JPH01268708A - Method for producing fluorine-containing copolymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a fluorine-containing copolymer containing a carboxyl group, which is useful as a raw material for fluororesin paints.

[Conventional technology and its problems]

When a vinyl ether having a carboxyl group is copolymerized with a fluoroolefin, a fluororesin having a carboxyl group can be produced, but a vinyl ether having a carboxyl group is difficult to synthesize. For example, if you attempt to synthesize a vinyl ether with a carboxyl group by reacting a hydroxyalkyl vinyl ether with a dibasic acid anhydride (half esterification), the carboxyl group and vinyl group will react and cyclize within the molecule, resulting in the desired goal. I can't look around for things.

Therefore, a fluorine-containing copolymer containing a carboxyl group is produced by, for example, producing a copolymer of a vinyl ether containing a hydroxyl group and a fluoroolefin, and then combining the hydroxyl group contained in the copolymer with a tribasic acid anhydride. Method for reacting (half-esterifying) substances (Special Publication 1981)
-49323). but,
In this method, since half-esterification is performed after copolymerization, there is a problem in that it is difficult to use inexpensive alcohols that react with tribasic acid anhydrides as a solvent for copolymerization.

As a result of intensive studies on the production method of vinyl ether containing a carboxyl group, the present inventors found that when reacting a hydroxyalkyl vinyl ether with a tribasic acid anhydride,
When a basic compound is present in the system, intramolecular cyclization reaction does not occur, and the carboxyl group of the obtained vinyl ether takes the form of a salt of the basic compound, improving stability. It has been found that the yield is significantly improved when copolymerized.

By the way, when such carboxyl group-containing fluorine-containing copolymers useful as general water-based paints and electrodeposition paints are polymerized, it is necessary to use a polymerization solvent that is soluble in water or has excellent dispersibility. be.

Among these solvents, amide solvents such as dimethylformamide and dimethylacetamide, and ester solvents such as methylcellosolve acetate generate miscellaneous ions in aqueous solutions, which may impair the stability of the copolymer when it is made water-soluble or generate ions. It may cause wrinkles or cracks in the appearance of the paint film. In addition, alcohol solvents such as methanol, ethanol, and isopropanol impair the stability of vinyl ether monomers due to the action of their hydroxyl groups, and also cause a decrease in the polymerization rate, resulting in similar effects to amide and ester monomers. This causes paint film defects. Such a decrease in coating film performance becomes more noticeable when a fluorine-containing polymer is used as an electrodeposition coating.

[Means to solve the problem]

The present invention has been made to solve such problems, and has the following formula: CH2-Cl0R100(-0)R'C(-0)0(H
)nM (I) (wherein, R1 has 2 to 10 carbon atoms
a divalent aliphatic group, R2 is a divalent organic group, R2 is an alkali metal, or a monofunctional basic compound containing a nitrogen or phosphorus atom and whose pKa is 6 to 12, n is 0 only for alkali metals, 1 for others
vinyl ether in which the carboxyl group is in the form of a salt (hereinafter referred to as vinyl ether (I)) and the formula (■): CH2=ClOR'QC('0)R2O(-0) O
vinyl ether (hereinafter referred to as vinyl ether (I)) having a free carboxyl group represented by H (II) (in the formula, R' and R2 are the same as above), and vinyl ether (I) is composed of vinyl ether (I). 1 mol%
When copolymerizing the vinyl ether monomer composition containing the above and the fluoroolefin, the formula (I10: % formula % (where yl is an alkyl group having 1 to 8 carbon atoms, Y2 is a hydrogen atom or The present invention relates to a method for producing a fluorine-containing copolymer, characterized in that a glycol ether represented by a methyl group (n is 0 or an integer from 1 to 20) is used as a polymerization solvent.

[Preferred Embodiment] As described above, the vinyl ether monomer composition used in the present invention has significantly improved storage stability compared to the case where vinyl ether (II) is used alone. The reason is,
This is presumed to be because the presence of stable vinyl ether (I1) in a proportion of 1 mol % or more of (II) reduces the concentration of He, which promotes cyclization of vinyl ether (II), in the system.

Among the vinyl ether monomer compositions, vinyl ether (I) is a hydroxyalkyl vinyl ether represented by the following formula: % formula % (wherein R1 is the same as above), and (2) formula 2 (wherein R2 is the same as above) dibasic acid anhydride represented by the formula; and (1) a monofunctional base which is an alkali metal compound or a compound containing a nitrogen atom or a phosphorus atom and whose pKa (acid dissociation index in water at 25°C) is 6 to 2. compound (hereinafter simply referred to as base ■ when the two are not distinguished)
It can be obtained by reacting.

Specific examples of hydroxyalkyl vinyl ethers that are raw materials for this production method include 4-hydroxybutyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxy-n-propyl vinyl ether, 2-hydroxy-1so-propyl vinyl ether, 2-hydroxy-
2-Methyl ethyl vinyl ether, 2-hydroxy-L
Examples include L-dimethylethyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 3-hydroxycyclohexyl vinyl ether, 2-hydroxycyclohexyl vinyl ether, and 4-hydroxybenzooxyvinyl.

Dibasic acid anhydride and vinyl ether (I) or (
As R2 contained in I[l, formula (I): [in the formula,
XI is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
x2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
p and q are 0 or an integer of 1 to 11 (however, they are not O at the same time)], a group represented by the formula (
-):→CH2←→CX3-C1lr (n)r
A group represented by S [in the formula, "is O or an integer of 1 to 3, S is an integer of 1 to 3, and x3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms]", formula: , R) is -(-CHX4→-- one group (however, x
4 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, t
is an integer of 1 to 4), Formula (to): [wherein, R8it +CllX5→- group (wherein,
) or f CX8- CX7+- group (where X6 and x7
are the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and V is an integer of 2 to 3.
ν) or a group represented by the formula QD: etc.

Specific examples of dibasic acid anhydrides include maleic anhydride,
Succinic anhydride, methylsuccinic anhydride, phthalic anhydride, adipic anhydride, glutaric anhydride, glutaconic anhydride, itaconic anhydride, 1,8-naphthalic anhydride, citraconic anhydride, 1,2-cyclohexanedicarboxylic anhydride, anhydride 4-Methyl-1,2-hexanedicarboxylic acid, Cl anhydride
Examples include s-4-cyclohexene-1,2-dicarboxylic acid, 1-cyclohexene-1,2-dicarboxylic anhydride, and an adduct of cyclopentadiene and maleic anhydride resulting from a Diels-Alder reaction.

Generally, the reaction between a hydroxyl compound and a dibasic acid anhydride proceeds according to the following formula in the presence of a basic catalyst.

In this case, it is sufficient to use at most 0.5 mol % (based on the tribasic acid anhydride) of the base to obtain the desired product in a yield of 90% or more. However, according to research conducted by the present inventors, when hydroxyvinyl ether, which is highly cationically reactive, is used as a hydroxyl compound, the reaction cannot be converted to the desired product in the absence of a base, as will be described later.
Moreover, if it is about 0.5 mol %, the yield of the target product is low and the stability is poor, so it is not suitable as a monomer for polymerization.

However, by making the base (1) present in an amount of 1 mol % or more, the yield exceeds 90%, and the resulting product is also stable, so that a decrease in the yield can be prevented. The reason is,
It is believed that the base (2) prevents the reaction between the carboxyl group and the vinyl group, and also prevents the cyclization of the vinyl ether (II) produced as described above. Note that the base (2) reacts stoichiometrically with the carboxyl group, but as mentioned above, it only needs to be present in the reaction system in an amount of 1 mol% or more based on the acid anhydride (2), and in that case, the base (I) and (It ) mixture can be changed.

In addition, the monomer composition includes vinyl ether (I) and (I[
) to the mixture with vinyl ether (l[)
It can also be obtained by reacting with The base (2) added later may be the same as or different from the base present during the reaction. In this case, the carboxyl group of the vinyl ether (I) and the base (2) react stoichiometrically.

As the base (2), as mentioned above, an alkali metal compound and a specific monofunctional basic compound are used.

The alkali metal compound is preferably a compound of Li, K or Na, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium methylate, sodium ethylate, potassium methylate, etc. can be given.

The specific monofunctional basic compound is a compound containing a nitrogen atom or a phosphorus atom as described above, and its p
It is a basic compound having a Ka of 6 to 12, preferably 8 to 11. Those with pKa in this range have high salt-forming ability,
Vinyl ether (II) has a large stabilizing effect. In other words, it has a higher pKa than the carboxylic acid of the dibasic acid anhydride (■).
Those having a high salt-forming ability are particularly preferred, and those having a pKa 3 to 8 higher than the corresponding carboxylic acid are particularly preferred. Suitable monofunctional basic compounds include ammonia,
Examples include amines and phosphines. Specific examples of amines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, 5eC-butylamine, and (2).

2-dimethylpropylamine, 2-ethylhexylamine, tridecylamine, dimethylamine, diethylamine, di-n-propylamine, di-isopropylamine, dibutylamine, di-isobutylamine, di-5e
e-butylamine, di-2-ethylhexylamine, trimethylamine, triethylamine, tri-n-propylamine, trilobylamine, N-methylbutylamine, N-ethylbutylamine, N,N-dimethylethylamine, N,N-dimethylisopropylamine, N
, N-dimethyltetradecylamine, N,N-dimethyloctadecylamine, 2-methoxyethylamine, 3-
Ethoxyethylamine, cyclohexylamine, N, N
-dimethylcyclohexylamine, dicyclohexylamine, benzylamine, N,N-dimethylbenzylamine, 4-methoxyphenylethylamine, ethanolamine, jetanolamine, triethanolamine, isopropanolamine, dimethylethanolamine, pyrrolidine, piperidine, ■ -Methylpiperidine, 4-methylpiperidine, morpholine and the like.

Specific examples of phosphines include trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, trilaurylphosphine, tristearylphosphine, dimethylphosphine, diethylphosphine, and dibutylphosphine. Di- or trialkylphosphines such as phosphine, dioctylphosphine, dilaurylphosphine; tris(3-hydroxypropyl)phosphine, tris(2-cyanoethyl)
Phosphine, tris(2-methoxyethyl)phosphine, tris(2-chloroethyl)phosphine, tris(2-methoxycarbonyl)phosphine, tris(
2-(2-dimethylaminoethoxy)carbonyl)phosphine, tris(2-ethoxycarbonyl)phosphine, bis(3-hydroxypropyl)phosphine,
Di- or tri-substituted alkylphosphines such as bis(2-cyanoethyl)phosphine; cycloaliphatic phosphines such as dicyclopentylphosphine, dicyclohexylphosphine, tricyclopentylphosphine, tricyclohexylphosphine; triphenylphosphine; , tris(4-methylphenyl)phosphine, diphenylphosphine, bis(4-methylphenyl)phosphine; tribenzylphosphine, triphenethylphosphine, dibenzylphosphine,
Di- or tri-aralkylphosphines such as diethylphosphine; tetramethylenephosphine;
Phosphines that have a phosphorus atom in the ring such as tetramethylene-methyl-phosphine;
Examples include phosphines in which one or three organic groups are bonded. Tertiary amines are particularly preferred.

The reaction temperature is usually -80 to 100°C, preferably 0 to 5°C.
It is 0°C. A solvent is usually used, but the process can be carried out without using it. Solvents can be used except for alcohols that react with tribasic acid anhydrides, but ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone may cause a decrease in the reactivity of the raw materials and coloration of the reaction mixture. It is preferable because there is no. The amount of base ■ to be used is as described above.
For the tribasic acid anhydride, usually 0, O1-1.2,
Preferably it is 0.05 to 1.0 (however, molar ratio).

The production method of the present invention is characterized in that a solvent represented by the above formula (2) is used as a heavy specific solvent when copolymerizing such a vinyl ether monomer composition and a fluoroolefin.

Examples of the glycol ether in the formula include monoglyme, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, and one or more of these may be used.

When glycol ether is used as a polymerization solvent, it does not have an adverse effect on each monomer, has an excellent polymerization yield, contains low molecular weight substances in the resulting polymer solution, and has excellent paintability and physical properties of the coating film.

The copolymerization system basically consists of a vinyl monomer composition, a fluoroolefin, a polymerization solvent, and a polymerization initiator. As the polymerization method, emulsion polymerization, suspension polymerization, solution polymerization, etc. can be adopted.

The polymerization temperature can be changed as appropriate depending on the type of initiator and solvent, but is usually -20 to 150°C, preferably 5°C.
~95°C. Although the reaction pressure can be selected as appropriate, it is usually 0 to 50 kg/cG.

Examples of the fluoroolefins include tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, trifluoroethylene, vinylidene fluoride, and vinyl fluoride.

In the present invention, the reaction molar ratio of vinyl ether (I), (II) and fluoroolefin is usually 20 to 99.9.

When using a fluorine-containing copolymer as a water-soluble paint,
In order to improve the water solubility of this copolymer, it is preferable that the vinyl ether (I) is contained in an amount of 5 to 80 mol%, and that its carboxyl groups are neutralized by 30% or more. is more preferable (in case of electrodeposition coating)
. Compounds used for neutralization include those exemplified in the above-mentioned base ①.

When a fluorine-containing copolymer is dissolved in an organic solvent and used as a so-called solvent-based paint, vinyl ether CI), (
The content of I) is 1 to 15 mol% in terms of adhesion to the base material.
is preferable, and from the viewpoint of pigment dispersibility, 2 to 10 mol% is preferable.

In addition to vinyl ether and fluoroolefin, the fluorine-containing copolymer may contain other types of ethylenically unsaturated compounds in an amount of 80 mol % or less relative to the fluorine-containing copolymer.

Other types of ethylenically unsaturated compounds include, for example, the formula: %Formula %) (wherein R3 is an aliphatic group having 1 to 17 carbon atoms, an alicyclic group having 3 to 17 carbon atoms, or an alicyclic group having 3 to 17 carbon atoms. a fluoroalkyl group having 1 to 20 carbon atoms, a hydroxyl group-containing alicyclic group having 1 to 7 carbon atoms, a hydroxyl group-containing alicyclic group having 3 to 17 carbon atoms, or a hydroxyl group-containing aromatic group having 6 to 20 carbon atoms, k represents 0 or 1), and specific examples include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether,
n-butyl vinyl ether, inbutyl vinyl ether, t-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, lauryl vinyl ether,
Stearyl vinyl ether, 2,2.2-trifluoroethyl vinyl ether, 2.2,3.3-tetrafluoropropyl vinyl ether, 2,2.3,3.3-pentafluoropropyl vinyl ether, 2,2.3.3.
4.4.

5,5-octafluoropentyl vinyl ether, 2,
2,3.3.4.4.4-Hebutafluorobutyl vinyl ether, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl laurate, vinyl versatate , cyclohexanecarboxylic acid vinyl ester, 4-hydroxybutyl vinyl ether, 2-hydroxyethyl vinyl ether, 3
-Hydroxy-n-propyl vinyl ether, 2-hydroxy-1so-propyl vinyl ether, 2-hydroxy-2-methylethyl vinyl ether, 2-hydroxy-1.1-dimethylethyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 3-hydroxycyclohexyl vinyl ether , 2-hydroxycyclohexyl vinyl ether, 4-hydroxybenzooxyvinyl, and the like.

Furthermore, the formula: %Formula% (where x8 is a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group or a trifluoromethyl group, and R9 is a hydrogen atom, a chlorine atom, an aliphatic group having 1 to 17 carbon atoms, a hydroxyl group Examples include compounds represented by an aliphatic group having 1 to 17 carbon atoms, an alicyclic group having 3 to 17 carbon atoms, or a fluoroalkyl group having 1 to 20 carbon atoms (- indicates 0 or 1). Specific examples include ethylene, propylene, -butene, isobutyne, styrene, vinyl chloride,
Vinylidene chloride, isobutyl acrylate, methyl acrylate, ethyl methacrylate, 2.2.3.3.3
-pentafluoropropyl α-fluoroacrylate,
2.2,3,3.4,4.5.5,8,8゜7.7-dozocafluoropentyl α-trifluoromethyl acrylate, 2-hydroxyethyl methacrylate, cyclohexyl acrylate, 2゜2. 3.3, 4.4.5,
5, 8, 6, 7, 7, 8, 8.9.9.10.10.1
1.11゜12.12.13.13.14.14.15
．． 15.15-Nonaphthafluoropentadecyl acrylate, 2-hydroxypropyl α-chloroacrylate, octyl α-chloroacrylate, octadecyl acrylate, and the like.

In addition, the formula: %Formula% (In the formula, t is a chlorine atom, a hydroxyl group, or a carbon atom number of 1 to 8
It is also possible to use compounds represented by the following aliphatic oxy groups: allyl alcohol, allyl chloride, allyl methyl ether, allyl isopropyl ether, allyl octyl ether, and the like.

Also, if necessary, a small amount of polyvalent metal (for example, M
gs Cas Zns Al, etc.) or polyfunctional nitrogen or phosphorus atom-containing compounds (e.g. polyamines such as alkyl diamines and alkyl triamines,
Divinyl ether or trivinyl ether, which is a salt of polyphosphines (alkylsiphosphine, alkyltriphosphine, etc.) and vinyl ether (I It can be used for purposes such as matting.

Examples of polymerization initiators include persulfates (ammonium persulfate, potassium persulfate, etc.), persulfates and sulfites (
Redox initiators consisting of potassium sulfite, sodium sulfite, etc.) or acidic sulfites (acidic potassium sulfite, acidic sodium sulfite, etc.), organic peroxides (diisopropyl peroxydicarbonate, tert-butyl peroxybutyrate, benzoyl peroxide) ,
isobutyryl peroxide, etc.) and azo compounds (azobisisobutyronitrile, etc.). The amount of initiator used is usually 0 based on the total monomers used.
．． 0.001 to 5% by weight, preferably 0.05 to 2.0% by weight.

There are no particular limitations on the operating method of the production method of the present invention, and methods such as batch, semi-continuous, and continuous methods can be employed.

Next, the present invention will be explained based on Examples, but the present invention is not limited to these Examples.

Reference Example 1 405 g (2,63
mol) and acetone tOW, and add triethylamine (base: pKa-10,72) 2.63
g (0.28 mol) and stirred for 5 minutes with a magnetic stirrer.

While cooling this mixture with ice water to a temperature of 0 to 10°C, add 305 g of hydroxybutyl vinyl ether (2
, 83 mol) was added dropwise at a rate of 2 g/min.

The reaction mixture was subjected to Fourier transform nuclear magnetic resonance analysis (FT
-NMR% ”C%tetramethylsilane standard) and the following vinyl ether (I) of the present invention (hereinafter referred to as cH
HEM salt) and the corresponding free vinyl ether (■
) (hereinafter referred to as cHHEM) was confirmed to be produced at a yield of approximately 10/85 (molar ratio). The chemical shift of each carbon atom (labeled am) is shown.

Wealth δ (ppH) -85.6 (Ta, 151.5 mountains),
67.2(C), 25.3-25.8 I small, 8
2, 8 (e), 173.3 (f), 42.9 (
(I), 27.4, 24.4(I), 43. s+j+
, 178.2 (io, 44.9 (I), 9.l <Blood Reference Example 2 C 11 in the same procedure as Reference Example 1 except that the amount of triethylamine in Reference Example 1 was changed to the amount shown in Table 1. It E
A monomer composition consisting of M salt and c) IHEM was produced. Table 1 shows the yield analyzed by FT-NMR.

Furthermore, the decomposition rate (%) of the obtained reaction product when stored at 20°C and -20°C was examined by 13C-NMR. The results are also listed in Table 1.

[Margin below]

Reference Example 3 The reaction product obtained under the conditions of Experiment No. 4 of Reference Example 2 (c
HHEM salt/cHHEM -0,1/84.9: molar ratio) was added with the base shown in Table 2 to convert cHHEM to ct(
It was converted into HEM salt, and the decomposition rate was examined in the same manner as in Reference Example 2. The results are shown in Table 2.

[Margin below]

As is clear from Table 2, basic compounds with a pKa of less than 6 have weak basicity and therefore contribute little to the stabilization of cHHEH.

Example 1 Monoglyme iaog was charged into a glass autoclave with a capacity of 800 ml and equipped with a stirrer, solidified with liquid nitrogen, and then degassed.

After that, chlorotrifluoroethylene (hereinafter referred to as CTPE)
), and the inside of the system was heated to 85°C. Next, a vinyl ether monomer composition separately obtained in Reference Example 1 (cHHEN salt/cHHEM-10/85,
molar ratio) 72.83 g, hydroxybutyl vinyl ether (hereinafter referred to as HBVE and Iu) 49.9 g, vinyl ester of carboxylic acid having an alkyl group having 10 carbon atoms [Beova 10 manufactured by Shell Chemical Co., Ltd. (hereinafter referred to as VA>161) .4g and azobisisobutyronitrile (
A monomer mixture of 1.64 g of AIBN (hereinafter referred to as AIBN), solidified with liquid nitrogen, and then degassed was continuously charged over a period of 4 hours. The system temperature was maintained at 65°C. After the preparation was completed, the reaction was continued at 85° C. for 18 hours to obtain a carboxyl group-containing fluorine-containing copolymer. The yield was 451 g, and the copolymer concentration was 64.3%.

Examples 2 to 3 and Comparative Examples 1 to 2 Copolymerization was carried out in the same manner as in Example 1 except that the polymerization solvents shown in Table 3 were used to obtain fluorine-containing copolymers. Their yields and copolymer concentrations are shown in Table 3.

[Margin below]

Example 4 The fluorine-containing polymer obtained in Example 1 was diluted with isopropyl alcohol (IPA) to a polymer concentration of 25% by weight. 100 g of the obtained varnish was placed in a flask equipped with a stirrer, MgOIO, og was added thereto, and the mixture was stirred at 60° C. for 24 hours and then filtered through a glass filter for dehalogenation treatment.

The 25% by weight varnish that had been dehalogenated was concentrated under reduced pressure to obtain a varnish with a concentration of 85%. 3.9 parts by weight of dimethylethanolamine (0.9 equivalent to the acid value of the polymer) was added to 100 parts by weight of this varnish for neutralization.

Using the obtained partially neutralized varnish, an electrodeposition coating composition was prepared according to the following formulation.

Parts by weight Varnish 100 Butyl cellosolve 1080% Methyl methylolated melamine resin (Melan 6200 manufactured by Hitachi Chemical, solid content 70%) 20 Deionized water 990 8063S aluminum anodized using this electrodeposition coating composition An alloy plate (9 times the thickness of the alumite film) was used as the object to be painted (anode), the temperature of the coating composition was 20°C, and the voltage was 140V.
The composition was coated on an aluminum alloy plate by applying electricity for 3 minutes, and then washed with water, and then baked and cured at 180°C for 30 minutes to obtain an electrodeposited coating.

The properties shown in Table 4 of the resulting coating film were investigated. The results are shown in Table 4.

(Film thickness) Measured using a film thickness meter (■ Permascope EV model manufactured by Kerato Scientific Research) (unit: knee).

(Gloss) Using a gloss meter (VC-2PD manufactured by Nippon Heavy Industries, Ltd.)
The 0° specular reflectance (unit: 2%) was measured.

(Weather resistance) Weather meter (manufactured by Suga Test Instruments, Ducycle,
60 minutes of irradiation/60 minutes of darkness, black panel temperature 63℃)
A 360-hour accelerated weathering test was conducted to determine the gloss retention rate (
Unit: %) was measured.

(Adhesion) 100 cuts of 1 square square were made in the coating film using a cutter knife, and a peel test was performed 10 times using cellophane adhesive tape to determine the number of remaining cuts.

(boiling water resistance) Conforms to JIS H8802.

(Alkali resistance after boiling water resistance test) The sample after the boiling water resistance test was immersed in a 1% by weight aqueous solution of sodium hydroxide for 72 hours, and then the appearance of the coating film was visually observed to check for the occurrence of blisters.

(Acid resistance) After immersion in a 5% hydrochloric acid solution for 7 days, changes in the coating film were visually determined.

(exterior) The appearance of the coating film was visually judged.

(Liquid Stability) The sample was left standing in an atmosphere at 30° C. for one month, and the change was visually judged.

Examples 5-6 and Comparative Examples 3-4 Electrodeposition coating compositions were prepared in the same manner as in Example 4, except that the fluorine-containing polymers produced in Examples 2-3 and Comparative Examples 1-2 were used, respectively. It was prepared and electrodeposited.

The results are shown in Table 4. - [Margins below] [Effects of the Invention] According to the present invention, by using a specific polymerization solvent, it is possible to increase the yield and provide a more homogeneous fluorine-containing copolymer. When such a fluorine-containing copolymer is used as a coating material, a coating film that is free from flaking and repelling and has excellent weather resistance can be obtained.

Patent applicant: Daikin Industries, Ltd. Procedural amendment stamp button

Claims (1)

[Claims] 1 Formula (I): CH_2=CHOR^1OC(=O)R^2C(=O)
O(H)_nM(I) (in the formula, R^1 is the number of carbon atoms 2
~10 divalent aliphatic groups, R^2 is a divalent organic group, M is an alkali metal, or a monofunctional compound containing a nitrogen atom or a phosphorus atom and whose pKa is 6 to 12. basic compound, n is 0 only in case of alkali metal
, others indicate 1) and the vinyl ether represented by the formula (II): CH_2=
CHOR^1OC(=O)R^2C(=O)OH(II)
(wherein R^1 and R^2 are the same as above), and the vinyl ether represented by formula (I) contains 1 mol% or more of the vinyl ether represented by formula (II). When copolymerizing a vinyl ether monomer composition and a fluoroolefin, formula (III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, Y^1 is an alkyl group having 1 to 8 carbon atoms. , Y^
2 is a hydrogen atom or a methyl group, and n is an integer of 0 or 1 to 20. 2 Vinyl ether represented by formula (I) is converted to formula (II)
The method according to claim 1, wherein the method contains 5 mol% or more of vinyl ether represented by: 3. Claim 1 wherein the alkali metal is Na, K or Li.
Manufacturing method described. 4. The manufacturing method according to claim 1, wherein the basic compound has a pKa of 8 to 11. 5. The production method according to claim 1, wherein the basic compound is ammonia, amines or phosphines. 6. The production method according to claim 5, wherein the basic compound is a tertiary amine. 7. The production method according to claim 1, wherein R^2 is a divalent hydrocarbon group. 8 R^2 is the formula (i): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(i) (In the formula, X^1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X^2 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, p and q represent 0 or an integer of 1 to 11 (however, they are not both 0 at the same time), formula (ii): ▲ Numerical formula, chemical formula , tables, etc.▼(ii) [In the formula, r is 0 or an integer of 1 to 3, s is an integer of 1 to 3, and X^3 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.] Group represented by formula (iii): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(iii) [In the formula, R^7 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ group (However, X^4 is hydrogen atom or an alkyl group having 1 to 3 carbon atoms, t is an integer of 1 to 4), -CH_2CH=CHCH_2- group, ▲numerical formula, chemical formula,
There are tables, etc. ▼ Groups or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Indicates groups] A group represented by formula (iv): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (iv) [In the formula, R^ 8 has ▲mathematical formulas, chemical formulas, tables, etc.▼group (X is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, u is 3
~4) or ▲Mathematical formulas, chemical formulas, tables, etc.▼groups (However,
and X^7 are the same or different, hydrogen atom or carbon atom number 1
~3 alkyl group, v is an integer of 2 to 3)]
A group represented by formula (v): -C(=CH_2)-CH
8. The production method according to claim 7, wherein the group represented by _2-(v) or formula (vi): ▲A mathematical formula, a chemical formula, a table, etc. ▼(vi). 9. The method according to claim 1, wherein the fluoroolefin is selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, trifluoroethylene, vinylidene fluoride, and vinyl fluoride.