JPS61272273A - Fluorine-based coating - Google Patents

Abstract

PURPOSE:To obtain the titled coating of good adhesivity to metal, etc. without requiring primer layer, by dissolving, in an organic solvent, a metal chelate compound and ambient temperature-curable fluorine-based polymer consisting essentially of both fluorolefin and vinyl ether. CONSTITUTION:The objective coating can be obtained by dissolving (A) a fluorine-based polymer with a number-average molecular weight 3,000-200,000 (determined by gel permeation chromatography) prepared from (i) 30-70mol%, based on the total mole number, of a fluorolefin, (ii) 20-60mol%, based on the total mole number, of vinyl ether and (iii) 1-25mol%, based on the total mole number, of an organosilicon compound having both olefinic unsaturated bond and hydrolyzable group and (B) a metal chelate compound (e.g., said metal being Ti, Zr, or Al) in (C) an organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a fluorine-based paint that has good adhesive properties, particularly to inorganic materials such as metals.

[Conventional technology]

Weather resistance,
Paints with excellent durability are required, and high-grade exterior paints based on polyester or acrylic are used. but,
Existing paints have a short outdoor service life, and even the above-mentioned high-quality paints lose their aesthetic appearance and substrate protection effect within a few years.

On the other hand, fluoropolymers are extremely stable both thermally and chemically, and have excellent weather resistance, water resistance, chemical resistance, solvent resistance, mold releasability, low friction, and water repellency. Suitable as a surface treatment agent for various substrates. However, conventionally known fluoropolymers suffer from the above-mentioned properties,
It is difficult to dissolve in organic solvents and form a coating film, making it extremely difficult to use as a paint. For example, most of the currently known fluoropolymer paints are powder paints, with only a small amount of PVdF.
(Polyvinylidene fluoride) is simply used as a solvent-dispersed paint by taking advantage of its ability to dissolve in specific solvents at high temperatures.

Moreover, these fluoropolymer paints require baking at a high temperature when forming a film, so their field of use is limited to areas where heating equipment is available. Furthermore, the presence of heating equipment and the baking process are not desirable from the viewpoint of the safety of workers and the environment of the workplace. Therefore, in recent years, attempts have been made to develop fluoropolymers that are solvent-soluble or do not require a baking process at high temperatures.

For example, JP-A-57-34107 discloses a quaternary copolymer consisting of fluoroolefins, cyclohexyl vinyl ethers, alkyl vinyl ethers, and hydroxyalkyl vinyl ethers, and this copolymer is soluble in organic solvents. It is also described that it can be cured at room temperature.

Another patent application filed by the applicant in Japanese Patent Application No. 59-263017 describes a ternary copolymer consisting of a fluoroolefin, a vinyl ether, an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group. It is disclosed that the copolymer is also soluble in organic solvents and can be cured at room temperature.

However, when these fluoropolymers are dissolved in an organic solvent and used as a paint, the coating formed on the base material has excellent weather resistance, chemical resistance, and low friction, but it does not bond well with the base material. There is a problem of poor adhesion, especially to inorganic substrates such as metals.

Therefore, when applying the above-mentioned paint onto a base material, a method is used in which a single layer of primer is formed on the surface of the base material in advance and the paint is applied thereon.

However, with this method, the painting work is complicated, and even though the fluoropolymer film has good properties, the presence of a single layer of primer reduces its solvent resistance and weather resistance. It also causes poor durability of the film.

[Problem that the invention seeks to solve]

Under these circumstances, the inventors of the present invention have conducted repeated studies to develop a solution-type fluorine-based paint that does not require a single layer of primer and can be cured at room temperature and has good adhesive strength even when applied directly onto a substrate. has been reached.

[Means for solving problems]

That is, the present invention is a fluorine-based paint characterized by dissolving a solvent-soluble fluorine-based polymer that can be cured at room temperature and containing a fluoroolefin and a vinyl ether as essential components, and a metal chelate compound in an organic solvent.

[For production]

The fluoropolymer that is the main component of the fluoropolymer of the present invention can be cured at room temperature and has the property of being soluble in organic solvents. Fluorine-based polymers with such properties contain fluoroolefin and vinyl ether as essential monomer components, and further undergo a crosslinking reaction and cure at room temperature in the presence or absence of a curing agent or curing accelerating catalyst. It also contains monomer components with organic functional groups. More specific examples of such fluoropolymers include the following polymers (A) and CB).

(A) A copolymer consisting essentially of (a) a fluoroolefin, (b) a vinyl ether, and (c) an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group; With respect to the total number of moles of (a) to (c) during coalescence, (al: 30 to 70 mol%, (b)
: 20 to 60 mol%, TC): 1 to 25 mol%, and the number average molecular weight (Fln) measured by gel permeation chromatography is 3000 to 2.
00000 fluorine-based polymer, or a copolymer consisting essentially of CB) (d) fluoroolefin, (e) cyclohexyl vinyl ether, (f) alkyl vinyl ether, (phantom hydroxyalkyl vinyl ether), During coalescence (d1 to (dl: 40 to 60 mol%, (e): 5 to 45 with respect to the phantom total number of moles)
Mol%, (f): 5-45 mol%, (g): 3
~15 mol%, and the intrinsic viscosity [η] measured in tetrahydrofuran at 30°C is 0.1 to 2.0 aj/g
fluoropolymer.

Here, the fluoropolymer (A) is a random copolymer consisting of at least the three types of monomer component units (al, (b), and (c) described above. However, this does not impair the purpose of the present invention. and small amounts of other copolymerizable monomer components, such as α-olefins, cycloolefins,
It does not matter if unsaturated carboxylic acids or the like are copolymerized.

The fluoroolefin (a), which is a monomer component constituting the fluoropolymer (A), has at least one fluorine atom in the molecule, and preferably all hydrogen atoms of the olefin are combined with fluorine atoms and other halogen atoms. Perhaloolefins substituted with are preferred. Furthermore, from the viewpoint of polymerizability and properties of the produced polymer, fluoroolefins having 2 or 3 carbon atoms are preferred.

Examples of such fluoroolefins include CF2=C
F2, CHF=CF2, CH2=CF2, CI2=C
HF 5CCIF Engineering CF2, CHCl-CF2, CC
l2=CF2, CCIF=CGIF, CIIP=
CCl2, Cth = CCIF, CCl2 = C
Fluoroethylene type such as GIF, CF3 CF-CF2
, CF3 CF=CIIF 5CF3 CH=CF2
, CF3 CF-CH2, C11F2 CF Gourd CIIF
.

CF3 CH=CH2, CB3 CF=CF2, CH
3CH=CF2, CH3CF=CH2, CF2 CC1
3CF2, CF3 CCI = CF2, CF3 CF
=CFCI, CF2 CICCl =CF2, CF
2 CC13CFCI, CFCl2 CFtomiCF2,
CF3 CCI = CCIF, CF3 CCI
= CCl2, CClF2 CF= CCl2
, CC11CF=CF2 , CF2 CICCl
= CCl2, CFCl2 CCI = C
Cl2, CF3 CF=CHC1, CClF2 C
F=CHC1゜CF3 CCI=CHC1, Cll
F2 CCI = CCl2, CF2 CICI
= CCl2, CF2 CICCl =CHC
1゜CC13CF ” CHCl, CF2 ICF
= CF2, CF2 BrCH=CF2, CF3
CBr=CHBr.

CF2 CICBr −CH2, CH2BrCF=
CCl2, CF3CBr=CH2, CF2
CH=C1lBr.

CF2BrCH=CHF, CF2BrCF-C
Fluoropropene series such as F2, CF3 CF2 CF=
CF2, CF3 CF=CFCF3, CF3 CH=
CH3F3, CF2 = CFCF2 CHF2, C
F3 CF2 CF=CH2, CF3 C11-ClC
F3, CF2 = CFCF2 CH3, CF2
=CHCH2C1h, CF3 CH2C8≠Cf1
2, CF3C3-CHCl3, CF2=CH
CH2CH3, CH3CF2 CH=CH2, CF3C
Br CH=CH2, CH3CF2 CH=CH3,
CH2=CHCH2CI+3, CF3 (cF2
)2 CF=CF2, CF3 (cF2) 3
Examples include fluoroolefins having 4 or more carbon atoms, such as CF=CF2.

Among these, as mentioned above, fluoroethylene and fluoropropene are preferred, with tetrafluoroethylene (cF2 = CF2), chlorotrifluoroethylene (cC13CF2) and hexafluoropropene (cF2 = CHCH2) being particularly preferred; From the viewpoint of safety and ease of handling, hexafluoropropene and chlorotolylfluoroethylene are preferred.

In addition, in the present invention, the fluoroolefins may be used alone or in combination.

Vinyl ether (bl) is a compound in which a vinyl group and an alkyl (including cycloalkyl) group, an aryl group, an aralkyl group, etc. are ether bonded, and among them, an alkyl vinyl ether, especially a carbon atom number of 8 or less, Preferably, an alkyl vinyl ether bonded with 2 to 4 alkyl groups is suitable, and an alkyl vinyl ether in which the alkyl group is a chain is most preferable.

Examples of such vinyl ethers include linear vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, tert-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, octyl vinyl ether, 4-methyl-1-pentyl vinyl ether, etc. Examples include alkyl vinyl ethers, cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether, aryl vinyl ethers such as phenyl vinyl ether, o+, m-, p-)rivinyl ether, and aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether. .

Among these, diluted alkyl vinyl ethers and cycloalkyl vinyl ethers are particularly preferred, and ethyl vinyl ether, propyl vinyl ether, and butyl vinyl ether are more preferred.

In addition, in the present invention, vinyl ethers may be used alone or in combination.

Organosilicon compound (c1 may be any compound having an olefinic unsaturated bond and a hydrolyzable group in the molecule,
Specifically, those shown in the following general formulas [1) to (3) can be exemplified.

R'R25iY'Y2 (1) RX5iY Y (21 RSiY Y Y (3) (In the formula, R' and R have an olefinic unsaturated bond and are composed of carbon, hydrogen and optionally oxygen, and there is They are different groups. Examples include vinyl, allyl, butenyl, cyclohexenyl, and cyclopentagenyl, with terminal olefinically unsaturated groups being particularly preferred.Other preferred examples include terminally unsaturated acid ester bonds. CH2=CH-0-(c1h) 3-1CH2=
C(cH3) COO(cH2) 3-1CH2=
C (clyo)Coo (cH2) 2 -0-
(cH2h-1CH2= C(cH3) C00CH
Groups such as 2CH20CH2CHCH20(cI)l -1H can be mentioned. Among these...
Vinyl groups are optimal. Specific examples of X include monovalent hydrocarbon groups such as methyl, ethyl, propyl, tetradecyl, octadecyl, phenyl, benzyl,
There are groups such as tolyl, which may also be halogen-substituted hydrocarbon groups.

Specific examples of Yl, Y', and Y3 include alkoxy groups such as methoxy, ethoxy, butoxy, and methoxyethoxy; alkoxyalkoxy groups; acyloxy groups such as formyloxy, acetoxy, and propionoxy; )2, -ON TomiCHCH, C2H5
and 10N=C(c4H6) 2 , or substituted amino and arylamino groups such as -NHCH3,
-NHCzH5 and -NH(c6Hs), etc.
Any other hydrolyzable organic group.

The organosilicon compound preferably used in the present invention is a compound represented by the general formula (3), particularly the group Y1,
Organosilicon compounds in which Y' and Y3 are equal are suitable. Among these, R' is a vinyloxyalkyl group (cI+2
=CHO(cH2)n) or a vinyl group, and Y
' - Y3 is preferably an alkoxy group or an alkoxyalkoxy group, such as vinyloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(methoxyethoxy)
Examples include silane. However, vinylmethyljethoxysilane, vinylphenyldimethoxysilane, etc. can be used as well.

The content ratio of the 7-mer components (al to (c)) in the fluoropolymer (A) is (a): 30 to 70 mol%, ('b) based on the total number of moles of (a) to (c). ):20~
60 mol%, (c): 1 to 25 mol% ((a) +
(b) + (c) = 100), many (is (
a): 40 to 60 mol%, (b): 20 to 50 mol%,
(c): In the range of 5 to 20 mol%.

The molecular weight can be determined using gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and monodisperse polystyrene of known molecular weight as a standard substance.
) The number average molecular weight (Fin) measured by
It is in the range of 0. By adopting such a composition ratio and molecular weight, it becomes solvent soluble and has excellent film coating properties, and after being cured by the method described below, it has excellent solvent resistance, chemical resistance, weather resistance, heat resistance, and mechanical resistance. It has excellent physical properties.

Another property of the fluoropolymer (A) is that it is non-quality or has low crystallinity, and is often non-quality. In general, the degree of crystallinity by X-rays is 0%, and the differential scanning calorimetry needle (D
In many cases, no melting point is observed in SC). Therefore, transparency is good.

The glass transition temperature (Tg), when measured by DSC at a heating rate of 10°C/min after cooling the sample to -120°C, is usually in the range of -60 to +20°C, and mostly in the range of -40 to +5°C.

As an optical property, there is a refractive index (no), which is usually 1.48.
~1.34, often in the range 1.44-1.36.

In order to produce a fluoropolymer, the method described in detail above (al
It is possible by copolymerizing each monomer of ~(c1) in the presence of a well-known radical initiator. Here, (al~(
Each component of c) is important; for example, copolymerization does not occur with components (a) and (c) alone, but by adding component (b), (al, (b), and (c)) Each component is copolymerized.

Various known radical initiators can be used for copolymerization. Specifically, organic peroxides, organic bersesters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2
,5-di(peroxybenzoate)hexyne-3,1
, 4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butylberacetate, 2,5-dimethyl-2,5-di(t
tert-butylperoxy)hexane-3,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylberbenzoate, tert
tert-butylperphenylacetate, tert-butylperisobutyrate, tert-butylberu 5e
c-octoate, tert-butylperpivalate,
Other azo compounds such as azobis-isobutylnitrile, dimethylazoisobutyrate, etc. Among these are dicumyl peroxide,
Di-tert-butylperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane-3,2,5-dimethyl-2,5-di(tert-lytylperoxy)hexane, 1, 4-bis(tert-
Dialkyl peroxides such as butylperoxyisopropyl)benzene are preferred.

The copolymerization takes place in a reaction medium consisting of an organic solvent. Solvents used here include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as n-hexane, cyclohexane, and n-heptane, chlorobenzene, bromobenzene, iodobenzene, O-bromotoluene, etc. and halogenated aliphatic hydrocarbons such as tetrachloromethane, 1.1.1-trichloroethane, tetrachloroethylene, and 1-chlorobutane.

Copolymerization is carried out by adding a radical initiator to the above solvent in a molar ratio of 10 to 2×10' based on the total number of moles of monomers. The polymerization temperature is -30 to 200℃, preferably 20 to 100℃, and the polymerization pressure is 0 to 100kg/-・G.
, preferably 0 to 50 kg/cd·G.

Like (A), the fluoropolymer (B) which is solvent-soluble and can be cured at room temperature is an alternating copolymer consisting of at least the four types of monomer components (dl to (a) described above. A small amount of other copolymerizable monomer components may be copolymerized within a range that does not impair the purpose of the invention.

The fluoroolefin (d), which is a monomer component constituting (B), is as described above. The alkyl vinyl ether (fl or hydroxyalkyl vinyl ether) contains a linear or branched alkyl group having 2 to 8 carbon atoms, preferably one having 2 to 4 carbon atoms.

The ratio of the monomer components (d1 to (g)) in the fluoropolymer CB) is (d) to (with respect to the phantom total number of moles).
di: 40-60 mol%, fe): 5-45 mol%
, (f): 5 to 45 mol%, (along: 3 to 15 mol%
, mostly (d): 45-55 mol%, (e): 10
~30 mol%, (f) 10-30 mol%, (gl: 5
~13 mol%.

In addition, its molecular weight is measured in tetrahydrofuran at 30°C with an intrinsic viscosity [η] of 0.1 to 2, Od1/g, and most are 0.15 to 0.8 d! / g, especially 0.2-0
．． 5d! /g.

It is. Further details of the fluoropolymer (B) and the polymerization method are described in JP-A-57-34107.

The metal chelate compound, which is another component of the paint of the present invention, is
Basically, any known metal chelate compound may be used. For example, as the central metal forming the chelate, TI%AI, Zrs Co, Mn, etc. can be used. Among them, Ti, Zr, and AI are preferred, and chelate compounds having Ti or Zr as the central metal are particularly preferred. A metal chelate compound can be easily obtained by reacting an alkoxide of the above metal with a chelating agent.

Examples of chelating agents include acetylacetone, 2
, β-diketones such as 4-hebutanedione, ketoesters such as methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, lactic acid, salicylic acid, malic acid, tartaric acid, methyl lactate, ethyl lactate, ethyl salicylate, phenyl salicylate, apple Hydroxycarboxylic acids or their esters or salts thereof, such as ethyl acid, methyl tartrate, ethyl tartrate, ammonium lactate, 4-hydroxy-
Kettle alcohols such as 4-methyl-2-pentanone, 4-hydroxy-2-pentanone, 4-hydroxy-2-heptanone, 4-hydroxy-4-methyl-2-heptanone, monoethanolamine, jetanolamine, N - Amino alcohols such as methyl-monoethanolamine, N-ethyl-monoethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, malonic acid diethyl ester, methylolmelamine, methylolurea, methylol acrylamide, etc. enol-type active hydrogen compounds and the like. In the present invention, from the viewpoint that the fluoropolymer as the main component is transparent, a transparent coating can be obtained by using a colorless or light-colored metal chelate compound.

Examples of such colorless to light-colored metal chelate compounds include Ti (0-iC3H7) 2 (oc, o, 6o
) 2, Ti (0-n(,4Hq) 2 (oc
8tt, 6o) 2.0■ Ti(0C3H7)2 (cH3CHCOOC285)
2, Zr(QC4■q)3 (c5Hwa02), etc.

The fluorine-based paint of the present invention is obtained by dissolving a solvent-soluble fluorine-based polymer that can be cured at room temperature and a metal chelate compound in an organic solvent. The ratio of the fluoropolymer to the metal chelate compound is 1 to 70 parts by weight, preferably 3 to 60 parts by weight, per 100 parts by weight of the polymer. If the proportion of metal chelate is too low, no improvement in adhesion is observed, and if it is too high, the coating film becomes brittle.

Examples of organic solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether and dipropyl ether, alcohols such as ethanol, and trichloromethane. , dichloroethane, and halogenated hydrocarbons such as chlorobenzene.

When the fluoropolymer (A) is the main component of the fluorine-based paint of the present invention, it has a hydrolyzable organic group derived from an organosilicon compound [C1], so it is not exposed to moisture. This causes a cross-linking reaction between the molecular chains of the polymer, resulting in curing. Therefore, as a matter of course, moisture in the atmosphere can also cause crosslinking.

In the case of (B), it can be cured by heating using a melamine curing agent, a urea resin curing agent, a polybasic acid curing agent, etc., or it can be cured at room temperature using a polyvalent isocyanate.

Due to the presence of the metal chelate compound, the fluorine-based paint of the present invention has improved adhesive strength to inorganic substrates such as metal and ceramic substrates, and can be directly coated without a single layer of primer. Therefore, the characteristics of the cured fluoropolymer film can be fully exhibited, and there is no fear that the primer layer will be attacked by, for example, organic solvents or light and the film will peel off from the primer layer. Furthermore, when the fluoropolymer (A) is used, the film dries quickly to the touch and exhibits a curing accelerating effect similar to that obtained by adding a silanol condensation catalyst.

The fluorine-based paint of the present invention is applied to the surfaces of metal, wood, plastic, ceramic, paper, glass, etc. using a brush, spray, roller coater, etc. in the same way as ordinary liquid paints.

After curing, the film has weather resistance, chemical resistance, solvent resistance, water resistance,
It has excellent heat resistance and low friction, as well as excellent transparency and gloss. Further, pigments and dyes may be blended to form a colored paint, and if necessary, various additives commonly blended with synthetic resins may be blended.

〔Example〕

The content of the present invention will be explained below using preferred examples, but unless otherwise specified, the present invention is not limited to these examples, and any embodiments are possible without impairing the purpose of the present invention. .

[Reference experiment]

The fluoropolymer used in the examples was polymerized in the following manner.

80 g of benzene, 1 ethyl vinyl ether (EV
E) 14.7g, butyl vinyl ether (BVE)
3g, trimethoxyvinylsilane (TMVS)8.
8 g of dilauroyl peroxide and 1 g of dilauroyl peroxide were charged, solidified with acetone and dry ice, and degassed to remove oxygen from the system. After that, hexafluoropropene (RFP) 4
7 g was introduced into an autoclave and the temperature was raised. When the temperature inside the autoclave reaches 65℃, the pressure is 8.1
kg/cIa. The reaction was continued for 8 hours with stirring, and when the pressure reached 4.6 kg/ci, the autoclave was cooled with water to stop the reaction. After cooling, the unreacted upper part was expelled, the autoclave was opened, and the reaction solution was taken out. After concentration, the mixture was washed with a benzene-methanol mixed solvent, concentrated again, and dried.

The number average molecular weight of the obtained polymer by GPC was 8×1
It was 0.

In addition, compositional analysis was performed using elemental analysis and NMR, and HFP/EVE/BVE/TMVS=50/35/
The molar ratio was 5/10.

Table 1 also shows the polymerization results obtained by changing the type and amount of hexamer.

Example 1 Dipoxy titanium bisoctylene glycolate 70% butanol solution (Orgatics [F] TC200, Matsumoto Pharmaceutical Department) was added to 100 parts by weight of the fluoropolymer of Experimental Example 1 at the weight part ratio shown in Table 2. 100 parts by weight of toluene was added and mixed with stirring to obtain a fluoropolymer solution. Next, the solution was applied to a steel plate using a 50μ applicator, and after being left at room temperature for 7B, a base peel test, a 24-hour immersion test in acetone, a 24-hour immersion test in toluene, and a pencil hardness test (JI
SK 5400-1979.6.14') was carried out. The results are shown in Table 2.

Incidentally, the substrate peeling test was conducted in the following manner. In other words, rJIs K is applied to the surface of the coating film applied to the steel plate.
A cut was made in accordance with ``5400-1979 Paint General Test Method 6.15 Base Test''. Next, apply a 20 m wide cellophane adhesive tape to the surface of the paint film at the base grains, rub it strongly with a 7-tsuru spatula to bring the tape into close contact with the paint surface, and then quickly move the cellophane tape vertically upwards. I pulled it up and peeled it off. This cellophane tape was adhered and peeled off a total of four times from each direction of the four sides of the base grains, and the number of base grains that remained without being removed was determined, and the test results were expressed as the number.

Example 2 The titanium compound in Example 1 was converted into diisopropoxytitanium acetylacetonate (Orgaticus[F]TC1
00, Matsumoto Pharmaceutical Co., Ltd.) The same procedure was carried out except that 75% isopropanol solution was used. The results are shown in Table 3.

Example 3 The solution used in Example 1 was applied to a steel plate at different thicknesses,
A substrate peeling test was conducted after curing at room temperature for 7 days. The results are shown in Table 4.

Example 4 A test was conducted in the same manner as in Example 1 except that the titanium compound in Example 1 was replaced with a 75% butanol solution of acetylacetone zirconium butoxide.

The results are shown in Table 5.

Example 5 When a test was conducted in the same manner as in Example 1 except that the titanium chelate in Example 1 was replaced with 10 parts by weight of aluminum dibutoxide monoethyl acetate, no peeling was observed in the base weight peeling test.

Examples 6 to 10 70% dibutoxytitanium bisoctylene glycolate to 100 parts by weight of each fluoropolymer of Experimental Examples 2 to 6
25 parts by weight of the butanol solution and 100 parts by weight of toluene were added to obtain a fluoropolymer solution.

The subsequent steps were the same as in Example 1. The results are shown in Table 6.

Example 11 Chlorotrifluoroethylene, ethyl vinyl ether,
Cyclohexyl vinyl ether, T-hydroxybutyl vinyl ether, each 50.25.15.10 mol%
(Intrinsic viscosity [η] measured in tetrahydrofuran at 30°C is approximately 0.4 d!/g) 100
parts by weight and 100 parts by weight of xylene, ORGATIX TC1
When a solution of 0.00.15 parts by weight was applied and cured in the same manner as in Example 1, no peeling was observed in the substrate-peeling test and immersion in acetone/toluene.

〔Effect of the invention〕

The fluorine-based paint of the present invention: ■ Can be applied to substrates with a brush, spray, roller coater, etc. in the same way as ordinary liquid paints, ■ Cures at room temperature and does not require a baking process, ■ Has excellent transparency, etc. Provides a film with excellent optical properties, weather resistance, chemical resistance, mechanical properties, low friction, and water repellency. ■ For inorganic substrates such as metal plates and ceramic products, and organic substrates such as plastic products. It has the following characteristics: strong adhesion without the need for a brimer. More specifically, fluoropolymer (A
Fluorine-based paints whose main component is CB) do not require a hardening agent, so they can be used as a one-component paint, and fluorine-based paints whose main component is CB) can be used as a two-component paint with a hardener. . Therefore metal, wood 1. It can be used as a coating agent for plastics, ceramics, paper, etc., and as a surface coating for optical fibers, optical disks, and liquid crystal display substrates.

Claims (4)

[Claims] (1) A solvent-soluble fluoropolymer that can be cured at room temperature and contains a fluoroolefin and a vinyl ether as essential components,
and a metal chelate compound dissolved in an organic solvent. (2) The fluoropolymer is (a) fluoroolefin, (
b) a vinyl ether; (c) an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group;
(a): 30 to 70 mol%, (b): 20 to 60 mol%, and (c): 1 to 25 mol% with respect to the total number of moles of ~(c), and gel permeation chromatography The number average molecular weight (@M@n) measured by the method is 3000
200,000. The fluorine-based paint according to claim 1. (3) The fluoropolymer is (d) fluoroolefin, (
e) A copolymer consisting essentially of cyclohexyl vinyl ether, (f) an alkyl vinyl ether, and (g) a hydroxyalkyl vinyl ether, with respect to the total number of moles of (d) to (g) in the copolymer. Te (d): 4
0 to 60 mol%, (e): 5 to 45 mol%, (f): 5
~45 mol%, (g): 3 to 15 mol%, and 30
The fluorine-based paint according to claim 1, which has an intrinsic viscosity [η] of 0.1 to 2.0 dl/g as measured in tetrahydrofuran at ℃. (4) The fluorine-based paint according to any one of claims 1 to 3, wherein the metal chelate compound is a chelate compound of a metal selected from Ti, Zr, and Al.