JPH09302050A - Fluorocopolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fluorocopolymer which gives a coating film excellent in weatherability, water repellency, etc., and is economically advantageous by synthesizing a fluorocopolymer comprising four specific types of monomer units and another type of units derived from a copolymerizable monomer, each type being in a specified mol%. SOLUTION: This fluorocopolymer has a number-average mol.wt. of 2,000-200,000 and comprises 20-70mol% (based on all the monomer units; the same applies hereunder) units derived from a fluoroolefin, 0.01-50mol% units derived from a macromonomer represented by the formula (wherein n is 5-1,000; R is H or methyl; X1 is alkoxy or alkyl; and X2 is an optionally fluorinated alkyl group), 10-50mol% units derived from a vinyl ether and/or a vinyl ester, 1-30mol% units derived from a monomer other than the macromonomer and having an olefinic double bond and a hydroxyl or alkoxysilyl group, and 0-30mol% units derived from another copolymerizable monomer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel fluorine-containing copolymer and a method for producing the same, and the fluorine-containing copolymer has a coating film excellent in weather resistance, water repellency and lubricity. Since it is formed, it is suitable for a special paint and a coating material for surface treatment.

[0002]

2. Description of the Related Art In recent years, a fluorine-containing copolymer obtained by copolymerizing chlorotrifluoroethylene, cycloalkyl vinyl ether, alkyl vinyl ether and hydroxyalkyl vinyl ether as a resin for coating having high weather resistance (JP-A-57-34107). JP-A-3-231906), and fluorinated copolymers obtained by copolymerizing chlorotrifluoroethylene, alkyl vinyl ether and / or vinyl ester and hydroxyalkyl crotonate are known. The coating compositions based on the copolymers are used in outdoor construction such as bridges and highway sidewalls. However, although these coating compositions are excellent in weather resistance, they are inferior in water repellency and lubricity and are not sufficiently satisfactory in practical use.

Further, based on a fluorine-containing copolymer comprising an alkyl (meth) acrylate, a fluorine-containing (meth) acrylate or a fluorine-containing allyl ether, a low-molecular-weight siloxane-containing (meth) acrylate and an alkoxysilyl group-containing monomer. A coating composition has been proposed (Japanese Patent Publication No. 7-68490). However, although this composition is excellent in water repellency and lubricity, it has a problem in weather resistance. On the other hand, the present inventors have found that a coating composition based on a copolymer composed of a fluoroolefin and a silicone macromonomer having a vinyl ester group at one terminal of the molecule has excellent weather resistance, water repellency and lubricity. Although it has been proposed (Japanese Patent Laid-Open No. 6-322053), it is difficult to industrially use because the silicone macromonomer is expensive.

[0004]

An object of the present invention is to provide a fluorine-containing copolymer which is excellent in weather resistance, water repellency and lubricity and is economically advantageous, and a method for producing the same. To provide.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have prepared a fluorocopolymer mainly containing a fluoroolefin and a silicone macromonomer having a (meth) acryloyl group at one end which is available at a relatively low cost. As a result of trial, when the reaction was carried out by a method in which all of the total amount of all the monomers was charged in a batch, the copolymer composition distribution of the fluoroolefin and the macromonomer was generated, so that the coating film was whitened and the coating film performance was not satisfactory. It was As a result of further intensive studies by the present inventors, the production of the fluorine-containing copolymer has a coating film excellent in weather resistance, water repellency, lubricity, etc. by performing a reaction by a specific charging method. They have found that a copolymer can be obtained, and completed the present invention. That is, the present invention, based on the total amount of all monomer units,
(A) Fluoroolefin-based unit: 20 to 70 mol%, (b) Macromonomer-based unit represented by the following formula (1): 0.01 to 50 mol%, (c) Vinyl ether and / or vinyl ester Units based on: 10
˜50 mol%, (d) a unit based on a monomer other than the above (b) having an olefinic unsaturated double bond and a hydroxyl group or an alkoxysilyl group: 1 to 30 mol%, and (e) other copolymerizable Units based on different monomers: 0
To 30 mol% and a number average molecular weight of 2,000 to 20
It is a fluorine-containing copolymer having a content of 10,000.

[0006]

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(Wherein n is an integer of 5 to 1000, R is a hydrogen atom or a methyl group, X ₁ is an alkoxy group or an alkyl group, X ₂ is an alkyl group which may be substituted with a fluorine atom, and X is ₁ and X ₂ may be the same or different)

In the second invention, the entire amount of fluoroolefin is charged into the reactor before the start of the reaction, and the entire amount or a part of the macromonomer is charged into the reactor by the sequential addition during the reaction, and the residual monomer is left alone. The monomer is a method for producing the above-mentioned fluorine-containing copolymer, which comprises charging it in a reactor and reacting it by an arbitrary method.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the (a) fluoroolefin in the present invention include tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, dichlorodifluoroethylene, trifluoroethylene, vinylidene fluoride and vinyl fluoride. From the viewpoint of polymerizability, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and trifluoroethylene are preferable, and chlorotrifluoroethylene, tetrafluoroethylene and trifluoroethylene are more preferable.

The macromonomer (b) in the present invention is a compound represented by the above formula (1), n in the formula (1) represents a siloxane unit of the macromonomer, and is an integer of 5 to 1000, preferably It is an integer of 10 to 500. n
If it is less than 5, the surface modification effect is insufficient, and if it is greater than 1000, the transparency of the resulting coating film decreases. X ₁ in the formula (1) is an alkoxy group or an alkyl group, and among them, a methoxy group, an ethoxy group and a methyl group are preferable, while X ₂ is an alkyl group which may be substituted with a fluorine atom, Of these, a methyl group, an ethyl group and a 3,3,3-trifluoropropyl group are preferable. The macromonomer is, for example, JP-A-63-2
It can be produced by the method described in Japanese Patent No. 27670.
Specifically, compounds represented by the following formulas (2) to (7) are exemplified, and all have radical-polymerizable (meth) at one end.
It is a compound having an acryloyl group and a hydroxyl group at the other end.

[0011]

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[0012]

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[0013]

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[0014]

[Chemical 6]

[0015]

[Chemical 7]

[0016]

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The vinyl ether and / or vinyl ester (c) in the present invention is used to improve the adhesion and processability of the coating film of the fluorine-containing copolymer, and the vinyl ether is methyl vinyl ether, ethyl vinyl ether or butyl vinyl ether. , Aliphatic vinyl ethers such as isobutyl vinyl ether, hexyl vinyl ether, nonyl vinyl ether and cyclohexyl vinyl ether, and aromatic vinyl ethers such as phenyl vinyl ether and benzyl vinyl ether. Among these, aliphatic vinyl ethers having 2 or more carbon atoms are preferable, more preferably ethyl vinyl ether, from the viewpoint of weather resistance and handling.
Butyl vinyl ether and cyclohexyl vinyl ether.

Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl versatate and vinyl cyclohexanecarboxylate. Aromatic vinyl carboxylates such as vinyl benzoate and p-tert-butyl vinyl benzoate are exemplified. From the viewpoint of weather resistance and solubility, a vinyl ester having an alkyl group having 2 or more carbon atoms or a cycloalkyl group in its side chain is preferable. The vinyl ether and vinyl ester monomers can be used in combination of two or more kinds at the same time.

The monomer (d) having an olefinically unsaturated double bond and a hydroxyl group or an alkoxysilyl group in the present invention is used for imparting room temperature curability. Examples of the monomer having an olefinically unsaturated double bond and a hydroxyl group include hydroxyethyl vinyl ethers such as hydroxyethyl vinyl ether and hydroxybutyl vinyl ether; hydroxyalkyl allyl ethers such as hydroxyethyl allyl ether and hydroxybutyl allyl ether; hydroxyethyl Examples include hydroxyalkyl crotonates such as crotonate and hydroxypropyl crotonate; hydroxyalkyl (meth) acrylates such as hydroxyethyl methacrylate and hydroxybutyl acrylate, and the like, in view of copolymerizability and reactivity with a curing agent, Preferred are hydroxyalkyl vinyl ethers, hydroxyalkyl crotonates and hydroxyalkyl acrylates. That hydroxyalkyl crotonates than stability of the fluorine-containing copolymer and a hydroxyalkyl acrylate are more preferred.

The monomers having an olefinically unsaturated double bond and an alkoxysilyl group include vinylsilanes such as trimethoxyvinylsilane, triethoxyvinylsilane and methyldimethoxyvinylsilane, trimethoxysilylpropyl methacrylate, triethoxysilylpropyl. Illustrative are silyl acrylates such as methacrylate and methyldimethoxysilylpropyl acrylate, with silyl acrylates being preferred because of their ready availability.

The fluorine-containing copolymer in the present invention may optionally contain (e) another copolymerizable monomer. Such monomers include olefins such as ethylene, propylene, vinyl chloride and vinylidene chloride; unsaturated acids such as crotonic acid and itaconic acid; allyl ethers such as allylglycidyl ether and methylallyl ether; methyl (meth) Acrylate,
Examples are (meth) acrylates such as cyclohexyl (meth) acrylate and butyl (meth) methacrylate.

The composition ratio in the fluorocopolymer in the present invention is based on the total amount of all monomer units.
(A) Fluoroolefin-based unit: 20-70 mol%, (b) Macromonomer-based unit: 0.01-
50 mol%, units based on (c) vinyl ether and / or vinyl ester: 10 to 50 mol%, (d) monomers other than (b) having an olefinically unsaturated double bond and a hydroxyl group or an alkoxysilyl group. Units based on 1 to 30 mol% and (e) units based on other copolymerizable monomers: 0 to 30 mol%, preferably (a): 35 to 50 mol%, (b): 0.1-15
Mol%, (c): 15 to 45 mol%, (d): 3 to 25
Mol% and (e): 0 to 20 mol%.

If (a) the unit based on fluoroolefin exceeds 70 mol%, it becomes insoluble in an organic solvent, and if it is less than 20 mol%, the weather resistance is deteriorated, and if the unit based on (b) macromomanomer exceeds 50 mol%. The coating film is soft and easily scratched, and when it is less than 0.01 mol%, the surface modification effect is lowered, and when the unit based on (c) vinyl ether and / or vinyl ester exceeds 50 mol%, the weather resistance is lowered and 10 When it is less than mol%, the solubility of the copolymer in an organic solvent and the adhesion of the coating film are deteriorated, and (d) a monomer other than the above (b) having an unsaturated double bond and a hydroxyl group or an alkoxysilyl group. If the unit based on 30 mol% is too fast, the pot life will be shortened, and if it is less than 1 mol%, the room temperature curability of the coating film will be lost. Units based on a monomer copolymerizable weather resistance is lowered and when it exceeds 30 mol%.

The molecular weight of the fluorine-containing copolymer is 20 in terms of number average molecular weight (in terms of polystyrene) by gel permeation chromatography (hereinafter referred to as GPC).
It is 00 to 200,000, and more preferably 3000 to 100,000. If the molecular weight exceeds 200,000, the viscosity increases and the coating workability deteriorates. If it is less than 2000, the mechanical properties of the resulting coating film deteriorate.

The fluorinated copolymer can be produced, for example, by copolymerizing each of the above monomers in the presence of a radical-generating polymerization initiator. As the polymerization method, suspension polymerization and emulsion polymerization in an aqueous medium, solution polymerization in an organic solvent and the like can be adopted, but a normal batch of charging all the total amount of all monomers into a reactor before the reaction. When charged, the copolymer composition is distributed due to the difference in the polymerizability of the fluoroolefin and the macromonomer, and as a result, the coating film is whitened and weather resistance or water repellency is not exhibited. Therefore, as a method for producing the fluorine-containing copolymer of the present invention, the total amount of the fluoroolefin and, if necessary, the total amount of a monomer other than the macromonomer or a part thereof is pre-reacted with the organic solvent and the initiator. It is preferable that the reaction mixture is charged into the reactor and the whole or a part of the macromonomer is sequentially added during the reaction to charge the reaction mixture in the reactor. Vinyl ether or vinyl ester, which is a monomer other than fluoroolefin and macromonomer, a monomer having an olefinically unsaturated double bond and a hydroxyl group or an alkoxysilyl group, and a method of charging other copolymerizable monomers are Any amount may be charged into the reactor before the reaction, or the whole amount or a part thereof may be sequentially added during the reaction similarly to the macromonomer. The ratio and time of addition of macromonomers sequentially during the reaction are not particularly limited, but in order to make the copolymerization as uniform as possible, use more than half of the total amount of macromonomers over half the reaction time. It is desirable to add continuously.

As the radical-generating type polymerization initiator,
Peroxides such as diisopropyl peroxydicarbonate, tertiary butyl peroxypivalate, benzoyl peroxide and lauroyl peroxide, azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile, ammonium persulfate and potassium persulfate Inorganic peroxides such as can be used. The amount used is preferably in the range of 0.001 to 10 parts by weight based on 100 parts by weight of all the monomers.

As the organic solvent used in the solution polymerization, organic hydrocarbons, fluorine-containing solvents and the like are suitable, and cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; acetic acid. Esters such as ethyl and butyl acetate;
Examples thereof include ketones such as acetone, methyl ethyl ketone and cyclohexanone; and fluorocarbons such as 1,1,2-trichloro-1,2,2-trifluoroethylene. These can be used alone or in combination of two or more kinds.

As the emulsifier for emulsion polymerization,
Examples thereof include perfluorooctanoic acid potassium salt or ammonium salt, perfluorooctanesulfonic acid ammonium salt, higher alcohol sulfate sodium salt and polyethylene glycol ether.
The amount of emulsifier used is 0.1 with respect to 100 parts by weight of all monomers.
The range of ˜50 parts by weight is preferred. The polymerization conditions are not particularly limited, but a suitable polymerization temperature in a preferable reaction is 20 to 100 ° C., and a suitable pressure is 1 to 200 kg.
/ cm ² , and a more suitable reaction time is 3 to 40 hours. Further, if necessary, potassium carbonate, sodium hydrogen carbonate, hydrotalcite, anion exchange resin or the like may be added as a pH adjusting agent.

When the fluorine-containing copolymer of the present invention has a hydroxyl group, it can be used as a room temperature curable coating composition by dissolving it in an organic solvent and then using it in combination with a polyvalent isocyanate compound. Examples of this polyvalent isocyanate compound include hexamethylene diisocyanate trimer and isophorone diisocyanate.
It is also possible to heat-cure using blocked isocyanate, methylated melamine and butylated melamine. A curing accelerator such as dibutyltin dilaurate and p-toluene sulfonic acid may be added.

On the other hand, when the fluorine-containing copolymer of the present invention contains an alkoxysilyl group, it is used as a moisture-curable coating composition by dissolving it in an organic solvent and then using a curing accelerator together. it can. Examples of this curing accelerator include tin compounds, titanium compounds and amines. As the organic solvent, aromatic hydrocarbons such as toluene and xylene, acetic acid esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbons such as trichloroethane and trifluorotrichloroethane. Examples thereof are acetic acid esters and ketones.

Further, in preparing the coating composition, in addition to the above-mentioned curing agent, curing accelerator and organic solvent,
Various additives such as pigments, flow control agents, ultraviolet absorbers, dispersion stabilizers and leveling agents, and other resins such as acrylic resins may be added if necessary.

[0032]

EXAMPLES Specific examples will be described below.

Example 1 200 g of ethyl acetate, 10 g of a macromonomer represented by the following formula (8) (hereinafter referred to as MSi), and 2-hydroxyethyl crotonate (hereinafter referred to as HECR) were placed in a 1-liter stainless steel autoclave equipped with a stirrer. 50 g and 25 g of vinyl pivalate (hereinafter referred to as VPv) were charged, deaeration and nitrogen substitution were repeated 3 times, and then deaerated, and chlorotrifluoroethylene (hereinafter referred to as CTFE) 350.
g was charged into the autoclave.

[0034]

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After the temperature was raised to 64 ° C., 2.5 g of tertiary butyl peroxypivalate (hereinafter referred to as PV) was injected under pressure to initiate polymerization. During the following 8 hours, 30 g of MSi and 30 g of VPv were added sequentially. After polymerization was carried out at 64 ° C. for a total of 10 hours, unreacted CTFE was purged, the autoclave was opened, and the resulting solution was put into methanol and washed and dried to obtain 180 g of a copolymer. GP
The polystyrene reduced number average molecular weight of this copolymer measured by C was 8000, and the glass transition temperature (hereinafter referred to as Tg) of the copolymer was 36.0 ° C. When the fluorine analysis of this copolymer was performed, it was 17.9% and the hydroxyl value was 83 (mg-KOH / g-resin). ¹
From 1 H-NMR and ¹³ C-NMR, the composition of the copolymer was CTFE / MSi / VPv / HECR = 46.7 / 0.
It was confirmed to be 3 / 31.9 / 21.1 (mol%).

Test Example 1 The copolymer obtained in Example 1 was dissolved in butyl acetate to obtain a colorless transparent solution having a solid content of 40% by weight. To 100 parts by weight of this solution, polyisocyanate [Takenate D
177N, manufactured by Takeda Pharmaceutical Co., Ltd.] 12 parts by weight (NCO / O
(Corresponding to H = 1/1) and 25 parts by weight of ethyl acetate, and then coated on a chromate-treated aluminum plate (thickness 0.8 mm) with an applicator so that the coating film thickness becomes 20 μ, A coated plate for test was prepared by drying and curing at room temperature for one week. The obtained coating film was transparent and was not cloudy. The following test was conducted using this sample, and the results are shown in Table 1 below.

(Test item and test method) Adhesion: 100 incisions were made in a square of 1 cm ² .
The residual rate when peeled off with cellophane tape is shown. -Dynamic friction coefficient (μ): Measured with a HEIDON type friction measuring machine. Contact angle (degree): The contact angle of water and hexadecane (HD) was measured. -Magic stain property: The repellency when applied with black magic ink and the remaining condition when applied with magic ink and left for 1 day and wiped off with ethanol were visually determined. Repellent: ○ Repels in a ball shape, △ Repels in a ball shape,
× Not repelled Remaining: ○ No remaining, △ Remaining thin, × Remaining clearly ・ Weather resistance: 70 by Atlas QUV weather resistance tester
After irradiation for 00 hours, the 60 ° gloss retention (%) was evaluated.

Example 2 300 g of CTFE, vinyl versatate [Veva-9 manufactured by Shell Kagaku Co., Ltd., hereinafter referred to as V-9] were initially charged in an amount of 35 g and 40 g, and MSi was initially charged in 10 g and 40 g, respectively. Example 1 except that HECR was 32 g, hydroxybutyl acrylate (hereinafter referred to as HBA) was initially charged to be 6 g, and sequentially added to be 15 g.
Polymerization was carried out in the same manner as above to obtain 200 g of a copolymer. The polystyrene equivalent number average molecular weight of the obtained copolymer measured by GPC was 7,500, and Tg was 56.5 ° C. When the fluorine analysis of this copolymer was performed, it was 14.8% and the hydroxyl value was 70 (mg-KOH / g-resin). ^{From 1} H-NMR and ¹³ C-NMR, the composition of the copolymer was CTFE / MSi / V-9 / HECR / HB.
A = 46.5 / 0.3 / 31.0 / 9.5 / 12.7
(Mol%). Test Example 2 A coated plate for test was prepared from the copolymer obtained in Example 2 in the same manner as in Test Example 1. The obtained coating film was transparent and was not cloudy. The same test as in Test Example 1 was performed using this sample. The results are shown in Table 1 below.

Example 3 200 parts of trifluoroethylene (hereinafter referred to as TrFE) was used.
g, vinyl propionate (hereinafter referred to as VPr) was initially charged 23 g and sequentially added 30 g, macromonomer represented by the following formula (9) (hereinafter referred to as MSi2) was initially charged 3 g and sequentially added 10 g, and HECR was set to 32 g Was polymerized in the same manner as in Example 1 to give 83 g of a copolymer.
I got

[0040]

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The polystyrene-reduced number average molecular weight of the obtained copolymer was 6000 and Tg was 26.8 ° C. The fluorine analysis value of this copolymer was 23.0%,
The hydroxyl value was 45. The same analysis as in Example 1 was carried out, and C
TFE / MSi2 / VPr / HECR = 42.8 / 0.
It was confirmed to be 4 / 48.4 / 8.4 (mol%). Test Example 3 A coated plate for test was prepared in the same manner as in Test Example 1 from the copolymer obtained in Example 3. The obtained coating film was transparent and was not cloudy. The same test as in Test Example 1 was performed using this sample. The results are shown in Table 1 below.

Example 4 30 parts of hexafluoropropylene (hereinafter referred to as HFP)
0 g of ethyl vinyl ether (hereinafter referred to as EVE) 5
1 g, a macromonomer represented by the following formula (10) (MS
i3) was initially charged 10 g and added sequentially 15
g, hydroxybutyl vinyl ether (hereinafter referred to as HBVE) 26 g, Kyoward 200 as an acid kitcher
[Kyowa Chemical Industry Co., Ltd.] 5 g, 2.5 g of azobisisobutyronitrile as an initiator and 30 g of ethyl acetate
Polymerization was performed in the same manner as in Example 1 except that 0 g was charged to obtain 210 g of a copolymer.

[0043]

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The number average molecular weight of the obtained copolymer is 100.
00 and Tg was 28.6 ° C. The fluorine analysis value of this copolymer was 38.9%, and the hydroxyl value was 47. The analysis is performed in the same manner as in Example 1, and HFP / MSi3 /
EVE / HBVE = 50.0 / 0.1 / 38.0 / 1
It was confirmed to be 1.9 (mol%). Test Example 4 A coated plate for test was prepared in the same manner as in Test Example 1 from the copolymer obtained in Example 4. The obtained coating film was transparent and was not cloudy. The same test as in Test Example 1 was performed using this sample. The results are shown in Table 1 below.

Example 5 300 g of CTFE, 60 g of EVE, 15 g of MSi initially charged and 16 g of sequential addition, 2 g of triethoxysilylpropyl methacrylate (hereinafter referred to as TESMA)
Polymerization was performed in the same manner as in Example 1 except that the amount was 9 g to obtain 130 g of a copolymer. The number average molecular weight of the obtained copolymer was 8000, Tg was 20.0 ° C., and the fluorine analysis value was 2
2.6%. Analysis was performed in the same manner as in Example 1, and CTFE was used.
/MSi/EVE/TESMA=46.6/0.1/4
It was confirmed to be 8.9 / 4.4 (mol%). Test Example 5 The copolymer obtained in Example 5 was dissolved in butyl acetate to obtain a colorless and transparent solution having a solid content of 40% by weight. Dibutyltin dilaurate (0.02) was added to 100 parts by weight of this solution.
After adding 10 parts by weight of methyl isobutyl ketone and 10 parts by weight of methyl isobutyl ketone, a chromate-treated aluminum plate (thickness: 0.
8 mm) was coated with an applicator so that the coating thickness would be 20 μ, dried and cured at room temperature for 1 week to prepare a test coated plate. The resulting coating film was transparent and was not cloudy. The same test as in Test Example 1 was performed using this sample. The results are shown in Table 1 below.

Example 6 All the monomers of Example 2 were initially charged all at once and batch polymerization was carried out to obtain 190 g of a copolymer. The polystyrene reduced number average molecular weight of this copolymer measured by GPC was 12000 and Tg was 51.2 ° C. The fluorine analysis result of this copolymer was 13.2%, and the hydroxyl value was 82 (mg-KOH / g-resin). ¹ H
From -NMR and ¹³ C-NMR, the composition of the copolymer was
CTFE / MSi / V-9 / HECR / HBA = 42.
4 / 0.3 / 31.1 / 13.4 / 12.8 (mol%)
Was confirmed. Test Example 6 A coated plate for test was prepared from the copolymer obtained in Example 6 in the same manner as in Test Example 1. The coating film obtained was cloudy. The same test as in Test Example 1 was performed using this sample.
The results are shown in Table 1 below.

[0047]

[Table 1]

Test Examples 7-9 To 100 parts by weight of the copolymers obtained in Examples 1, 2 and 6, was added 61.3 parts by weight of TAIPAKE CR-97 (titanium oxide manufactured by Ishihara Sangyo Co., Ltd.). Then, butyl acetate was added so that the solid content was 40% by weight, 250 parts of glass beads were added, and the mixture was dispersed with a paint conditioner.
After removing the glass beads with a filter cloth, 0.01 part of dibutyltin dilaurate was added as a curing accelerator to form a white paint. Next, Takenate D177N was added to NCO / OH = 1 /
Mix so as to be 1 (equivalent ratio), and coat on a chromate-treated aluminum plate with a thickness of 0.6 mm coated with 5 μ of epoxy base coat so that the film thickness after drying will be 30 μ, and mix at room temperature. Dried for a week. The following tests were conducted using this sample, and the results are shown in Table 2 below. (Test Examples 7 and 8
And 9 correspond to coatings made from the copolymers obtained in Examples 1, 2 and 6, respectively)

(Test Items and Test Method) The adhesion, dynamic friction coefficient, contact angle, magic stain resistance, and weather resistance are the same as in Test Examples 1 to 6 above. -Gloss (60 ° C gloss): Measured according to JIS-K5400. DuPont impact test: A weight of 500 g was dropped on the coating film, and the limit height (cm) at which the coating film was not broken was measured.

Test Example 10 Using the copolymer obtained in Example 5, white paints were prepared in the same manner as in Test Examples 7-9. 0.05 part by weight of dibutyltin dilaurate was mixed as a curing accelerator and dried at room temperature for one week. The above test was conducted using this sample, and the results are shown in Table 2 below.

Comparative Example A white paint was prepared in the same manner as in Test Examples 7 to 9 using ZAFLON FC220 [trade name: manufactured by Toagosei Co., Ltd.] as a fluororesin in which no macromonomer was copolymerized. The above test was conducted using this paint, and the results are shown in Table 2 below.

[0052]

[Table 2]

[0053]

The fluorine-containing copolymer of the present invention is required to be wax-free because it can exhibit water repellency, lubricity, etc. for a long period of time in addition to the high weather resistance that conventional fluororesin coating materials have. It is suitable for special paints such as automotive paints, anti-graffiti paints, anti-posting paints and anti-icing paints, and coating materials for surface treatment. Further, from the fluorine-containing copolymer obtained by the production method of the present invention, a solution without clouding or a transparent coating film can be obtained, and the physical properties thereof are also extremely excellent.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08F 230/08 MNU C08F 230/08 MNU // C09D 127/12 PFG C09D 127/12 PFG (72) Inventor Yasuomi Maruyama 1 Toa Gosei Co., Ltd. Nagoya Research Institute, 1 Funami-cho, Minato-ku, Nagoya, Aichi

Claims (2)

[Claims] 1. Based on the total amount of all monomer units,
(A) Fluoroolefin-based unit: 20 to 70 mol%, (b) Macromonomer-based unit represented by the following formula (1): 0.01 to 50 mol%, (c) Vinyl ether and / or vinyl ester Units based on: 10
˜50 mol%, (d) a unit based on a monomer other than the above (b) having an olefinic unsaturated double bond and a hydroxyl group or an alkoxysilyl group: 1 to 30 mol%, and (e) other copolymerizable Units based on different monomers: 0
To 30 mol% and a number average molecular weight of 2,000 to 20
A fluorine-containing copolymer having a content of 10,000. Embedded image (In the formula, n is an integer of 5 to 1000, R is a hydrogen atom or a methyl group, X ₁ is an alkoxy group or an alkyl group, X ₂
Represents an alkyl group which may be substituted with a fluorine atom, and X ₁ and X ₂ may be the same or different) 2. The whole amount of the fluoroolefin is charged into the reactor before the reaction is started, and the whole amount or a part of the macromonomer is charged into the reactor by the sequential addition during the reaction, and the remaining monomer is optional. The method for producing a fluorine-containing copolymer according to claim 1, wherein the reaction is carried out by charging it in a reactor by the method.