JPH09176245A - Fluorocopolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fluorocopolymer which is suitable for a one-pack coating soln. excellent in weatherability and stain resistance. SOLUTION: This fluorocopolymer has a number-average mol.wt. of 10,000-500,000 and contains 20-70mol% fluoroolefin-based structural units, 1-80mol% structural units having a photocuring functional group, and 0-70mol% other structural units.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fluorine-containing copolymer and a method for producing the same.

[0002]

2. Description of the Related Art A coating material composition containing a fluorine-containing copolymer as a main component is known to have many advantages such as excellent weather resistance, corrosion resistance, antifouling property and water repellency. However, the coating material composition containing a fluorine-containing copolymer as a main component has a problem in workability because it is difficult to dissolve in a solvent.

As a coating material composition containing a fluorine-containing copolymer as a main component for solving these problems, a fluoroolefin-vinyl ether copolymer is known and is used as a coating composition. The resin composition has excellent weather resistance, and industrial benefits such as enhancing durability of buildings are being recognized.

However, these resins required a polyisocyanate type curing agent or a melamine type curing agent. In the former case, it can be cured at room temperature, but there is a disadvantage that it is necessary to mix the two liquids at the time of use. In the latter case, the above-mentioned inconvenience is solved, but a high temperature baking operation is required, and the heat resistance of the base material is restricted.

In order to avoid such restrictions, a one-part curable resin curing composition in which a photopolymerization site is introduced into a side chain of a polymer containing fluorine in the main chain skeleton has been proposed (Japanese Patent Laid-Open No. 1-1999).
51418) requires the simultaneous polymerization of a fluorine-containing copolymer with another monofunctional or polyfunctional (meth) acrylic monomer.

[0006]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art, is not restricted by the base material, can be used as a single liquid, and can be cured at room temperature and has a short curing time. Further, the present invention provides a cured resin product which does not require simultaneous polymerization of a fluorinated copolymer and another monofunctional or polyfunctional (meth) acrylic monomer and can be cured alone to provide sufficient weather resistance.

[0007]

SUMMARY OF THE INVENTION The present invention is the following invention. 20 to 70 mol% of polymerized units (1) based on fluoroolefin, 1 to 80 mol% of polymerized units (2) having a photocurable functional group, and other polymerizations. Unit (3) is 0 to all polymerized units
A fluorine-containing copolymer having a ratio of 70 mol%,
A fluorinated copolymer having a number average molecular weight of 10,000 to 500,000.

Monomer (B) copolymerizable with fluoroolefins (A) and (A) and having a photocurable functional group
And other monomers (C) are copolymerized in a proportion of 20 to 70 mol% of (A), 1 to 80 mol% of (B) and 0 to 70 mol% of (C) with respect to all the monomers. A method for producing a fluorinated copolymer, comprising:

Monomers (E) and other monomers (C) containing a functional group copolymerizable with the fluoroolefins (A) and (A) and capable of introducing a photocurable functional group are all included. (A) 20 to 70 mol%, (B) 1 to 80 relative to monomer
At least one of the functional groups capable of introducing the photocurable functional group in (D) after obtaining the fluorine-containing copolymer (D) by copolymerizing at a ratio of mol% and (C) 0 to 70 mol%. A method for producing a fluorinated copolymer, which comprises introducing a photocurable functional group into a part.

A composition containing the above-mentioned fluorine-containing copolymer.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The fluorine-containing copolymer of the present invention comprises 20 units of a polymer unit (1) based on a fluoroolefin (A).
˜70 mol%. The polymerized unit (1) based on fluoroolefin is a polymerized unit obtained by polymerizing the fluoroolefin (A).

The fluoroolefin (A) is a compound having an ethylenically unsaturated group, and one or more hydrogen atoms directly connected to the carbon atom forming the ethylenically unsaturated group are substituted with fluorine atoms. Refers to a compound. Particularly, a compound having 2 to 6 carbon atoms is preferable, and a compound having 2 to 4 carbon atoms is particularly preferable. The fluoroolefin (A) may be a compound containing a halogen atom other than a fluorine atom in addition to the fluorine atom. Particularly preferred is a perhaloolefin in which a hydrogen atom directly connected to a carbon atom forming an ethylenically unsaturated group is completely replaced by a halogen atom.

Specific examples of the fluoroolefin (A) include tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride and hexafluoropropylene.

When the content of the polymerized units (1) based on the fluoroolefin (A) is less than 20 mol%, sufficient weather resistance is not exhibited and stains may become remarkable during long-term use, which is not suitable. When the polymerized units based on fluoroolefin exceeds 70 mol%, the adhesion to other materials is lowered and the solubility in a solvent is lowered, which is not suitable. In particular, the polymerized units (1) based on the fluoroolefin (A) are 30 to
It is preferable to contain 60 mol%.

The fluorinated copolymer of the present invention has the polymerized unit (2) having a photocurable functional group in a proportion of 1 to 80 mol%. Because of having this photocurable functional group, the composition containing the fluorine-containing copolymer of the present invention is cured immediately upon irradiation with light such as ultraviolet rays to form a film.
It is particularly preferred that the photocurable functional group is located at the end of the side chain with respect to the polymerization main chain. It is considered that the cured product having a crosslinked bond formed on the basis of the curable site at the terminal of the side chain exhibits particularly excellent weather resistance and solvent resistance due to the specific crosslinked structure.

Polymerized unit (2) having a photocurable functional group
Is preferably a polymerized unit obtained by polymerizing a monomer having a polymerizable site and a polymerized unit having a photocurable functional group.

As the photocurable functional group in (2),
It is preferably a group selected from an acryloyl group, a methacryloyl group, a cinnamoyl group and an azido group.

Polymerized unit (2) having a photocurable functional group
On the one hand, it is preferably a polymerized unit obtained by polymerizing the monomer (B) copolymerizable with (A) and containing a photocurable functional group. On the other hand, (A)
After polymerizing a monomer (E) containing a functional group capable of introducing a photocurable functional group, the photocurable functional group can be introduced into at least a part of the functional group. It is preferably a polymerized unit obtained by introducing a functional group.

The monomer (B) having a photocurable functional group has a polymerizable site which is copolymerizable with (A).
Examples of the polymerizable site copolymerizable with (A) include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, and an isopropenyl group.

The monomer (B) is a photocurable resin containing a polymerizable monomer having a polymerizable site capable of copolymerizing with (A) and having a hydroxyl group (hydroxyl group-containing monomer (F)). A compound obtained by reacting a compound having both a functional group and a hydroxyl group-reactive group is preferable.

The photocurable functional group in the monomer (B) is preferably a cinnamoyl group or an azide group. Specific examples of the compound having both a photocurable functional group and a hydroxyl group reactivity include cinnamoyl chloride.

Examples of the hydroxyl group-containing monomer (F) include allyl alcohol, hydroxyalkyl vinyl ether and hydroxyalkyl allyl ether. Also,
A monomer obtained by reacting a diol with a monomer having a functional group capable of reacting with a hydroxyl group such as acrylic acid, methacrylic acid, or allyl glycidyl ether may also be used.

Further, the monomer (B) is photocurable by directly reacting such a hydroxyl group-containing monomer (F) with a compound having both a photocurable functional group and a hydroxyl reactive group. Not only those having a functional group introduced therein, but also those having a photocurable functional group introduced through a spacer selected from a polyether chain, a polyurethane chain, a polyamide chain and a polyester chain are preferable.

The upper limit of the degree of polymerization of polymerized units in the polyether chain, polyurethane chain, polyamide chain or polyester chain is preferably about 20. If the distance from the polymerizable site to the photocurable functional group becomes too long, the film obtained by curing the fluorocopolymer becomes too flexible, and the weather resistance,
It is not preferable because the stain resistance is lowered.

The spacer is especially a polyether chain and / or
Alternatively, it is preferably a polyester chain. The polyether chain has about 2 to 10 carbon atoms, particularly 2 to 6 carbon atoms.
A polyether chain obtained by ring-opening polymerization of the alkylene oxide of is preferable. A polyether chain obtained by ring-opening polymerization of propylene oxide is particularly preferable. As the polyester chain, a polyester chain obtained by ring-opening polymerization of a cyclic ester such as caprolactone is preferable.

In the present invention, it is particularly preferable that the spacer has a polyether chain or a polyester chain having a degree of polymerization of 2 to 10.

Specifically, a hydroxyl group-containing monomer (F) is polymerized with a cyclic ether or a cyclic ester to introduce a polyether chain or a polyester chain, and then a photocurable functional group and a hydroxyl group reactive group are both present. A method of reacting a compound can be adopted.

Examples of the compound having a photocurable functional group and a hydroxyl group-reactive group include (meth) acrylic acid derivatives such as (meth) acrylic acid and (meth) acrylic acid chloride in addition to the above-mentioned cinnamoyl chloride. .

The monomer (E) having a functional group copolymerizable with (A) and capable of introducing a photocurable functional group is
Examples thereof include the monomers before the introduction of the photocurable functional group. That is, a polymerizable monomer capable of introducing a photocurable functional group such as a hydroxyl group-containing monomer (F) or a monomer having a spacer formed on the hydroxyl group-containing monomer (F), It is a monomer before the introduction of a functional group.

When the monomer (E) is used, it is polymerized with the fluoroolefin (A) and the like to give a fluorine-containing copolymer (D).
Then, a photocurable functional group is introduced.

The polymer unit (2) having the photo-curable functional group is contained in a proportion of 1 to 80 mol% based on the total polymer units. If this ratio is less than 1 mol%, the crosslink density is lowered and a film having good weather resistance and stain resistance cannot be obtained. On the other hand, if it exceeds 80 mol%, the resulting film becomes too brittle, and the curing time becomes long, which is not suitable for work. The number of polymer units (2) having a photocurable functional group is 5 based on all polymer units.
It is particularly preferable that the content is ˜40 mol%.

A fluoroolefin (A) consisting of only one kind and a monomer (B) having a photocurable functional group consisting of only one kind, or a monomer containing a functional group other than the photocurable functional group consisting of only one kind. When the monomer (E) is copolymerized, there is a high possibility of alternating copolymerization. In particular, the monomer (B) or the monomer (E) is a vinyl monomer or an allyl monomer. This is extremely likely in some cases.

When the alternating copolymerization is carried out, the number of other polymerized units existing between the polymerized units (2) having a photocurable functional group becomes about one, and the film provided by the resulting fluorocopolymer tends to be brittle. It is in.

Therefore, the fluoroolefin (A)
Alternatively, at least one of the monomer (B) and the monomer (E) is preferably a mixture of two or more monomers of different types. Alternatively, in addition to the fluoroolefin (A) and the monomer (B) having a photocurable functional group, a method of copolymerizing another monomer (C) copolymerizable therewith, is used to obtain a fluorine-containing compound. In the copolymer, it is preferable that a large number of other polymer units exist between the polymer units having a photocurable functional group. Usually, the latter method of copolymerizing the other monomer (C) is adopted.

The fluorinated copolymer of the present invention may be composed of only the polymer units of (1) and the polymer units of (2), and the polymer units (3) other than (1) and (2), That is, it may have a polymerized unit (3) based on a monomer (C) other than (A) and (B). In this case, polymerized units (3)
Is required to be 0 to 70 mol% with respect to all polymerized units. That is, polymerized unit (1) and polymerized unit (2)
It is necessary that the total of the above is contained in a proportion of 30 mol% or more with respect to all polymerized units. When the proportion of the two types of polymerized units contained is less than 30 mol%, sufficient weather resistance and stain resistance cannot be exhibited.

The other monomer (C) does not have a hydrogen atom directly connected to a carbon atom forming an ethylenically unsaturated group replaced with a fluorine atom, and has no photocurable functional group. The monomer (C) includes vinyl group, allyl group,
Examples thereof include monomers having a polymerizable site such as an acryloyl group, a methacryloyl group and an isopropenyl group.

Specifically, vinyl ethers, olefins, allyl ethers, vinyl esters, allyl esters, acrylic acid esters, methacrylic acid esters, isopropenyl ethers, isopropenyl esters and crotonic acid esters, Is mentioned. Among these, compounds having a linear, branched or alicyclic alkyl group having about 1 to 15 carbon atoms are preferable. The alkyl group may have a hydrogen atom substituted with a halogen atom such as a fluorine atom.

Specific compounds include vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, chloroethyl vinyl ether and vinyl perfluoroalkyl ether, and olefins such as ethylene, propylene, 1-butene, isobutylene and cyclohexene. Allyl ethers such as methyl allyl ether, ethyl allyl ether, butyl allyl ether, cyclohexyl allyl ether, 2-hydroxyethyl allyl ether, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, caproic acid Vinyl, vinyl caprylate, Veova 9 and Veova 10 (trade name of vinyl ester of branched fatty acid having 9 or 10 carbon atoms, manufactured by Shell Chemical Co., Ltd.), Versa Fatty acid vinyl esters such as vinyl Ikku acid, allyl esters such as allyl acetate, ethyl acrylate, methyl methacrylate, butyl acrylate,
Acrylic acid esters or methacrylic acid esters such as butyl methacrylate and cyclohexyl methacrylate,
Examples thereof include crotonates such as ethyl crotonate, butyl crotonate and cyclohexyl crotonate.

Among the above monomers, vinyl ethers, vinyl esters, allyl ethers, allyl esters,
Monomers selected from isopropenyl ethers, isopropenyl esters, and crotonic acid esters are particularly preferable, and vinyl ethers are more preferable, and the use of vinyl ethers makes it possible to carry out alternating copolymerization with fluoroolefin (A). Is high and is preferable in terms of weather resistance.

The fluorine-containing copolymer has a number average molecular weight of 100.
It is 00-500000. Number average molecular weight is 50,000
If it exceeds 0, the solubility in the solvent is low, and the viscosity becomes too high, which is inconvenient for work. When the number average molecular weight is less than 10,000, physical properties such as weather resistance are poor. Preferably 10,000
~ 30,000.

The fluorine-containing copolymer of the present invention is obtained by the following production method. Fluoroolefin (A), monomer (B) and other monomer (C) are (A) 20 to 70 mol%, (B) 1 to 80 mol% and (C ) A method of copolymerizing at a ratio of 0 to 70 mol%.

Fluoroolefin (A), monomer (E)
And other monomers (C) are copolymerized in a proportion of 20 to 70 mol% of (A), 1 to 80 mol% of (B) and 0 to 70 mol% of (C) with respect to all the monomers. A method of introducing a photocurable functional group into at least a part of the functional group capable of introducing the photocurable functional group in (D) after obtaining the fluorinated copolymer (D).

The polymerization method may be any of solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization, and the polymerization is carried out by causing a predetermined amount of a monomer to act on a polymerization initiation source such as a polymerization initiator. . In addition, other various conditions may be the same as those used in ordinary solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization and the like.

When the method using the monomer (E) is adopted, the photocurable functional group is introduced after the fluorine-containing copolymer (D) is obtained. At this time, when a hydroxyl group-containing polymer (F) is used as the monomer (E), after obtaining the fluorine-containing copolymer (D), directly or after forming a spacer, a photocurable functional group and a hydroxyl group are formed. A photocurable functional group is introduced by reacting a compound having a reactive group. When a monomer having a spacer such as a polyether chain is used as the hydroxyl group-containing polymer (F), a photo-curable functional group and a hydroxyl group-reactive group are added after the fluorine-containing copolymer (D) is obtained. A photo-curable functional group is introduced by directly reacting the compound having.

When a monomer having a functional group capable of reacting with a hydroxyl group such as acrylic acid, methacrylic acid or allyl glycidyl ether is used, the fluorocopolymer (D) is used.
After reacting with dialcohol and then or after forming a spacer, a photocurable functional group is introduced.

The present invention is also a composition containing the above-mentioned fluorine-containing copolymer. Since the fluorine-containing copolymer of the present invention gives a film having good weather resistance and stain resistance, the composition is suitable as a one-component curing type coating material. In particular, the fluorine-containing copolymer in the present invention does not need to be copolymerized with other monomers or oligomers. A cured product obtained by curing the fluorinated copolymer as a curing component has sufficiently excellent physical properties.

Particularly, the fluorine-containing copolymer is dissolved in a solvent,
Use as a solution composition is preferable because it facilitates the coating operation. As such a solvent, various solvents can be used, and aromatic hydrocarbons such as xylene and toluene, esters such as butyl acetate, ketones such as methyl isobutyl ketone, and glycol diene such as diethyl cellosolve. Ethers or the like may be used, and various commercially available thinners may be used. Further, these may be mixed and used in various ratios. It is preferable to appropriately select such an organic solvent in consideration of the state of the material to be coated, the evaporation rate, the working environment, and the like.

The composition containing such a fluorine-containing copolymer is further added with a filler, a light stabilizer, a heat stabilizer, a leveling agent, a plasticizer, a physical property modifier, an ultraviolet absorber and the like. May be.

[0049]

EXAMPLES Synthesis examples (Examples 1 to 10) and Examples (Example 1) will be described below.
1, 12, 15 to 20) and comparative examples (Examples 13 and 14)
The present invention will be described below.

(Example 1) 100.0 g (0.86 mol) of hydroxybutyl vinyl ether and 491.3 g (4.30 mol) of ε-caprolactone were weighed in a 1 L flask, and 178 mg of tetrabutyl titanate was added thereto. By reacting at 150 ° C. for 6 hours under stirring,
A lactone-modified hydroxybutyl vinyl ether having a number average molecular weight of 687 was obtained.

(Example 2) In a pressure-resistant reactor made of stainless steel with an internal volume of 550 cm ³ equipped with a stirrer, 120.0 g (1.03 mol) of hydroxybutyl vinyl ether and 0.9 g of potassium hydroxide were weighed, and then propylene oxide was added. 18 total
0 g (3.10 mol) was gradually added at 3 kg / cm ² and the reaction was carried out at 110 ° C. for 2 hours. The obtained liquid was purified with synthetic magnesia to have a number average molecular weight of about 300.
To obtain propylene oxide-modified hydroxybutyl vinyl ether.

Example 3 100 g of the lactone-modified hydroxybutyl vinyl ether obtained in Example 1 was placed in a 1 L flask.
Weigh out (containing 0.15 mol of hydroxyl group), and further add 100 g of acetone and 17.7 g of triethylamine (0.1 g).
7 mol), and hydroquinone monomethyl ether 15
mg was added, and the mixture was stirred under a nitrogen stream at 40 ° C. for 10 minutes.

Then, 26.6 g of cinnamoyl chloride
A solution of (0.16 mol) in 100 g of acetone was added dropwise over 30 minutes. Then, raise the temperature to 57 ° C and
The reaction was completed by stirring for half an hour. Then, the ammonium salt was filtered off, and the filtrate was added dropwise to 3 L of stirred water to reprecipitate the resin. Then, the precipitated resin was washed twice with water and then dried to obtain a desired lactone-modified hydroxybutyl vinyl ether having a photocurable functional group introduced therein.

(Example 4) The propylene oxide-modified hydroxybutyl vinyl ether obtained in Example 2 was introduced with a cinnamoyl moiety in the same manner as in Example 3 to obtain a desired propylene oxide-modified hydroxybutyl vinyl ether into which a photocurable functional group was introduced. It was

(Examples 5 to 10) A stainless steel pressure-resistant reactor equipped with a stirrer having an internal volume of 550 cm ³ was charged with 252 g of xylene, 71 g of ethanol, 1.4 g of potassium carbonate and 2.2 g of azoisobutyronitrile. A monomer having the composition shown (unit: g, mol% in parentheses) was polymerized.

Polymerization was carried out by using chlorotrifluoroethylene (C
TFE) or monomers other than tetrafluoroethylene (TFE) are charged, residual air is removed by liquid nitrogen, then CTFE or TFE is introduced, and the temperature is gradually raised and then maintained at 65 ° C. Then, the polymerization reaction was continued for 6 to 10 hours under stirring, and then the reactor was water-cooled to stop the polymerization. After cooling the reactor to room temperature, unreacted monomers were withdrawn and the reactor was opened. After the polymer solution was filtered, ethanol was removed at 50 ° C. using an evaporator to obtain a xylene solution of a fluorinated copolymer. Table 1 shows the molecular weight of the obtained fluorocopolymer.

However, in the table, EVE is ethyl vinyl ether, CHVE is cyclohexyl vinyl ether, and HBV.
E represents hydroxybutyl vinyl ether.

(Examples 11 to 14) Monomers having the compositions shown in Table 2 were polymerized in the same manner as in Examples 5 to 10 to obtain fluorine-containing copolymers.

(Examples 15 to 20) The fluorine-containing copolymer (D) obtained in Examples 5 to 10 was weighed into a flask having a weight of 1 L containing 0.15 mol of hydroxyl group, and acetone 100 was added.
g, triethylamine 17.7 g (0.17 mol), and hydroquinone monomethyl ether 15 mg,
The mixture was stirred under a nitrogen stream at 40 ° C for 10 minutes.

Then, 26.6 g of cinnamoyl chloride
A solution of (0.16 mol) in 100 g of acetone was added dropwise over 30 minutes. Then, raise the temperature to 57 ° C and
The reaction was completed by stirring for half an hour. Then, the ammonium salt was filtered off, and the filtrate was added dropwise to 3 L of stirred water to reprecipitate the resin. Then, the precipitated resin was washed twice with water and then dried to obtain a desired fluorocopolymer having a photocurable functional group introduced therein. Table 3 shows a list of the fluorine-containing copolymer (D) used in each example.

To 100 parts (weight part, the same applies hereinafter) of each of the photocurable site-containing fluorocopolymers obtained in Examples 11 to 20, 400 parts of xylene and 1-hydroxycyclohexyl phenyl ketone (Irgacure 1 manufactured by Ciba-Geigy Co., Ltd.) were used.
84) 3 parts was added to prepare a photocurable coating liquid. This composition was applied on a clean glass plate, the solvent was evaporated, and then light was irradiated from a height of 10 cm at a line speed of 5 m / min using a 1200 W high-pressure mercury lamp. The weather resistance of each coating film thus obtained was evaluated by a sunshine weatherometer (83 ° C., direct irradiation, 500 hours). The evaluation method was as follows: ○: no change in appearance, Δ: surface roughness is noticeable. Table 4 shows the results.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

[Table 4]

[0066]

As described above, the fluorine-containing copolymer of the present invention gives a one-pack type coating solution, and instantaneously gives a fluorine-based resin film having a strong crosslinked structure by irradiation with light such as ultraviolet rays, Exhibits excellent weather resistance and stain resistance.

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[Procedure amendment]

[Submission date] February 1, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 2

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Claim 5

[Correction method] Change

[Correction contents]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

Monomers (E) and other monomers (C) containing a functional group copolymerizable with the fluoroolefins (A) and (A) and capable of introducing a photocurable functional group are all included. (A) 20 to 70 mol%, ( E ) 1 to 80 relative to monomer
At least one of the functional groups capable of introducing the photocurable functional group in (D) after obtaining the fluorine-containing copolymer (D) by copolymerizing at a ratio of mol% and (C) 0 to 70 mol%. A method for producing a fluorinated copolymer, which comprises introducing a photocurable functional group into a part.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction contents]

Fluoroolefin (A), monomer (E)
And other monomers (C) are copolymerized in a proportion of 20 to 70 mol% of (A), 1 to 80 mol% of ( E ) and 0 to 70 mol% of (C) with respect to all the monomers. A method of introducing a photocurable functional group into at least a part of the functional group capable of introducing the photocurable functional group in (D) after obtaining the fluorinated copolymer (D).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C09D 127/12 PFG C09D 127/12 PFG

Claims (6)

[Claims] 1. A polymer unit (1) based on a fluoroolefin is 20 to 70 mol% based on all polymer units, and a polymer unit (2) having a photocurable functional group is 1 to 80 mol based on all polymer units. %, And other polymerized units (3) in a proportion of 0 to 70 mol% based on all polymerized units, having a number average molecular weight of 10,000 to 500,000.
Is a fluorocopolymer. 2. A polymerized unit (2) having a photocurable functional group.
Is a polymerized unit obtained by polymerizing a monomer having a polymerizable unsaturated group, and a polyether chain,
The fluorinated copolymer according to claim 1, which is a polymerized unit having a photocurable functional group introduced through a spacer composed of at least one selected from a polyurethane chain, a polyamide chain and a polyester chain. 3. The fluorine-containing copolymer according to claim 1, wherein the photocurable functional group is a group selected from an acryloyl group, a methacryloyl group, a cinnamoyl group and an azido group. 4. A monomer (B) copolymerizable with fluoroolefins (A) and (A) and having a photocurable functional group.
And other monomers (C) are copolymerized in a proportion of 20 to 70 mol% of (A), 1 to 80 mol% of (B) and 0 to 70 mol% of (C) with respect to all the monomers. A method for producing a fluorinated copolymer, comprising: 5. A monomer (E) and another monomer (C) having a functional group copolymerizable with the fluoroolefins (A) and (A) and capable of introducing a photocurable functional group. , (A) 20 to 70 mol%, (B) 1 to 80 relative to all monomers
At least one of the functional groups capable of introducing the photocurable functional group in (D) after obtaining the fluorine-containing copolymer (D) by copolymerizing at a ratio of mol% and (C) 0 to 70 mol%. A method for producing a fluorinated copolymer, which comprises introducing a photocurable functional group into a part. 6. A composition containing the fluorine-containing copolymer according to claim 1, 2 or 3.