JPH041216A - Fluorinated copolymer and fluorinated coating material based thereon - Google Patents

Abstract

PURPOSE:To obtain a fluorinated copolymer improved in solubility in an organic solvent and compatibility with a curing agent and comprising two specified kinds of units and optional units derived from a functional monomer and other units derived from other monomers. CONSTITUTION:A fluoroolefin (A) having at least one F atom in the molecule (e.g. chlorotrifluoroethylene) is copolymerized with a cyclic vinyl ether (B) of formula I [wherein R<1> and R<2> are each H, 1-8C aliphatic or alicyclic hydrocarbon group; and R<3> is a bivalent (substituted) organic group], e.g. hydroxybutyl vinyl ether, and optionally a functional monomer (C) and other monomers (D) at 0-100 deg.C under a pressure of 1-100kg/cm<2> to obtain the title copolymer comprising 20-95mol% units derived from component A of formula II [wherein V, X, Y and Z are each H, F, Cl or 1-6C (halo)alkyl], 5-80mol% units derived from component B of formula I, 0-40mol% units derived from component C and 0-40mol% units derived from component D.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel fluorine-containing copolymer and a fluorine-based paint containing the same as a main component.

More specifically, the present invention provides a fluorine-containing copolymer that is soluble in an organic solvent, has good compatibility with a curing agent, and is curable at room temperature, and a glossy copolymer containing this copolymer as a main component. The present invention relates to a fluorine-based paint that can provide a coating film that is hard and has excellent weather resistance.

(Prior Art) Fluorine-containing copolymers have been widely used in many fields due to their excellent heat resistance, mechanical properties, chemical resistance, weather resistance, etc. One of its uses is as a film-forming component in paints.For example, fluororesin paints using tetrafluoroethylene polymers and vinylidene fluoride polymers are known, and these have excellent lubricity. Because it has non-adhesive properties, weather resistance, and chemical resistance, it is used as a coating material in fields such as the chemical industry, food, architecture, and machinery.

However, the above-mentioned fluororesin paints have the disadvantage of requiring baking at high temperatures, which inevitably limits their range of use. Attempts have been made to develop solvent-based paints using fluorine-containing copolymers with reactive groups.

In order to solubilize a fluoropolymer in an organic solvent, it is necessary to disrupt the crystallinity of the fluoropolymer and internally plasticize it by introducing an appropriate copolymer component. As examples, various copolymers have been disclosed so far (JP-A-5734107, JP-A-61-27).
No. 5311, No. 61-57609, No. 62-
174213, 63-182312).

However, in these copolymers, alkyl vinyl ethers and special carboxylic acid vinyl esters are used as copolymerization components, but while these copolymerization components give flexibility to the coating film, they also reduce the hardness of the coating film. In addition, the coating film has low gloss and has insufficient compatibility with the curing agent.

(Problems to be Solved by the Invention) The present invention overcomes the drawbacks of conventional fluorine-containing copolymers that are soluble in organic solvents, and has good solubility in organic solvents and compatibility with curing agents. The purpose of this invention is to provide a novel room-temperature-curable fluorine-containing copolymer, and a fluorine-based paint containing this copolymer as a main component that can provide a glossy, hard, and weather-resistant coating. It is something.

(Means for Solving the Problems) In view of the above points, the present inventors have conducted intensive research and found that the above problems can be solved by using a specific monomer as a polymerization monomer of a fluorine-containing copolymer. found that it can be solved,
The present invention has now been completed.

That is, the present invention provides: (1) A fluorine-containing copolymer comprising the following (A) and (B) as essential constituents, and optionally also containing (C) and/or (D) as a constituent.

(A) formula; % formula % (1) (in the formula, ■,
and 1 selected from a halo-substituted alkyl group having 1 to 6 carbon atoms.
species, at least one of which is F. ) Copolymerized units of fluoroolefin: 20
~95 mol% Formula (B); (In the formula, R1 and Rt may be the same or different and each represents hydrogen or an aliphatic or alicyclic hydrocarbon having 1 to 8 carbon atoms, and R3 is optionally substituted. Copolymerized units of endocyclic vinyl ether represented by: 5 to 5.
80 mol% (C) 20 to 40 mol% of copolymerized units of functional group-containing monomer (D) 20 to 40 mol% of copolymerized units of other monomers, and ■ The above fluorine-containing copolymer The present invention provides a fluorine-based paint containing as a main component.

The present invention will be explained in detail below.

In the copolymer of the present invention, the fluoroolefins forming the unit (A) are olefins having at least one fluorine atom in the molecule, and are preferably:
Examples include perhaloolefins in which all hydrogen atoms of the olefin are replaced with fluorine atoms and other halogen atoms.

Specific examples of such fluoroolefins include CC
4=CC, CHF=CF! , CHz=CFz, CH
z=CHF, CCf F=CF, ,CHCf Engineering CF,,
CCl2=CF, ,CCI! , FYCCIF ,
CHF=CC12, CC4=CCIF XCC1z=C
Fluoroethylene type such as C1, F; CC4=CFz, CF3CF=CHF, CFsC
H=CFz, CF3CF=CHI, CFsCF=C
HF, CHFzCF=CHF, CFiCH=CH
z, C3scF=cFz, CHzCH=Ch, C
HzCF=CHz, CFtCj2CF=CF2, CF
sCCl = Ch, CF, CF = CFCl, ChC
I CCl = CF2, CF zc I CF=CFC
l,CFCjl! ICP=CFZ, CF3 CC4=
CC42F, CF1CC1=CC1□, CCj!
hCF=CC12z, CC15cF=ch, CFt
CfCCICCj! z, CFCf, CCl = CCl
z, CF3CF=CHCl, CCl hcF=
cl (Cl.

CFiCCj! =CHCj! , CHFzCC1=CC
1z, CFtCl, CH=CCffi! ,CFZ
CffiCCICHCl, CCj! 5cF=cHc
f, ChjICF=CF! , CFJrCH=CFt,
CFsCBr=CHBr,,ChCl CBr=CH
z, CHJrCF=CCj! t, CFsCB
r=C)lx, CC4=CHBr, ChBrCH=C
Fluoropropene series such as HF, C3scF=cFz; ChCFzcF Ch, CFiCF=CFCF+, C
FiCH=CFCh, CF2=CFCF2CHFZ,
ChCF2CF=CHz, CC4=CHCh, Ch=C
FChCHs, Ch=CFCHzCH*, CF, pH2
C1 (technical CH2, CF3cH=cHcHz, CFz=
CHCHHzCHz, CHffCF2CH-CH2, CP
H2CJI=CHCFHz, C)lrcFzcH=c
) Is, CIIz□CFCHzCH:+, CF.

(Ch)zCF=Ch, CF3(CF2)3CF=C
Fluoroolefin compounds having 4 or more carbon atoms such as F2 can be mentioned, and among these, the formula; ) and fluoropropene compounds are preferred, particularly tetrafluoroethylene (CFx = CFz
), chlorotrifluoroethylene (CFz=CFC
f) and hexafluoropropene (CFz = CFCF
! ) is preferred. These fluoroolefins may be used alone or in combination of two or more.

In the copolymer of the present invention, the content of units formed from the fluoroolefins needs to be in the range of 20 to 95 mol%, preferably 40 to 60 mol%.

In the copolymer of the present invention, as the endocyclic vinyl ether forming the unit (B), -Funzo: (in the formula, R',
R'' may be the same or different and each represents hydrogen or an aliphatic or alicyclic hydrocarbon having 1 to 8 carbon atoms, and R3
represents a divalent organic group which may be optionally converted into IF,
) is used.

Specific examples of the endocyclic vinyl ether include 2.
Dihydrofurans i3 such as 3-dihydrofuran, 2,3-dihydro5-methylfuran, 2,2-dimethyl-3-hydrofuran, 3,3-dimethyl-2-hydrofuran, 2-methoxy-2,3-dihydrofuran .4-dihydro-
2H-pyran, 3,4-dihydro-2-methoxy-2H
-pyran, 3,4-dihydro-2-ethoxy-2H- and ran, 3,4-dihydro-6-methyl-pyran, 2-carboxy-3,4-dihydro-2H-pyran, 2-formyl-3, Dihydropyrans 11 such as 4-dihydro-2H-pyran, 3,4-dihydro-3,3-dimethyl-2H-pyran; 1,3-dioxole, 2,2-dimethyl-
Dioxoles such as 1,3-dioxole; furan, α
- Furans such as methylfuran; and benzofuran, naphthofuran, p-dioxene, etc. Among these, dihydrofurans and dihydropyrans are particularly preferred from the viewpoint of weather resistance. These may be used alone or in combination of two or more.

In the copolymer of the present invention, the content of (B) units is 5
It is necessary that the amount is in the range of 80 mol% to 80 mol%, preferably 10 to 60 mol%. If this content is less than 5 mol%, the rigidity will be poor and the compatibility with the curing agent will be low;
If it exceeds this, weather resistance will decrease.

In the copolymer of the present invention, the above (A) and (B
) In addition to the units, it may contain (C) copolymerized units of a functional group-containing monomer and/or (D) copolymerized units of other monomers, if necessary, within a range not exceeding 40 mol% of each. I can do it.

Examples of the functional group-containing monomer forming the unit (C) include - hydroxy group-containing unsaturated ethers represented by Funazura (i), and epoxy group-containing unsaturated ethers represented by Funazura (ii). Examples thereof include saturated ethers, hydrolyzable silyl group-containing vinyl monomers represented by -funazo (ji), and the like.

(i) CH*=CH-(CHz)t-0-R'-
0R (wherein, R4 is an alkylene group having 1 to 6 carbon atoms, and i represents O or 1) (wherein, j is O or 1, k represents an integer of 0 to 5, and 1 represents an integer of 1 to 5) (in the formula, m and n are 0 or 1, R' and RR? represent a monovalent organic group, and at least one is an alkoxy group having 1 to 6 carbon atoms) ).

Specific examples of hydroxy group-containing unsaturated ethers include hydroxymethyl vinyl ether,
Hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxy-2-methyl pro-ruvinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyethyl vinyl ether, Examples include ethylene glycol monoallyl ether.

Epoxy group-containing unsaturated ether Ii [formula (ii)]
As a specific example, for example, CH,, C) I-0-CH2-CH2-CH-C0\1 CHz=CH-CHz-0-CHz-CH-CT.

\1 etc.

Specific examples of hydrolyzable silyl group-containing vinyl monomer formula 1 (city) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxymethylsilane, allyltrimethoxysilane, allyltriethoxysilane, allyl Examples include dimethoxymethylsilane, vinyloxypropyltrimethylsiloxysilane, vinyloxtoxypropyltrimethylsiloxysilane, and the like.

The functional group-containing monomers forming the unit (C) may be used alone or in combination of two or more.

In addition, examples of the copolymerizable monomer forming the unit (D) include olefins such as ethylene, propylene, and isobutylene; haloolefins such as vinyl chloride and vinylidene chloride; vinyl acetate, vinyl n-butyrate, Carboxylic acid vinyl esters such as vinyl benzoate, pt-butyl vinyl benzoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl versatate; carboxylic acid isopropenyl esters such as isopropenyl acetate, isopropenyl propionates, etc. Chain alkyl vinyl ethers such as 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, 4-methyl-1-pentyl vinyl ether; pentafluoro Fluorovinyl ethers such as vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether; aryl vinyl ethers such as phenyl vinyl ether, o-1m-p-)') rubinyl ether; aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether; Aromatic vinyl compounds such as styrene and vinyltoluene; Allyl carboxylates such as allyl formate, allyl acetate, allyl propionate, allyl butyrate, allyl caproate, allyl benzoate, allyl cyclohexanecarboxylate, and allyl cyclohexylpropionate; allyl ethyl Allyl ethers such as ether and allyl phenyl ether; di- or monoesters and acid anhydrides of unsaturated bond-containing polybasic acids such as fumaric acid and maleic acid; hydroxyethyl acrylate, hydroxyethyl methacrylate, methyl methacrylate, glycidyl methacrylate and esters of acrylic acid and methacrylic acid; and acrylamides such as acrylamide and N-methylolacrylamide.

These monomers may be used alone or in combination of two or more.

The fluorine copolymer of the present invention can be produced by copolymerizing a monomer mixture of a predetermined ratio in the presence or absence of a solvent using a polymerization initiator, ionizing radiation, etc. as a polymerization initiation source. I can do it.

As the polymerization initiator, water-soluble or oil-soluble ones are appropriately used depending on the type of polymerization and the type of solvent used as desired.

Examples of the oil-soluble initiator include azo compounds such as azobisisophthyronitrile and 2,2'-azobis-(2,4dimethylvaleronitrile); t-butylperoxyisobutyrate, t-butylperoxyacetate, and the like; Examples include peroxy ester type peroxidants; dialkyl peroxy dicarbonates such as diisopropylberoxy dicarbonate; benzoyl peroxide, and the like.

Examples of water-soluble polymerization initiators include redox initiators consisting of persulfates such as potassium persulfate, hydrogen peroxide, or combinations of these with reducing agents such as sodium bisulfite and sodium thiosulfate; Inorganic initiators such as systems in which small amounts of iron, ferrous salts, silver nitrate, etc. coexist; dibasic acid peroxides such as disuccinic acid peroxide, diglutaric acid peroxide, monosuccinic acid peroxide, azobisisobutylamidine dibase Examples include organic initiators such as acid salts.

The amount of these polymerization initiators to be used is appropriately selected depending on the type thereof, copolymerization reaction conditions, etc., but is 0.005 to 5% by weight, preferably 0.005 to 5% by weight, based on the total amount of monomers normally used.
The amount is selected within the range of 0.05 to 0.5% by weight.

There are no particular restrictions on the polymerization method, and for example, bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, etc. can be used, but from the standpoint of stability of the polymerization reaction, xylene, toluene, Lower alkyl substituted benzenes such as;
Ketones such as methyl isobutyl ketone; alcohols such as t-butanol; esters such as butyl acetate; solution polymerization using solvents such as saturated halogenated hydrocarbons having one or more fluorine atoms; Emulsion polymerization methods, bulk polymerization methods that do not require separation from a solvent, and the like are preferably used.

(C) When using hydroxyl group-containing unsaturated ethers as the functional group-containing monomer forming the unit, bases such as potassium carbonate or amine compounds should be used for the purpose of producing fluorine-based copolymers with good reproducibility. Addition of sexual substances is effective.

Furthermore, there are no particular restrictions on the polymerization format; batchwise,
Either a semi-continuous type or a continuous type can be used.

The reaction temperature in the copolymerization reaction is usually -30 to +15
Within the range of 0°C, appropriately selected depending on the polymerization initiation source and the type of polymerization medium, usually 0 to 100°C, preferably 10 to 9
Selected within the range of 0°C. Further, the reaction pressure is not particularly limited, but is usually selected within the range of 1 to 100 kg/cj, preferably 2 to 50 kg/cj. Furthermore, the copolymerization reaction can be carried out by adding a suitable chain transfer agent.

The product thus obtained has the following formula in the main chain: 6 alkyl group,
and 1 selected from a halo-substituted alkyl group having 1 to 6 carbon atoms.
species, at least one of which is F. , ), more preferably, the structure is: Formula;

It contains fluorine with a structure of and R2 represents an optionally substituted divalent organic group) as an essential component, and preferably has the following formulas (i) to (
It is a fluorine-containing copolymer which also has at least one kind of functional group having the structure shown in ui).

(In the formula, R4 is an alkylene group having 1 to 6 carbon atoms, and i
indicates 0 or 1. ) (In the formula, j is 0 or 1, k is an integer from O to 5.1 and 1 to 5.) (ii) (In the formula, m and n are O or 1, R', R', R' is 1
represents a valent organic group, at least one of which has 1 to 1 carbon atoms.
6 shows an alkoxy group. ) The molecular weight of the fluorine-containing copolymer of the present invention is the number average molecular weight determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and monodisperse polystyrene of known molecular weight as a standard substance. (Mn) is 1,000 to 20
0,000, preferably in the range of 2,000 to 1oo, ooo, and the glass transition temperature (Tg) is usually -50 to 1
20°C, preferably -10 to 100°C.

The fluorine-containing copolymer of the present invention having such a composition, molecular weight, and glass transition temperature is soluble in organic solvents and has excellent compatibility with curing agents, and can be used in paints containing the copolymer as a main component. The cured coating film is glossy, hard, and has excellent weather resistance.

In the fluorine-containing copolymer of the present invention, when a hydroxy group-containing unsaturated ether is used as the functional group-containing monomer forming the unit (C), the obtained fluorine-containing copolymer can be cured. It contains a hydroxyl group as a moiety, and can be used as a curing agent used in ordinary thermosetting acrylic paints, such as polyvalent isocyanates, blocked polyvalent isocyanates, melamine curing agents, urea resin curing agents, and polybasic acid curing agents. It can be cured by heating using an agent or the like.

Furthermore, the hydroxy group-containing fluorine-containing copolymer can also be cured at room temperature by using polyvalent isocyanates.

Preferred examples of the polyvalent isocyanates include non-yellowing diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, adducts thereof, and polyvalent isocyanates having an isocyanurate ring. Polyhydric isocyanates having isocyanurate rings with good compatibility with coalescence are preferred. When curing at room temperature using these polyvalent isocyanates, curing can be accelerated by adding a known catalyst such as dibutyltin dilaurate.

In the fluorine-containing copolymer of the present invention, when an epoxy group-containing unsaturated ether is used as the functional group-containing monomer forming the unit (C), the resulting fluorine-containing copolymer has It contains an epoxy group as
Polyaddition type curing agents such as polyamines, acid anhydrides, polyphenols, polymercaptans, etc.; catalytic curing agents such as imidazoles, BF, etc. are used as curing agents to perform heat curing or room temperature curing. I can do it.

In addition, in the fluorine-containing copolymer of the present invention, when a hydrolyzable silyl group-containing vinyl monomer is used as the functional group-containing monomer forming the unit (C), the obtained fluorine-containing copolymer The polymer contains a hydrolyzable silyl group as a curing site, and can be moisture-cured using an amine compound such as butylamine or a curing catalyst such as dibutyltin dilaurate.

Furthermore, the fluorine-containing copolymer of the present invention can be used as a lacquer-type coating material even when it does not contain the (C) unit.

The present invention provides the above-mentioned novel fluorine-containing copolymer as well as a fluorine-based paint containing this fluorine-containing copolymer as a main component. can be used.

Examples of the solvent include aromatic hydrocarbons such as toluene and xylene; alcohols such as n-butanol; ketones such as methyl isobutyl ketone; glycol ethers such as ethyl cellosolve; and various commercially available thinners. It will be done. Solutions obtained by dissolving the fluorine-containing copolymer in these solvents are colorless and transparent.

The solution-type paint is prepared by mixing the fluorine-containing copolymer and a solvent using a mixer commonly used for preparing paints, such as a ball mill, Peyton shaker, sand mill, jet mill, three-roll mill, kneader, etc. This can be done by mixing homogeneously using At this time, if desired,
Pigments, dispersion stabilizers, viscosity modifiers, leveling agents, anti-gelling agents, ultraviolet ray absorbing agents, etc. can also be added.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

It should be noted that all percentages in the examples indicate weight percentages, and the abbreviations used are as follows.

[Monomer] CTFE: Chlorotrifluoroethylene HBVE: Hydroxybutyl vinyl ether IBVE: Isobutyl vinyl ether 2.3-DHF: 2,3-dihydrofuran 3.4-DH
-2-MP=34-dihydro-2-methoxypyran (■) Molecular weight of various resins; Determined from polystyrene standard calibration curve using gel permeation chromatography.

(Equipment used)・Apparatus: Shimadzu LC-3A・Column: Tosoh■ TSKgel G-5000HXL # G-4000HXL 〃G-20001(XL・Detector: Shimadzu RID-6A・Data processing: Shimadzu C-1? 4A・Carya 12 Tetrahydrofuran ■ Glass transition temperature (Tg) of various resins: Measurement was carried out using the following equipment and measurement conditions.

(Equipment used) Simultaneous differential thermogravimetric measurement device (manufactured by Seiko Electronics Co., Ltd.)
5SC5000DSC200 (measurement conditions) -80→9
0°C temperature increase (5°C/min) ■ Hydroxyl value: Performed according to JIS K-0070.

■ Gloss/Flexibility: Measured according to JIS K-5400.

■ Paint film hardness: 150-1522.

■ Weather resistance: It was determined in accordance with ASTM G-53.

(2) Infrared absorption spectrum (IR spectrum) Measured using FT/IR-5M model manufactured by JASCO Corporation.

Example 1 7.7 g of potassium carbonate was charged into a stainless steel autoclave with an internal volume of 1 ffi and equipped with a stirrer, and the inside of the autoclave was purged with nitrogen gas three times.

Next item, 2.3-DHF 58g, HBVE 20g,
CTFE 117g, 2.2″-azobis-(2,4
-dimethylvaleronitrile) 2.5 g, and xylene 1
95 g was charged and the internal temperature was gradually raised to 65°C.

After 8 hours of polymerization, unreacted CTFE was removed, the autoclave was opened, and the resulting copolymer solution was taken out. After removing potassium carbonate from this copolymer solution by filtration, it was reprecipitated with n-hexane and dried. The yield of copolymer was 93 g.

The number average molecular weight of the obtained copolymer was 4,000,
Glass transition temperature is 76°C1 Hydroxyl value is 74■KOH/
It was g. Further, the composition ratio of this copolymer determined from the results of elemental analysis was a CTFE unit/2.3-DHF unit/HBVE unit molar ratio of 48/39/13.

The IR spectrum of the obtained copolymer is shown in Figure 1, 2
．． The absorption of the endocyclic C-O stretching derived from the 3-DHF unit is 9
40CII-', and the absorption of the intracyclic C-H bending vibration is 1
450CIl-', respectively.

Example 2 7.7 g of potassium carbonate was charged into a stainless steel autoclave with an internal volume IIl equipped with a stirrer, and the inside of the autoclave was purged with nitrogen gas three times. Then, 2.3-DHF
21g, IBVB 50g, HBVE 23g
, CTFE 117g, 2゜2゛-azobis-(2,
2.5 g of 4-dimethylvaleronitrile) and 210 g of xylene were charged, and the internal temperature was gradually raised to 65°C.

After 8 hours of polymerization, unreacted CTFE was removed, the autoclave was opened, and the resulting copolymer solution was taken out.

After filtering and removing potassium carbonate from this copolymer solution,
It was reprecipitated with n-hexane and dried.

The yield of copolymer was 160 g.

The number average molecular weight of the obtained copolymer was 10,000, the glass transition temperature was 31°C, and the hydroxyl value was 65 KOH.
/g.

The IR spectrum of the obtained copolymer is shown in FIG.

Example 3 7.7 g of potassium carbonate was charged into a stainless steel autoclave with an internal volume of 11 and equipped with a stirrer, and the inside of the autoclave was purged with nitrogen gas three times. Then, 3.4-DH-2
-MP 34g, IBVE 50g, HBVE
23g, CTFE 117g, 2.2'-azobis-
2.5 g of (2,4-dimethylvaleronitrile) and 225 g of xylene were charged, and the internal temperature was gradually raised to 65°C.

After 8 hours of polymerization, unreacted CTFE was removed, the autoclave was opened, and the resulting copolymer solution was taken out.

After filtering and removing potassium carbonate from this copolymer solution,
It was reprecipitated with n-hexane and dried.

The yield of copolymer was 116 g.

The number average molecular weight of the obtained copolymer was 10,000, the glass transition temperature was 25°C, and the hydroxyl value was 85 ■KOH/
It was g.

The IR spectrum of the obtained copolymer is shown in FIG.

Examples 4 to 6 10 g of each fluorine-containing copolymer obtained in Examples 1 to 3
was dissolved in 10 g of xylene, and "Duranate TPA" (manufactured by Asahi Kasei Industries) was added as a curing agent to NC010H=1.
/l, and after adjusting for 15 seconds with Ford Cup #4 using xylene as a thinner, it was painted.

After baking the obtained coating film at 120° C. for 1 hour, the physical properties of the coating film were measured. (Examples 4 to 6) The results are shown in Table 1.

Comparative Example 1 7.7 g of potassium carbonate was charged into a stainless steel autoclave with an internal volume of 11 and equipped with a stirrer, and the inside of the autoclave was purged with nitrogen gas three times. Tsuite, IBVE 80
g5HBVE 23g, CTFE 117g, 2.
2'~Azobis-(24-dimethylvaleronitrile)1
．． Prepare 5g of xylene and 220g of xylene, and raise the internal temperature to 65°.
The temperature was gradually raised to C. After 8 hours of polymerization, unreacted CTFE was removed, the autoclave was opened, and the resulting copolymer solution was taken out.

After filtering potassium carbonate from this copolymer solution,
It was reprecipitated with n-hexane and dried.

The yield of copolymer was 192 g.

The number average molecular weight of the obtained copolymer was 27,000, the glass transition temperature was 20°C, and the hydroxyl value was 52 KOH/
It was g.

FIG. 4 shows the TR spectrum of the obtained copolymer.

Comparative Example 2 The fluorine-containing copolymer obtained in Comparative Example 1 was baked into a film in the same manner as in Examples 4 to 6, and the physical properties of the film were measured.

The results are shown in Table 1.

As shown in Table 1, the fluorine-containing copolymer of the present invention has a high glass transition temperature, and when used as a coating resin, exhibits excellent coating film transparency and gloss, and also exhibits high coating film transparency and gloss. It has film hardness.

(Effects of the Invention) According to the present invention, the fluoroolefin has good solubility in organic solvents, good compatibility with a curing agent, and can be cured at room temperature without being subject to restrictions on the type of fluoroolefin used. A fluorine-containing copolymer can be easily provided.

Furthermore, the fluorine-based paint of the present invention containing the fluorine-containing copolymer as a main component can provide a glossy, hard, and weather-resistant coating film under mild conditions. Baking for colored aluminum plates and aluminum sashes is useful as a paint or as an air-drying paint that can be applied on-site.

Furthermore, regarding the material of the base material, including metal materials, inorganic materials such as glass and concrete, FRP, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, nylon, acrylic resin, polyester, ethylene-vinyl acetate copolymer,
It is suitably used for coating plastics such as polyvinyl alcohol copolymers, polyvinyl chloride, and polyvinylidene chloride, and organic materials such as wood.

The fluorine-based paint is also useful in specific applications such as aluminum boules, exterior colored glass, and cement roofs.

[Brief explanation of the drawing]

Figures 1 to 3 show IR spectra of the copolymers obtained in Examples 1 to 3, respectively. FIG. 4 shows the IR spectrum of the copolymer obtained in Comparative Example 1. (1 other person)

Claims (2)

[Claims] (1) A fluorine-containing copolymer characterized in that it contains the following (A) and (B) as essential constituents, and optionally also contains (C) and/or (D) as a constituent. (A) Formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, V, X, Y, and Z may be the same or different, and each represents H, F, Cl, and the number of carbon atoms. A copolymerized unit of a fluoroolefin, which represents one selected from an alkyl group having 1 to 6 carbon atoms and a halo-substituted alkyl group having 1 to 6 carbon atoms, and at least one of them is F.) :20
~95 mol% Formula (B); ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (In the formula, R^1 and R^2 may be the same or different, and each represents hydrogen or the number of carbon atoms. 1 to 8 aliphatic or alicyclic hydrocarbon, R^3 may be optionally substituted 2
represents a valent organic group. ) Copolymerized unit of endocyclic vinyl ether represented by: 5-
80 mol% (C) Copolymerized units of functional group-containing monomer: 0 to 40 mol% (D) Copolymerized units of other monomers: 0 to 40 mol% (2) A fluorine-containing copolymer comprising the following (A) and (B) as essential constituents, and optionally containing (C) and/or (D) as a constituent. The main ingredient is paint. (A) Formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, V, X, Y, and Z may be the same or different, and each represents H, F, Cl, and the number of carbon atoms. A copolymerized unit of a fluoroolefin, which represents one selected from an alkyl group having 1 to 6 carbon atoms and a halo-substituted alkyl group having 1 to 6 carbon atoms, and at least one of them is F.) :20
~95 mol% Formula (B); ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (In the formula, R^1 and R^2 may be the same or different, and each represents hydrogen or the number of carbon atoms. 1 to 8 aliphatic or alicyclic hydrocarbon, R^3 may be optionally substituted 2
represents a valent organic group. ) Copolymerized unit of endocyclic vinyl ether represented by: 5-
80 mol% (C) Copolymerized units of functional group-containing monomer: 0 to 40 mol% (D) Copolymerized units of other monomers: 0 to 40 mol%