JPH03212464A - Fluorine-based coating compound - Google Patents

Abstract

PURPOSE:To obtain the title coating compound having excellent shelf stability, comprising a fluorine-based copolymer prepared by copolymerizing fluoroolefin with a specific radically polymerizable monomer and a specific organosilicon compound as a coating film-forming component. CONSTITUTION:The objective coating compound comprising a fluorine-based copolymer prepared by copolymerizing (A) a fluoroolefin (preferably chlorotrifluoroethylene) with (B) a radically polymerizable monomer (preferably 4-vinyloxybutoxytrimethylsilane) containing an olefinic unsaturated bond and a group which will be hydrolyzed into hydroxyl group and is bonded to carbon, (C) an organosilicon compound (preferably vinyltrimethoxysilane) containing an olefinic unsaturated bond and a group which will be hydrolyzed into hydroxyl group and is bonded to silicon and preferably (D) an alkyl vinyl ether as a coating film-forming component.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a fluorine-based paint, and more particularly, to a fluorine-based paint that has particularly excellent storage stability.

[Conventional technology]

BACKGROUND ART Paints with excellent weather resistance and durability are required for the exterior of buildings, vehicles, ships, aircraft, etc., and high-quality polyester-based or acrylic-based exterior paints are used. However, 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.

Fluorine-based copolymers are extremely stable both thermally and chemically, and have excellent properties such as weather resistance, chemical resistance, solvent resistance, water resistance, water repellency, and low friction. It is expected to be applied to functional paints.

However, on the other hand, since fluorine-based copolymers are insoluble or poorly soluble in solvents at room temperature, there are problems in that they cannot be used as solution-type coatings and that they have poor adhesion to substrates.

[Problem to be solved by the invention]

The purpose of the present invention is to dissolve in organic solvents at room temperature, harden at room temperature, and have weather resistance, chemical resistance, solvent resistance, water repellency, low friction, water resistance, heat resistance, transparency, etc. An object of the present invention is to provide a fluorine-based paint that has excellent adhesion, extensibility, and storage stability while maintaining the excellent properties of the fluorine-based copolymer.

[Means to solve the problem]

The present invention relates to the following fluorine-based paint.

(1) (a) fluoroolefin, (b) a radically polymerizable monomer having an olefinic unsaturated bond and a group that becomes a hydroxyl group when hydrolyzed is bonded to a carbon atom, and (c) Contains as a coating film-forming component a fluorine-based copolymer obtained by copolymerizing an organosilicon compound that has an olefinic unsaturated bond and a group that becomes a hydroxyl group when hydrolyzed is bonded to a silicon atom. A fluorine-based paint that is characterized by

(2) (a) Fluoroolefin, (b) A radically polymerizable monomer having an olefinic unsaturated bond and a group that becomes a hydroxyl group when hydrolyzed is bonded to a carbon atom, (c) Olefin A fluorine-based copolymer obtained by copolymerizing an organosilicon compound that has a sexually unsaturated bond and a group that becomes a hydroxyl group when hydrolyzed is bonded to a silicon atom, and (d) an alkyl vinyl ether. A fluorine-based paint characterized by containing it as a film-forming component.

In the fluorine-based paint of the present invention, the fluorine-based copolymer used as a coating film-forming component is fluoroolefin (a).
, a radically polymerizable monomer (b) having an olefinically unsaturated bond and having a group bonded to a carbon atom that becomes a hydroxyl group upon hydrolysis; A random copolymer obtained by copolymerizing an organosilicon compound (c) in which a group that decomposes to become a hydroxyl group is bonded to a silicon atom, or the above (,)
In addition to or C), further alkyl vinyl ether (
It is a random copolymer obtained by copolymerizing d).

The fluoroolefins (a) include perfluoroolefins or perfluoroolefins having at least one fluorine atom in the molecule, preferably in which all the hydrogen atoms of the olefin are replaced with fluorine atoms, or with fluorine atoms and other halogen atoms. Perhaloolefins are preferred, and from the viewpoint of polymerizability and properties of the resulting copolymer, those having 2 or 3 carbon atoms are preferred.

Specifically, such fluoroolefins (a) include CF2=CF2, CHF=CF2, CH,=CF,
, CH2=CHF, CHF=CF2, CHCQ:CF2
, CF2=CF2, CCQF=CCQF, CH=CH2
, CH2=CHF, CCQ, =CCnF and other fluoroolefins having 2 carbon atoms (fluoroethylene type); CF
, CF=CF2, CF, CF=CHF, CF, CH
=CF, CF, CF=CH2, CHF, CF=CH
F, CF, CH=CH,, CH, CF=CF2, CH,
CH=(1,F2,CH3CF=CH,,CF2(4C
F=CF2, CF, CF2=CF2, C'F3CF=C
FCQ, CF, CQCCQ=CF2, CF2CQCF=
C.F.C.Q.

CF(,Q2CF=CF2,CF,CCU=CCnF,
CF, CH=CH2, CCQF2CF=CCQ2, CC
,Q, CF=CF2, CF2Cf1CC4=CCQ2
, CFCQ2CCQ: CCQ2, CF, CH=CH2Ω
, CCQF2CF=CHCQ, CF2CH=CHCQ,
CHF, CH=CH2, CF2CMCFI=CCQ2,
CF2C (lccQ=cHcQ, CCQ, CF3CBr
, Q, CF2=CF=CF2, CF2BrCH=CF2
．． CF3CBr:CHBr, CF2Cf1CBr:CH
2, CH2BrCF: CCQ2, CF, CBr=CH2
, CF2CH=CHBr, CF2BrCH=CHF,
CF2=CF2fluoroolefin (fluoropropene type); CF3CH=CHCF3, CF, =CFCF2C
CQF,,CF2=CF2(42CCQ,,CH2:C
FCCQ, 2CCQ3, CF3(cF2)2CCQ=
CF2, CF 3 (cF z ) a CCQ = CF
2, CF a CF 2 CF = CFz, CF
, CF=CFCF3, CF3CH=CHCF3, CF
2=CFCF2CHF2. CF, CF, CF=CH2,
CF3CH=CHCF3, CF, =CFCF2CH□
, cF2=CFCH2CH3, CF, CH2CH=CH
2, CF2CH=CH2H, CF, =CHCH2C
H,,CH,CF2CH=CH2,CFH,CH=C)
ICFI(,, CHa CF 2 CH” CH2, C
H,=CFCI(2CH,, CF, (cF2), C
Examples include fluoroolefins having 4 or more carbon atoms, such as F=CF2, CF, (cF2)3CF=CF2.

Among these, as mentioned above, fluoroethylene and fluoropropene are preferred, and fluoroethylene and fluoropropene, in which all hydrogen atoms are replaced with fluorine and chlorine atoms, are particularly preferred, and among these, chlorotrifluoroethylene (cCΩF =CF2) is suitable.

The fluoroolefins (a) may be used alone or in combination of two or more.

The radically polymerizable monomer (b) having an olefinic unsaturated bond and a group that becomes a hydroxyl group when hydrolyzed is bonded to a carbon atom is represented by the following general formula [I] or (II). The compounds represented are listed below.

(In the formula, R1 is an alkylene group having 1 to 1 o carbon atoms, R2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and Z is a hydrolyzable group.) The above general formula (1) or [■] Examples of Z include tetrahydropyranyl group, 4-methoxytetrahydropyranyl group, 3-bromotetrahydropyranyl group, tetrahydrofuranyl group, ■-ethoxyethyl group, l-methyl-
1-methoxyethyl group, l-inpropoxyethyl group,
Trimethylsilyl group, triethylsilyl group, isopropyldimethylsilyl group, tert-butyldimethylsilyl group, methyldiisopropylsilyl group, tert-butyldiphenylsilyl group, methyldi-tert-butylsilyl group, tribenzylsilyl group, tri-p-xylylsilyl group, triisopropyl group Examples include silyl group and triphenylsilyl group.

Specific examples of the compounds represented by the general formula (1) include 1, for example, 4-vinyloxybutyltetrahydrobilanyl ether, 2-vinyloxyethyltetrahydrobilanyl ether, 4-vinyloxybutyl-1'-ethoxyethyl ether, and 2-vinyloxybutyltetrahydrobilanyl ether. Vinyloxyethyl-17-ethoxyethyl ether, 4-vinyloxybutoxytrimethylsilane, 2-vinyloxyethoxytrimethylsilane, 4-vinyloxybutoxytriethylsilane, 2-vinyloxyethoxytrimethylsilane, 4-vinyloxybutoxyisopropyldimethylsilane, 2 -Vinyloxyethoxyisopropyldimethylsilane and the like.

Specific compounds represented by the general formula (n) include, for example, 2-acryloyloxyethyltetrahydropyranyl ether, 2-methacryloyloxyethyltetrahydropyranyl ether, 2-acryloyloxyethyl-1'-ethoxyethyl ether, and 2-acryloyloxyethyltetrahydropyranyl ether. Methacryloyloxyethyl-1'-ethoxyethyl ether, 2
-acryloyloxyethoxytrimethylsilane, 2-
Methacryloyloxyethoxytrimethylsilane, 2-
Acryloyloxyethoxytriethoxysilane, 2-
Methacryloyloxyethoxytriethoxysilane, 2
-acryloyloxyethoxyisopropyldimethylsilane, 2-methacryloyloxyethoxyisopropyldimethylsilane, and the like.

Among the specific compounds represented by the general formula (1) or [■], compounds in which Z is a trialkylsilyl group are preferred, and 4-vinyloxybutoxytrimethylsilane is particularly preferred.

The radically polymerizable monomer (b) may be used alone or in combination of two or more.

Organosilicon compounds (c) having an olefinic unsaturated bond and in which a group that becomes a hydroxyl group upon hydrolysis is bonded to a carbon atom are represented by the following general formulas [■] to (V). Examples include compounds.

R3R'SiY" Y2...[■]R
3X1SIY1Y2・= (TV ]R35iY”Y
” Y3 ... [■] (In the formula, R3,
R4 has an olefinic unsaturated bond and is composed of a carbon atom, a hydrogen atom, and optionally an oxygen atom, each of which represents the same or different groups.

xl is an organic group having no olefinic unsaturated bond, Y"
, Y2 and Y3 each represent the same or different hydrolyzable groups. ) Specific examples of R3 or R4 include a vinyl group, an allyl group, a butenyl group, a cyclohexenyl group, a cyclopentagenyl group, and a terminal olefinically unsaturated group is particularly preferred. . Further, R3 or R4 has an ester bond of a terminal unsaturated acid.

CH2=CHCOO(cH□)3-1 CH2=C(cH3)COO(cH2), -1CH2=
C (cH,)Coo (cH2)2-0- (cH,)
3-1CH□=C(cH3)C00CH2CH20CH
It may also be a group such as 2CHCH20(cH2L-H). Among these, R3 and R
It is preferable that 4 does not contain an oxygen atom and is composed of a carbon atom and a hydrogen atom, and a vinyl group is particularly suitable.

Specifically, xl includes a methyl group, an ethyl group, a propyl group, a tetradecyl group, an octadecyl group, a phenyl group,
Examples include monovalent hydrocarbon groups such as benzyl group and 1-lyl group. These groups may be halogen-substituted hydrocarbon groups.

Yl, Y2 or Y3 specifically includes an alkoxy group or an alkoxyalkoxy group such as a methoxy group, an ethoxy group, a butoxy group, or a methoxyethoxy group; an acyloxy group such as a formyloxy group, an acetoxy group, or a propionoxy group; -0N=C (cH3)2.0N=CHC82C2
Oximes such as H6, -0N=C(cc Hs) 2;
Other arbitrary hydrolyzable organic groups can be mentioned.

As the organosilicon compound (c), a compound represented by the general formula [■] is preferable, and an organosilicon compound in which Yl, Y2, and Y3 are the same is particularly preferable. Among these, organosilicon compounds in which R3 is a vinyl group and Y1 to Y3 are an alkoxy group or an alkoxyalkoxy group are particularly preferred, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(methoxyethoxy)silane, and the like. Also preferably used are vinyloxypropyltrimethoxysilane, vinylmethyljethoxysilane, vinylphenyldimethoxysilane, and the like.

The organosilicon compound (c) may be used alone or in combination of two or more.

As the alkyl vinyl ether (d), a compound in which a vinyl group and an alkyl group are bonded via an ether bond can be used.

Examples of such alkyl vinyl ether (d) include ethyl 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, and 4-methyl-1
- Chain alkyl vinyl ethers such as pentyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether;

Among these, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether and the like are particularly preferred.

Alkyl vinyl ether (d) may be used alone,
Moreover, two or more types may be mixed and used.

Component (a) or c) in the fluorine-based copolymer or (
a) None (d) The content ratio of component (a) is 25 to 60
mol%, preferably 30-55 mol%, (b) is 0.5
~60 mol%, preferably 1-50 mol%, (c) is 1
~25 mol%, preferably 3-20 mol%, (d) is 0
~50 mol%, preferably 10-40 mol%.

The fluorine-based copolymer may be a copolymer consisting only of (a) to c) or (a) to d), but in addition to these components, there may be Small amounts of other copolymerizable monomers, such as α-olefins,
Cycloolefins, vinyl carboxylates, allyl carboxylate esters, etc. may be copolymerized.

The average molecular weight of the fluorine-based copolymer is a number average molecular weight of 3,000 to 200,000, preferably 4 as measured by gel permeation chromatography (GPC).
000 to 100,000 is desirable.

The fluorine-based copolymer has 1, for example, benzene,
Aromatic hydrocarbons such as toluene and xylene; acetone,
Ketones such as methyl ethyl ketone; diethyl ether,
Ethers such as dipropyl ether, methyl cellosolve, and ethyl cellosolve; esters such as ethyl acetate and butyl acetate; alcohols such as ethanol; halogenated hydrocarbons such as nitrichloromethane, dichloroethane, and chlorobenzene; and mixtures thereof. dissolve.

The fluorine-based copolymer used in the present invention can be produced by copolymerizing the above monomers in the presence of a known radical initiator.

Various known radical initiators can be used as such radical initiators. Specifically, organic peroxides, organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t
ert-butyl peroxide, 2,5-dimethyl-2,
5-di(peroxybenzoate)hexyne-3,1,
4-bis(tert-butylperoxyisopropyl)
Benzene, lauroyl peroxide, dilauroyl peroxide, tert-butyl peracetate, 2,5
-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(ta
tert-butyl peroxy)hexane, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl perisobutyrate, tert-butylperoxy)hexane
tert-butylperu 5ec-octoate, tert-butyl perpivalate, cumyl perpivalate, tert
-Azo compounds such as butyl perdiethyl acetate,
For example, azobis(isobutyronitrile), dimethylazoisobutyrate, etc. are used. Among these are dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2,5-
Di(tert-butylperoxy)hexane, ■, 4-
Dialkyl peroxides such as bis(tert-butylperoxyisopropyl)benzene are preferred.

The copolymerization reaction is preferably carried out in a reaction medium consisting of an organic solvent. Such organic solvents include benzene,
Aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as n-hexane, cyclohexane, and n-hebutane;
Chlorobenzene, bromobenzene, iodobenzene, O
- Halogenated aromatic hydrocarbons such as bromotoluene; halogenated aliphatic hydrocarbons such as tetrachloromethane, 1,1.1-trichloroethane, tetrachloroethylene, 1-chlorobutane, etc. can be used.

The copolymerization reaction is carried out using a radical initiator in a molar ratio of I x 1 to the total number of moles of monomers in a reaction medium as described above.
It is preferable to add in a range of 0-2 to 2 x 10-3. The polymerization temperature is -30 to 200°C, preferably 2
0-100°C1 polymerization pressure is O-100kg/aI-G
, preferably 0 to 50 kg/ff1-G, reaction time 0
．． Desirable time is 5 to 60 hours, preferably 2 to 30 hours.

In addition, when producing a fluorine-based copolymer using a fluoroolefin containing chlorine as the fluoroolefin (a), a chlorine scavenger is added to the system during the polymerization reaction and/or during the purification of the obtained copolymer. It is desirable to leave it present.

As such a chlorine scavenger, the following compounds (a) to (c) can be used.

(A) MxAfly(OH)zx+ay-2z(A)z
-aHzO (wherein M is Mg, Ca or Zn,
A is CO or HPO4, x, y, z are positive numbers, and a is O or a positive number. ) is a complex compound represented by

Specific examples of such complex compounds (a) include the following compounds.

Hg6AQz (OH)□6CO3'48zO1Mgs
Al2 (OH)2 o CO3・5H20, Mg5
Affz (OH)x4c03・4H20, Mgx. A
l2(OH)2□CO,・4020, Mgs AQz
(OH)t 6 HPO4・4H20, Ca, Al2(
OH),, Co3・4H20, Zn, Al2G (OH
)16cO3・4820 Such a complex compound (a) may be a compound that is not exactly represented by the above formula, for example, a compound in which part of the OH of Mg2AQ (OH)i・3H20 is replaced with CO3. Mgs −
It may be a compound such as s AQz (OH) t a CO3·3.5H,0. Also, these compounds are
Crystal water may have been removed.

In these complex compounds (a), M is Mg,
Compounds in which A is 003 are preferred.

(b) Basic compound of alkaline earth metal As the basic compound (b) of alkaline earth metal, specifically, MgO1C
Alkaline earth metal oxides such as aO; Mg(OH)z, C
Alkaline earth metal hydroxide such as a(OH)z; MgC0
, , CaC0, and other alkaline earth metal carbonates.

Such basic compounds (b) of alkaline earth metals are
(Agco,)z.Mg(OH)z.5H20 and other double salts may be used, and these compounds may have water of crystallization removed.

Among these alkaline earth metal basic compounds (b), Mg-containing compounds are preferred.

(c) Epoxy group-containing compound Epoxy group-containing compound (c) specifically includes γ-glycidoxypropyltrimethoxysilane, β-(3,4
Examples include silicon-containing epoxy compounds such as -epoxycyclohexyl)ethyltrimethoxysilane; aliphatic epoxy compounds such as trimethylolpropane polyglycidyl ether and neopentyl glycol diglycidyl ether.

Among these, silicon-containing epoxy compounds such as γ-glycidoxypropyltrimethoxysilane are preferred.

Among the chlorine scavengers mentioned above, chlorine scavengers that are inorganic compounds react faster with chlorine (hydrochloric acid) than chlorine scavengers that are organic compounds, and do not dissolve in polymerization or purification systems. Therefore, it is preferably used because it can be easily removed from the system. Particularly preferred are the composite compounds shown in (a).

By making the chlorine scavenger present during the polymerization reaction, during the purification of the obtained copolymer, or both, coloring of the obtained fluorine-based copolymer can be effectively prevented. In particular, by allowing a chlorine scavenger to be present in the system during the polymerization reaction, coloring of the resulting fluorine-based copolymer can be effectively prevented.

In addition, when the obtained fluorine-based copolymer is purified with alcohol, a chlorine scavenger is present in the system, and this fluorine-based copolymer is dissolved in the organic solvent described below to form a paint. When a paint is applied to a base material such as metal to form a coating film, it is possible to effectively prevent rust from forming on the base material.

When a chlorine scavenger is used during the polymerization reaction, the amount of chlorine scavenger is 0.0% per mole of chlorine atom contained in the fluoroolefin (a).
It is desirable to use amounts of 5 to 100 g, preferably 1 to 70 g.

When a chlorine scavenger is used during purification, it is desirably used in an amount of 0.5 to 100 g, preferably 1 to 70 g, per 100 g of the obtained fluorine-based copolymer.

By dissolving the fluorine-based copolymer obtained as described above in an organic solvent, the fluorine-based coating material of the present invention having particularly excellent adhesiveness, elongation properties, and storage stability can be obtained.

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; trichloromethane, dichloroethane, and chlorobenzene. and mixtures thereof.

There is no particular restriction on the amount of organic solvent used.

Since the fluorine-based copolymer used in the present invention contains hydrolyzable organic groups derived from components (b) and (c), cross-linking occurs between the molecular chains of the copolymer upon contact with moisture. A reaction occurs and hardens. Therefore, naturally, crosslinking can occur due to moisture in the atmosphere. However, in the fluorine-based paint of the present invention, it is preferable to add a curing catalyst such as a silanol condensation catalyst so that the coating film of the fluorine-based copolymer applied to the substrate is rapidly cured.

In this case, it is preferable that the first solution prepared by dissolving the fluorine-based copolymer in an organic solvent and the second solution prepared by dissolving the silanol condensation catalyst in an organic solvent are mixed immediately before use.

Known silanol condensation catalysts can be used, such as dibutyltin dilaurate, stannous acetate, stannous octoate, dihydroxydibutyltin chloride, dihydroxybutyltin dichloride, dihydroxybutyltin octoate, dihydroxybutyltin laurate, lead naphthenate, - Carboxylic acid metal salts such as iron ethylhexanoate and cobalt naphthenate; metal hydroxides; acids such as mineral acids and organic fatty acids. Among these, tin hydroxide compounds and alkyltin salts of carboxylic acids are preferred, and dihydroxybutyltin laurate and dibutyltin dilaurate are particularly preferred.

Such a curing catalyst is used in an amount of 0.03 to 30 parts by weight, preferably o, 1 to 10 parts by weight, based on 100 parts by weight of the fluorine-based copolymer.
Preferably, it is used in parts by weight.

The curing reaction (crosslinking reaction) of the fluorine-based paint of the present invention is carried out at room temperature (
Although the reaction proceeds satisfactorily at a temperature of 0 to 40'C), the reaction may be carried out under heating if necessary.

In addition to the fluorine-based copolymer, the paint contains pigments, dyes, dehydrating agents (trimethyl orthoformate, etc.), dispersants, other paint additives (leveling agents, wetting agents, etc.), and alkyl silicates as necessary. and their oligomers, as well as their hydrolysates (tetramethylorthosilicate oligomers, etc.) may be blended.

The fluorine-based paint of the present invention can be applied to the surface of a base material such as 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 coating film has weather resistance, chemical resistance,
It has excellent solvent resistance, water repellency, water resistance, heat resistance, low friction, and transparency, as well as excellent adhesion.

〔Effect of the invention〕

According to the present invention, since the fluorine-based copolymer obtained by copolymerizing the components (a) to C) or the components (a) to d) is used as a coating film forming component, A fluorine-based copolymer that dissolves in organic solvents at room temperature, hardens at room temperature, and has weather resistance, chemical resistance, solvent resistance, water repellency, low friction, water resistance, heat resistance, transparency, etc. A fluorine-based paint with excellent adhesion, extensibility, and storage stability can be obtained while maintaining the excellent properties of .

〔Example〕

Next, examples of the present invention will be described.

Example 1 After replacing the interior of a stainless steel autoclave with an internal volume of 1.5Q with a stirrer with nitrogen, 500 m of benzene was added under a nitrogen stream.
Q, trimethoxyvinylsilane (hereinafter referred to as TMV)
S) 31.1g, ethyl vinyl ether (hereinafter referred to as
EVE) 60.6g, 4-vinyloxybutoxytrimethylsilane (hereinafter abbreviated as 4-VOBOTMS)
83.8g, synthetic hydrotalcite (Mg, SA
9.3 g of a fired product of R2(OH), 1 cOa -3,5H,0) powder (hereinafter abbreviated as SHT) and 5.43 g of dilauroyl peroxide were charged. Then chlorotrifluoroethylene (hereinafter abbreviated as CTFE) 1
83 g was introduced into an autoclave, heated to 65° C., and reacted for 7.5 hours.

After that, the autoclave was cooled with water to stop the reaction, and after cooling, unreacted monomer was expelled, and the autoclave was opened.
The reaction solution was taken out into an IQ eggplant flask. 150 g of xylene was added to this reaction solution, residual monomers and solvent were distilled off under reduced pressure using an evaporator, then 400 g of xylene was added, and the solvent was distilled off under reduced pressure using an evaporator again.

Then add 500 g of xylene, filter the solution and
) IT was removed and concentrated under reduced pressure to obtain a colorless and transparent copolymer (1
) 296g was obtained.

The number average molecular weight of the obtained copolymer (I) by GPC was 16,000. In addition, when the composition of this copolymer (I) was analyzed using elemental analysis and NMR, it was found that C
TFE/4-VOBOTMS/TMVS/EVE=43
/22/7/28 (mol%).

52.1 parts by weight of the above copolymer (1), 2.6 parts by weight of tetrasilicic acid oligomer as a paint additive, 2.6 parts by weight of methyl orthoformate as a dehydrating agent, and 42 parts by weight of xylene.
A mixture consisting of 7 parts by weight was allowed to stand at room temperature in a sealed state, and the time required for the mixture to harden was measured. Table 1 shows the results.
Shown below.

Comparative Example 1 The interior of a stainless steel autoclave with an internal volume of 1.5Q and a stirrer was replaced with nitrogen, and 180m12 of benzene was added under a nitrogen stream.
, 2VE 115.1g, hydroxybutyl vinyl ether (hereinafter abbreviated as HyBVE) 24.4g-TMV
43.6 g of S and 3.0 g of 5 t (TI) were charged. Thereafter, 257 g of CTFE was introduced into the autoclave, and the temperature was raised to 65°C.

To this, add 7.6 g of dilauroyl peroxide to 1 part of benzene.
An initiator solution dissolved in 20 mQ was fed over 4 hours. After further reacting at 65° C. for 6 hours, the autoclave was cooled with water to stop the reaction.

After cooling, unreacted monomers were expelled, the autoclave was opened, and the reaction solution was taken out into a 1.5Q eggplant-shaped flask.

To this, 210 g of xylene, 120 g of methanol and S
13.0 g of HT was added, and the mixture was heated at 50° C. for 1.5 hours and then at 60° C. for 1.5 hours while stirring.

After the treatment, residual monomers and solvent were distilled off under reduced pressure using an evaporator, and then 550 g of xylene was added and stirred to form a homogeneous solution. This solution was filtered to remove SHT and concentrated under reduced pressure to obtain a colorless and transparent copolymer (n) 32
2g was obtained.

The number average molecular weight of the obtained copolymer (n) by GPC was 10,300. In addition, when the composition of this copolymer (■) was analyzed using elemental analysis and NMR, it was found that C
TFE/TMVS/EVE/HyBVE=49.
/6/39/6 (mol%).

In Example 1, storage stability was measured in the same manner as in Example 1 except that the copolymer (n) was used instead of copolymer (1). The results are shown in Table 1.

Table 1 From the results in Table 1, paints whose film-forming component is a fluorine-based copolymer obtained by copolymerizing components (a) or d) are (a), (c) j (d), and HyBVE
It can be seen that it has superior storage stability compared to paints whose film-forming component is a fluorine-based copolymer obtained by copolymerizing.

Claims (2)

[Claims] (1) (a) fluoroolefin, (b) a radically polymerizable monomer having an olefinic unsaturated bond and a group that becomes a hydroxyl group when hydrolyzed is bonded to a carbon atom, and (c) Contains as a coating film-forming component a fluorine-based copolymer obtained by copolymerizing an organosilicon compound that has an olefinic unsaturated bond and a group that becomes a hydroxyl group when hydrolyzed is bonded to a silicon atom. A fluorine-based paint that is characterized by (2) (a) Fluoroolefin, (b) A radically polymerizable monomer having an olefinic unsaturated bond and a group that becomes a hydroxyl group when hydrolyzed is bonded to a carbon atom, (c) Olefin A fluorine-based copolymer obtained by copolymerizing an organosilicon compound that has a sexually unsaturated bond and a group that becomes a hydroxyl group when hydrolyzed is bonded to a silicon atom, and (d) an alkyl vinyl ether. A fluorine-based paint characterized by containing it as a film-forming component.