by taking advantage of the thinness and smoothness of the coating.

For example, copper, aluminum, non-magnetic metals such as zinc and polyethylene terephthalate, polyesters such as polyethylene-2,6-naphthalate, polyolefins such as polypropylene, plastics such as cellulose derivative polycarbonate such as cellulose acetate, and further, depending on the case. Ferromagnetic alloys deposited on ceramics such as glass, paper, wood, fibers, porcelain and earthenware (based on iron, cobalt and / or nickel, with small amounts of aluminum, silicon, chromium, manganese, molybdenum, titanium, (Including various heavy metals, rare earth metals, etc.) or a trace amount of oxygen, magnetic materials such as iron, cobalt and chromium are vapor-deposited on a plastic film such as polyester porcelain tape, or a protective coating such as the magnetic layer of a porcelain disc, etc. ,
It is also suitable as a back surface treating agent for porcelain tapes, which requires particularly low friction. Further, by dispersing magnetic powder in the coating film forming composition of the present invention, an energy ray-curable magnetic binder having smoothness, antifriction property, and rust prevention property can be obtained.

On the other hand, the coating film-forming composition of the present invention can form a transparent and smooth thin film on a glass surface, and therefore requires oil resistance and wiping resistance as an oil stain preventive agent for various optical devices. Can also be used for

Furthermore, it is also suitable as a protective coating agent for optical fibers, optical fiber cables, optical discs, magneto-optical discs, etc., which are particularly required to have moisture resistance.

Moreover, since the coating film forming composition of the present invention can form a coating film having excellent scratch resistance, it can be used as a hard coating agent for various molded products 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 examples of the present invention will be described, but it goes without saying that the present invention is not limited to such examples. In the text, "part" and "%" are based on weight.

<Examples> Examples 1 to 7 and Comparative Examples 1 to 10 Tables on steel plates (JIS G3141) or aluminum plates (JIS H4000)-
The composition of the present invention shown in 1 was applied, the solvent was evaporated at room temperature, and then the coating layer was cured by ultraviolet rays or electron beams under the following conditions, and various properties of the coating film were examined.
Further, the same examination was carried out when the coating layer was thermally cured under the heating condition of 170 ° C. for 5 minutes. The results are shown in Table-1.

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

Coating method: Two or more (meta) in the molecule relating to the present invention
A composition comprising a polyfunctional monomer or a polyfunctional oligomer (A) having an acryloyl group (A), a substantially water-insoluble organic solvent-soluble polymer (B) and other blends was diluted to 5% with ethyl acetate, and Apply with a coater,
A coating layer having a nonvolatile content of 0.5 μm was formed.

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 was only slightly bumpy, 2: The surface was slightly bumpy, 1: All were bumpy, and the larger the value, the better.

Surface dryness; ◎ Marked by finger touch No stickiness ○ Marked stickiness is slightly felt △ Mark There is some stickiness × Mark There is stickiness Surface hardness: It was carried out based on the method of JIS 5400.

Contact angle: The contact angle was measured at 25 ° C. by dropping 6 μm of n-dodecane or water on the measuring surface and using a goniometer-type contact angle measuring instrument manufactured by Elma.

Corrosion resistance; dip the test piece in 20% sodium chloride solution,
Observe the time until rust is generated on the coating film, and observe it in 5 stages (5:20
0 hours or more, 4: 150 to 200 hours, 3: 100 to 150 hours, 2:50 to 1
It was evaluated at 00 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, a piece of cellophane tape (Sekisui Chemical S-832) was adhered and peeled off at a stretch to show the number of squares left. .

The UV indications in the columns of Examples and Comparative Examples No. indicate the formation of a polymer coating by ultraviolet curing, EB indications indicate electron beam curing, and HEATs indicate heat curing. The symbols A, B, and C in the table represent the compounds in the text, respectively.

As shown in Examples 1 to 7, the examples of the present invention have surface smoothness,
It is found that it has extremely excellent performances in surface dryness, surface hardness, contact angle, salt water resistance and cross-cut test.

On the other hand, Comparative Examples 1 to 10 show the case where one component of the composition of the present invention is absent or other type of additive is blended instead of the polymer of the present invention. In the comparative examples, it is clear that many of the surface properties tested show poor performance.

As described above, the remarkable characteristics of the composition of the present invention can be understood by comparing the examples with the comparative examples.

Examples 8 to 12, Comparative Examples 11 to 15 Next, a coating film was formed on the polyester film with the same composition as the examples shown in Table-1, and the surface smoothness, surface dryness,
The contact angle and the falling angle of n-dodecane, and the friction resistance reducing property were examined. The results are shown in Table-2.

The dynamic friction coefficient is measured according to the American Society for Testing Materials standard D-18.
A friction test jig manufactured by Toyo Baldwin Co., Ltd. was used according to the method of 94 (weight weight: 236 g, tensile strength: 100 m
m / min).

From the above table, a clear difference was observed between the present invention example and the comparative example, demonstrating the relevance of the present invention.

Examples 13 to 14, Comparative Examples 16 to 20 The solvent resistance of the coating film formed on the polyester film was examined, and the results are summarized in Table 3.

Acetone and chloroform were used as the solvent. The coating film-forming film was immersed in acetone for 1 hour and then pulled up, and the state of the coating film was displayed in three stages.

Coating thickness: 15μm From the above table, a clear difference is recognized between the present invention example and the comparative example, and the effectiveness of the present invention is understood.

Examples 15 to 16 and Comparative Examples 21 to 25 The cured protective coating films used in Examples 13 to 14 and Comparative Examples 16 to 20 were examined for weather resistance, light resistance, and humidity resistance.
The results are summarized in Table-4.

The weather resistance was evaluated by a cross-cut test of the adhesion after 1,000 hours of the sunshine weatherometer. For the light resistance, the appearance of the coating film was visually observed after 1,000 hours of irradiation with a fade meter. The moisture resistance was examined by a cross-cut test for the appearance and adhesion of the coating film after 100 hours had passed at 70 ° C and 85% RH.

From the above table, a clear difference was observed between the inventive examples and comparative examples,
The prominence of the present invention has been demonstrated.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09D 175/04 PHN PHW (56) References JP-A 61-97367 (JP, A) JP-A Sho 59-120661 (JP, A) JP 58-34867 (JP, A) JP 54-43244 (JP, A) JP 48-38465 (JP, B1) JP 56-44893 (JP, B2) JP-B-54-15077 (JP, B2) JP-B-52-47763 (JP, B2)

Claims (1)

[Claims] 1. A water-insoluble and organic solvent-soluble average molecular weight of 2,
Polymerization-curable coating film mainly composed of 000 or more perfluoroalkyl group-containing polymer and polymerization-curable polyfunctional monomer and / or polyfunctional oligomer having two or more (meth) acryloyl groups in the molecule Composition.