TW201410716A - Fluorine-containing polymer and method for producing same - Google Patents

Abstract

The purpose of the present invention is to provide a novel fluorine-containing polymer which can be easily cured, while having solvent resistance, gas barrier properties, transparency and heat resistance. The present invention is a fluorine-containing polymer which is characterized by comprising a polymerization unit based on a fluorine-containing monomer, and as optional polymerization units, a polymerization unit based on vinyl alcohol and a polymerization unit represented by general formula (1). -CH2-CH(-O-(L)l-Rb)- (1) (In the formula, Rb represents an organic group having at least one hydrolyzable metal alkoxide; L represents a divalent organic group; and l is 0 or 1.)

Description

Fluoropolymer and method of producing the same

This invention relates to fluoropolymers and methods for their manufacture.

The polyvinyl alcohol or the ethylene-vinyl alcohol copolymer exhibits hydrophilicity, and has a property that it is difficult to permeate a gas such as oxygen or nitrogen, and is excellent in fuel barrier properties.

Patent Document 1 proposes a fluorinated copolymer film which is a copolymer of tetrafluoroethylene and vinyl acetate or a B contained in the copolymer in terms of a copolymer film excellent in water resistance. A copolymer obtained by saponification of at least a portion of an acid ester group, and the tetrafluoroethylene content of the copolymer is from 1 to 70 mol%.

The copolymer proposed in the patent document 1 is indicated to be inferior in productivity and heat resistance, and the quality is lowered due to coloring. In Patent Document 2, a fluorine-containing olefin and a vinyl alcohol are proposed. After the hydrogen atom of the hydroxyl group is copolymerized with a vinyl ether substituted with a deprotectable protecting group, a fluorine-containing olefin/vinyl alcohol is produced by substituting a protective group for a hydrogen atom by a deprotection reaction to produce a hydroxyl group. The method of copolymer is used as a solution.

Further, in Patent Document 3, a proposal is made to introduce a hydrolyzable metal alkoxide by a transesterification reaction in a fluorine-containing olefin/vinyl ester copolymer.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 5-261256

[Patent Document 2] International Publication No. 2011/126056

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-81547

The fluorine-containing olefin/vinyl alcohol copolymer disclosed in Patent Document 2 does not have a hardened portion suitable for the curing reaction, and cannot be easily hardened. Further, as disclosed in Patent Document 3, a copolymer obtained by introducing a hydrolyzable metal alkoxide into a fluorine-containing olefin/vinyl ester copolymer by a transesterification reaction has a hydrolyzability due to a portion introduced by a transesterification reaction. High, it can not be said to be practical, but there is room for improvement.

The present invention provides a novel fluoropolymer which has solvent resistance, gas barrier properties, transparency and heat resistance and can be easily hardened.

The invention further provides a novel method for producing a fluoropolymer, which can easily produce a polymer which is solvent-resistant, gas barrier, transparent and heat-resistant and can be easily hardened, and can be easily used. Ground The amount of the hardened portion of the obtained polymer was adjusted.

The present invention is a fluoropolymer characterized by containing a polymerization unit based on a fluorine-containing monomer, a polymerization unit based on a vinyl alcohol as an arbitrary polymerization unit, and a polymerization unit represented by the general formula (1) -CH ₂ - CH(-O-(L) _l -R ^b )- (1)

(wherein R ^b is an organic group having at least one hydrolyzable metal alkoxide; L is a divalent organic group; l is 0 or 1).

R ^b is preferably a base represented by the following general formula (2).

-R ¹¹ _a (R ¹² O) _b M{O-MR ¹¹ _g (OR ¹² ) _h } _f -R ¹¹ _d (OR ¹² ) _e (2)

(In the formula, the M-based metal and R ¹¹ may be the same or different, and are a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² may be the same or different, and is an alkyl group, an alkoxyalkyl group, or an aryl group, a system 1 An integer of ~3, an integer of b to 0~4, a+b=2~5, d is 0 or 1, e is 0 or 1, d+e=1, f is an integer of 0~10, g is 0 An integer of ~3, an integer of h system 0~3, at least one of g+h=1~3, b, e, and h is 1 or more).

The L system is preferably an organic group represented by the general formula (3).

-(C=O) _s -(NH) _p - (3)

(where s is 0 or 1, p is 0 or 1)

It is preferred that the L system is a single bond.

The molar ratio based on the polymerization unit of the fluorine-containing monomer, the polymerization unit based on the vinyl alcohol, and the polymerization unit represented by the general formula (1) is (30 to 70) / (0 to 69) / (1 to 70) It is better.

The present invention relates to a process for producing the above fluoropolymer, which comprises a process for producing a fluoromonomer/vinyl ester copolymer by copolymerizing a fluoromonomer with a vinyl ester monomer. a step of obtaining a fluoromonomer/vinyl alcohol copolymer by hydrolyzing the fluoromonomer/vinyl ester copolymer, and by using the fluoromonomer/vinyl alcohol copolymer and the general formula (4): O=C=NR ^b (4)

A step of reacting a compound represented by the formula (wherein R ^b is an organic group having at least one hydrolyzable metal alkoxide) to obtain a fluorine-containing polymer.

The present invention is also a process for producing the above fluoropolymer, characterized by comprising the steps of: copolymerizing a fluoromonomer with a vinyl ester monomer to obtain a fluoromonomer/vinyl ester copolymer a step of obtaining a fluoromonomer/vinyl alcohol copolymer by hydrolyzing the fluoromonomer/vinyl ester copolymer, by using the fluoromonomer/vinyl alcohol copolymer and the general formula (6): X ^b -R ^c (6)

a step of reacting a compound represented by (wherein X ^b is Cl, Br or I, R ^c is an organic group having at least one olefin) to obtain an olefin-containing fluoropolymer, and by using the aforementioned olefin-containing compound The fluoropolymer is reacted with trichloromethane or trialkoxydecane hydroformylation, and when trichloromethane is used, it is further subjected to alkoxylation with an aliphatic alcohol to obtain a fluorine-containing polymerization containing a hydrolyzable metal alkoxide. The steps of the object.

The present invention is also a process for producing the above fluoropolymer, which comprises the following steps: a method for producing a fluorine-containing monomer and a general formula (8): CH ₂ =CH-OR (8)

a step of copolymerizing a vinyl ether monomer represented by the formula (wherein R is a protecting group for conversion to a vinyl alcohol by a deprotection reaction) to obtain a fluorine-containing monomer/vinyl ether copolymer, by the aforementioned a step of deprotecting a fluorine-containing monomer/vinyl ether copolymer to obtain a fluorine-containing monomer/vinyl alcohol copolymer, and by using the above-mentioned fluorine-containing monomer/vinyl alcohol copolymer with a general formula (4): O =C=NR ^b (4)

A step of reacting a compound represented by the formula (wherein R ^b is an organic group having at least one hydrolyzable metal alkoxide) to obtain a fluorine-containing polymer.

The present invention is also a process for producing the above fluoropolymer, which comprises the following steps: a method for producing a fluorine-containing monomer and a general formula (8): CH ₂ =CH-OR (8)

a step of copolymerizing a vinyl ether monomer represented by the formula (wherein R is a protecting group for conversion to a vinyl alcohol by a deprotection reaction) to obtain a fluorine-containing monomer/vinyl ether copolymer, by the aforementioned The step of deprotecting the fluoromonomer/vinyl ether copolymer to obtain a fluoromonomer/vinyl alcohol copolymer by using the above fluoromonomer/vinyl alcohol copolymer with the general formula (6): X ^b -R ^c (6)

a step of reacting a compound represented by (wherein X ^b is Cl, Br or I, R ^c is an organic group having at least one olefin) to obtain an olefin-containing fluoropolymer, and by using the aforementioned olefin-containing compound The fluoropolymer is reacted with trichloromethane or trialkoxydecane hydroformylation, and when trichloromethane is used, it is further subjected to alkoxylation with an aliphatic alcohol to obtain a fluorine-containing polymerization containing a hydrolyzable metal alkoxide. The steps of the object.

The compound represented by the general formula (4) is represented by the following general formula (5): O = C = NR ¹¹ _a (R ¹² O) _b M{O-MR ¹¹ _g (OR ¹² ) _h } _{f -} R ¹¹ _d ( OR ¹² ) _e (5)

(In the formula, the M-based metal and R ¹¹ may be the same or different, and are a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² may be the same or different, and is an alkyl group, an alkoxyalkyl group, or an aryl group, a system 1 An integer of ~3, an integer of b to 0~4, a+b=2~5, d is 0 or 1, e is 0 or 1, d+e=1, f is an integer of 0~10, g is 0 Preferably, an integer of ~3, an integer of h to 0 to 3, a compound of at least one of g+h=1 to 3, b, e, and h is preferably 1 or more.

The compound represented by the general formula (6) is represented by the following general formula (7): X ^b -R ¹³ -(R ¹⁴ -CH=CH ₂ ) _c (7)

(wherein X ^b is Cl, Br or I, R ¹³ may be the same or different, and is a hydrocarbon group having a carbon number of 1 to 20 (c+1), and R ¹⁴ may be the same or different, and is -O-, Preferably, the compound represented by -OC(=O)-, a single bond, and the c-number is an integer of 1 to 10).

The present invention is also a curable composition containing the above fluoropolymer.

The curable composition of the present invention is preferably a coating agent or an antifouling agent.

The present invention is also a cured product characterized by curing the above-mentioned curable composition.

The fluoropolymer of the present invention is easily cured. The cured product obtained by curing the fluoropolymer of the present invention has solvent resistance, gas barrier properties, transparency, and heat resistance.

The manufacturing method of the present invention can be easily produced to have solvent resistance and gas The fluoropolymer which is barrier-like, transparent, and heat-resistant and which is easily hardened can also easily adjust the amount of the hardened portion of the obtained copolymer.

[Formation for implementing the invention]

Hereinafter, the present invention will be specifically described.

The fluoropolymer of the present invention is characterized by comprising a polymerization unit based on a fluorine-containing monomer, a polymerization unit based on a vinyl alcohol as an arbitrary polymerization unit, and a polymerization unit represented by the general formula (1).

The above fluorine-containing monomer is a monomer having a fluorine atom.

The above fluorine-containing monomer is derived from tetrafluoroethylene [TFE], vinylidene fluoride [VdF], chlorotrifluoroethylene [CTFE], fluorinated ethylene, hexafluoropropylene [HFP], hexafluoroisobutylene, CH ₂ =CZ ¹ (CF ₂ ) _n1 Z ² (wherein Z ¹ is H, F or Cl, Z ² is H, F or Cl, n1 is an integer from 1 to 10), CF ₂ =CF -ORf ¹ (wherein Rf ¹ represents a perfluoroalkyl group having 1 to 8 carbon atoms), and perfluoro(alkyl vinyl ether) [PAVE], and CF ₂ =CF-OCH ₂ -Rf ² In the above, at least one fluorine-containing monomer selected from the group consisting of an alkyl perfluorovinyl ether derivative represented by Rf ² is a perfluoroalkyl group having 1 to 5 carbon atoms is preferred.

Examples of the monomer represented by CH ₂ =CZ ¹ (CF ₂ ) _n1 Z ² include CH ₂ =CFCF ₃ , CH ₂ =CHCF ₃ , CH ₂ =CFCHF ₂ , CH ₂ =CClCF ₃ and the like.

Examples of the PAVE include perfluoro(methyl vinyl ether) [PMVE], perfluoro(ethyl vinyl ether) [PEVE], perfluoro(propyl vinyl ether) [PPVE], and perfluoro(butyl). Vinyl ether), etc. It is better to use PMVE, PEVE or PPVE.

The alkyl perfluorovinyl ether derivative is preferably a perfluoroalkyl group having Rf ² as a carbon number of 1 to 3 and CF ₂ =CF-OCH ₂ -CF ₂ CF ₃ .

In terms of the above fluorine-containing monomer, at least one selected from the group consisting of TFE, CTFE and HFP is more preferable, and TFE is more preferable.

The fluoropolymer of the present invention contains the following general formula (1): -CH ₂ -CH(-O-(L) _l -R ^b )- (1)

(In the formula, R ^b is a polymerization unit represented by at least one organic group of a hydrolyzable metal alkoxide, an L-based divalent organic group, or a l-form 0 or 1). The fluoropolymer of the present invention is a polymer having a hydrolyzable metal alkoxide as a hardened portion, and the number of hardened portions can be easily adjusted in the production of a fluoropolymer.

Further, the R ^b system may have one hydrolyzable metal alkoxide, and may have two or more.

Further, the polymerization unit represented by the general formula (1) is based on the general formula: CH ₂ =CH-O-(L) _l -R ^b

(wherein R ^b is a polymerization unit of a monomer having at least one organic group of a hydrolyzable metal alkoxide, an L-based divalent organic group, or a 1-based 0 or 1).

L is the following general formula (3): -(C=O) _s -(NH) _p - (3)

The organic group represented by the formula (where s is 0 or 1, p is 0 or 1) is preferred. When s and p in the general formula (3) are 1, the R ^b of the general formula (1) is bonded to the main chain of the fluoropolymer through the urethane bond, when s is 1 and when p is 0, R ^b is bonded to the main chain of the fluoropolymer through ester bonding, and when either s or p is 0, L represents a single bond, and R ^{b is an} ether bond. The backbone of the fluoropolymer is bonded.

R ^b is represented by the following general formula (2): -R ¹¹ _a (R ¹² O) _b M{O-MR ¹¹ _g (OR ¹² ) _h } _f -R ¹¹ _d (OR ¹² ) _e (2)

(In the formula, the M-based metal and R ¹¹ may be the same or different, and are a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² may be the same or different, and is an alkyl group, an alkoxyalkyl group, or an aryl group, a system 1 An integer of ~3, an integer of b to 0~4, a+b=2~5, d is 0 or 1, e is 0 or 1, d+e=1, f is an integer of 0~10, g is 0 An integer of ~3, an integer of h to 0 to 3, a base of at least one of g+h=1 to 3, b, e, and h is preferably 1 or more.

In the general formula (2), the metal represented by M may, for example, be cerium (Si), titanium (Ti), aluminum (Al), zirconium (Zr), tin (Sn), iron (Fe), or sodium ( Na), magnesium (Mg), phosphorus (P), sulfur (S), potassium (K), calcium (Ca), strontium (Sc), vanadium (V), chromium (Cr), manganese (Mn), cobalt ( Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), antimony (Rb), antimony (Sr), antimony ( Y), niobium (Nb), molybdenum (Mo), cadmium (Cd), indium (In), antimony (Sb), tellurium (Te), antimony (Cs), barium (Ba), barium (La), barium ( Hf), tantalum (Ta), tungsten (W), mercury (Hg), tantalum (Tl), lead (Pb), Bi (Bi), lithium (Li), beryllium (Be), boron (B), antimony (Ce), antimony (Pr), antimony (Nd), antimony (Pm), antimony (Sm), antimony (Eu), At least one selected from the group consisting of Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

In the above M aspect, among these, bismuth (Si), titanium (Ti), aluminum (Al), zirconium (Zr), tin (Sn), and iron (Fe) are more preferable.

In the general formula (2), the "hydrocarbon group having 1 to 20 carbon atoms" in R ¹¹ is preferably an alkylene group having 1 to 20 carbon atoms and an alkylene group having 1 to 10 carbon atoms. The alkylene group may be linear or branched.

In the general formula (2), the "alkyl group" in R ¹² may, for example, be a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a cyclopentyl group, and the like. Hexyl, cyclohexyl, octyl, cyclodecyl and the like.

Further, the "alkoxyalkyl group" in R ¹² may, for example, be an alkoxyalkyl group having 2 to 12 carbon atoms. The "aryl group" in R ¹² may, for example, be an aryl group having 6 to 12 carbon atoms.

In the general formula (2), the number of alkoxy groups to be contained is preferably from 1 to 12, more preferably from 1 to 4.

In the general formula (2), f is preferably an integer of 0 to 4.

The "organic group having at least one hydrolyzable metal alkoxide" of R ^b , even in the group represented by the general formula (2), may be, for example, the following general formula (2-1): -R ¹¹ _k M(OR ¹² ) _j (2-1)

(wherein j is an integer of 2 to 5, k is 1 or 2, j+k is an integer of 3 to 6, and R ¹¹ and R ¹² are the same as those of the general formula (2)).

In the general formula (2-1), j is preferably 3 or 4, and k is preferably one.

Preferred examples of the "organic group having at least one hydrolyzable metal alkoxide" of R ^b include, for example, the following general formula (2-2): -(C _n H _2n )-Si-(OR ¹² ) ₃ (2-2)

(wherein, n is an integer of 1 to 10, and R ¹² is the same as the general formula (2)).

In terms of the organic group represented by R ^b , among these, more specifically, for example, the following general formula:

The organic group shown.

The fluoropolymer of the present invention is a molar ratio based on a polymerization unit of a fluorine-containing monomer, a polymerization unit based on a vinyl alcohol, and a polymerization unit represented by the general formula (1) (a polymerization unit based on a fluorine-containing monomer) ) / (based on the polymerization unit of vinyl alcohol) / (the polymerization unit represented by the general formula (1)) is preferably (30 to 70) / (0 to 69) / (1 to 70).

More preferably (30~70)/(1~69)/(1~69).

The fluoropolymer of the present invention may be a polymerization unit containing a vinyl ester monomer or a vinyl ether monomer in addition to the above three polymerization units. The fluoropolymer of the present invention is a polymerization unit based on a fluorine-containing monomer, a polymerization unit based on a vinyl alcohol, a polymerization unit represented by the general formula (1), and a vinyl ester-based monomer or a vinyl ether-based single Mohr ratio of the polymerization unit of the body (polymerization unit based on fluorine-containing monomer) / (polymerization unit based on vinyl alcohol) / (polymerization unit represented by general formula (1)) / (based on vinyl ester monomer or The polymerization unit of vinyl ether monomer is preferably (30~70)/(0~69)/(1~70)/(0~69), (30~70)/(0~65)/( 5~70)/(0~65) is better.

More preferably (30~70)/(1~65)/(5~69)/(0~65).

Especially good (30~70)/(1~65)/(5~68)/(1~65).

Examples of the vinyl ester monomer include vinyl acetate, vinyl versatate, vinyl laurate, vinyl stearate, and vinyl cyclohexyl carboxylic acid. In terms of the vinyl ester monomer, vinyl acetate or vinyl stearate is preferred.

More preferred is vinyl acetate.

In terms of vinyl ether monomer, t-butyl vinyl ether, 1,1-dimethylpropyl vinyl ether, methoxymethyl vinyl ether, tetrahydrofuranyl vinyl ether, tetrahydropyranyl vinyl Ether, hydroxytrimethylnonane, or hydroxydimethylphenyl decane.

In terms of vinyl ether monomer, t-butyl vinyl ether is preferred.

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

The fluoropolymer of the present invention may also be a polymerization unit comprising a fluoromonomer and another monomer copolymerizable. The above-mentioned polymerization unit based on other monomers is based on a polymerization unit of a monomer having no fluorine atom (except that a polymerization unit based on a vinyl alcohol, a polymerization unit represented by the general formula (1), and a vinyl ester-based monomer are excluded. Unit of polymerization).

The other monomer may be, for example, ethylene, propylene, 1-butene, 2-butene, ethylene chloride, vinyl chloride, a hydroxyl group-containing vinyl ether monomer, and an unsaturated carboxylic acid. It is preferred that at least one non-fluorine-containing ethylenic monomer selected from the group is preferred. Examples of the hydroxyl group-containing vinyl ether monomer include 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether.

The fluoropolymer of the present invention has a weight average molecular weight of preferably from 1,000 to 3,000,000, more preferably from 5,000 to 1,000,000, and even more preferably from 10,000 to 600,000.

First manufacturing method

The fluoropolymer of the present invention can be preferably produced by a production process comprising the steps of copolymerizing a fluoromonomer with a vinyl ester monomer to obtain a fluoromonomer/vinyl ester copolymer. a step of obtaining a fluorine-containing monomer/vinyl alcohol copolymer by hydrolyzing the above fluorine-containing monomer/vinyl ester copolymer, and by using the above fluorine-containing monomer/vinyl alcohol copolymer with a general Formula (4): O=C=NR ^b (4)

A step of reacting a compound represented by the formula (wherein R ^b is an organic group having at least one hydrolyzable metal alkoxide) to obtain a fluorine-containing polymer. This manufacturing method is referred to as the first manufacturing method of the present invention.

A method of copolymerizing a fluorine-containing monomer with a vinyl ester monomer and a method of hydrolyzing a fluorine-containing monomer/vinyl ester copolymer have been known from the past, and a conventionally known method can also be carried out in the present invention. By hydrolyzing the fluorine-containing monomer/vinyl ester copolymer, the acetate group is converted into a hydroxyl group, and a fluorine-containing monomer/vinyl alcohol copolymer is obtained.

The fluorine-containing monomer/vinyl ester copolymer obtained by copolymerizing a fluorine-containing monomer and a vinyl ester monomer is a molar ratio of a fluorine-containing monomer to a vinyl ester monomer (fluorinated monomer) / (ethylene) The base ester monomer is preferably (30~70)/(70~30), and more preferably (40~60)/(60~40). When the molar ratio falls within the above range and the degree of saponification falls within the range described later, a fluoropolymer having a molar ratio of each of the polymerization units falling within the above range can be produced.

The hydrolysis of the fluorine-containing monomer/vinyl ester copolymer is preferably carried out so that the degree of saponification is from 1 to 100%, preferably from 30 to 100%.

The above saponification degree is ¹ H-NMR, and the integral value of protons derived from ethyl hydrazino (CH ₃ C(=O)-) in the vicinity of 2.1 ppm before and after saponification is quantitatively determined from 2.2 to 2.7 ppm from the main chain methylene group ( The integral value of the proton of -CH ₂ -CH-) is applicable.

¹ H-NMR: GEMINI-300 manufactured by VARIAN

The vinyl ester single system does not contain fluorine atoms. Examples of the vinyl ester monomer include vinyl acetate, vinyl versatate, vinyl laurate, vinyl stearate, and vinyl cyclohexyl carboxylic acid. In terms of the vinyl ester monomer, vinyl acetate or vinyl stearate is preferred.

More preferred is vinyl acetate.

In the step of obtaining a fluoropolymer, the compound represented by the general formula (4) used is represented by the following general formula (5): O = C = NR ¹¹ _a (R ¹² O) _b M{O-MR ¹¹ _g (OR ¹² ) _h } _f -R ¹¹ _d (OR ¹² ) _e (5)

(In the formula, the M-based metal and R ¹¹ may be the same or different, and are a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² may be the same or different, and is an alkyl group, an alkoxyalkyl group, or an aryl group, a system 1 An integer of ~3, an integer of b to 0~4, a+b=2~5, d is 0 or 1, e is 0 or 1, d+e=1, f is an integer of 0~10, g is 0 Preferably, an integer of ~3, an integer of h to 0 to 3, a compound of at least one of g+h=1 to 3, b, e, and h is preferably 1 or more.

In the aspect of the compound represented by the general formula (4), the following general formula (5-1) is used: O=C=N-(CH ₂ ) _a1 -Si(OR ¹² ) ₃ (5-1)

(Wherein, A1-based integer of 1 to 10, the same as (5) in the general formula R ¹² R ¹² lines) of the compound represented by the better.

In the case of the compound represented by the general formula (4), the specific compound among these is, for example, the following chemical formula: O=C=N-(CH ₂ ) ₃ -Si(OCH ₂ CH ₃ ) ₃

O=C=N-(CH ₂ ) ₃ -Si(OCH ₃ ) ₃

O=C=N-(CH ₂ ) ₂ -Si(OCH ₂ CH ₃ ) ₃

O=C=N-(CH ₂ ) ₂ -Si(OCH ₃ ) ₃

O=C=N-(CH ₂ )-Si(OCH ₂ CH ₃ ) ₃

The compound represented by O=C=N-(CH ₂ )-Si(OCH ₃ ) ₃ is more preferably.

In the first production method of the present invention, the amount of the compound represented by the general formula (4) varies depending on the number of hydroxyl groups in the molecule of the fluorine-containing monomer/vinyl alcohol copolymer, for example, one. In the case of a hydroxyl group, an amount sufficient to react a compound represented by the general formula (4) can be used.

The amount of the compound represented by the general formula (4) is usually 0.5 to 100 moles per mole of the hydroxyl group 1 mole of the fluorine-containing monomer/vinyl alcohol copolymer. Preferably, 0.67 to 10 m is used, and more preferably 0.83 to 2 m.

In the first production method of the present invention, the intramolecular hydroxyl group of the fluorine-containing monomer/vinyl alcohol copolymer is subjected to a urethanization reaction with an isocyanate group of a compound represented by the general formula (4) ( The addition reaction) forms a urethane bond. On the other hand, the hydrolyzable metal alkoxide present in the compound represented by the general formula (4) is substantially unreacted, and is a cured portion of the fluoropolymer of the present invention.

Fluorine polymerization obtained by the first manufacturing method of the present invention In the case where an unreacted OH group is present, the unreacted OH group acts as a site for improving the compatibility and solubility of the fluoropolymer of the present invention.

The above urethanization reaction is easily carried out by mixing a fluorine-containing monomer/vinyl alcohol copolymer with a compound represented by the general formula (4) or heating a mixture.

The heating temperature (reaction temperature) of the above urethanization reaction is usually about 5 to 90 ° C, preferably about 10 to 90 ° C, more preferably about 20 to 80 ° C.

In the first production method of the present invention, the fluorine-containing monomer/vinyl alcohol copolymer and the compound represented by the general formula (4) may be reacted in the presence of a catalyst. The above-mentioned catalyst is not particularly limited, and a commercially available product can be easily obtained if it is conventionally used for a urethanation reaction.

Examples of the catalyst include organotitanium compounds such as tetraethyl titanate and tetrabutyl titanate, and organotin compounds such as tin octylate, dibutyltin oxide, and dibutyltin dilaurate. A halogen-based divalent tin such as tin dichloride or tin dibromide. Among these, organotin compounds are preferred.

As the catalyst, an amine-based catalyst can also be mentioned. Ethanolamine, N-methylethanolamine, triethanolamine, N,N-dimethylethanolamine, n-butylamine, diethylamine, triethylenediamine, triethylamine, tetramethylenediamine, cyclohexyl The amine or the like is preferably triethylenediamine or triethylamine, more preferably triethylamine.

In the first manufacturing method of the present invention, by using a catalyst, The urethanation reaction can be carried out in a shorter period of time to obtain the desired fluoropolymer.

The amount of the catalyst to be used in the urethanation reaction is not particularly limited and may be appropriately adjusted. For example, for 100 parts by mass of the compound represented by the general formula (4), it is usually 0.00001 to 3 It is about 0.0001 to 1 part by mass, preferably about 0.0001 to 1 part by mass.

In the first production method of the present invention, a solvent can be further used. In the case of the solvent, a solvent which does not interfere with the progress of the urethanization reaction may be used, and a conventionally known solvent which is generally used may be used.

As the solvent, for example, a ketone solvent such as methyl isobutyl ketone (MIBK) or methyl ethyl ketone (MEK); an ester solvent such as ethyl acetate or butyl acetate; and an ether system such as THF can be used. A solvent such as a solvent, a fluorine-based solvent such as HCFC225 (CF ₃ CF ₂ CHCl ₂ /CClF ₂ CF ₂ CHClF mixture) or a guanamine-based solvent such as N,N-dimethylformamide (DMF). An alcohol-based solvent having an OH group is disadvantageous in that it hinders the progress of the urethanization reaction. Further, even if water is present in the system, the progress of the urethanization reaction is hindered, and it is more preferable that each solvent is dehydrated before use.

Further, in the first production method of the present invention, other components may be added as needed. Examples of other components include an antioxidant, a leveling agent, an inorganic filler, and an organic filler.

When the antioxidant is used, it is preferably used in an amount of 0.01 to 10 parts by mass, preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the compound represented by the general formula (4). More preferably, it is 0.5 to 1 part by mass.

Second manufacturing method

The fluoropolymer of the present invention can be produced by a production method comprising the steps of: copolymerizing a fluoromonomer with a vinyl ester monomer to obtain a fluoromonomer/vinyl ester copolymer, and borrowing a step of obtaining a fluorine-containing monomer/vinyl alcohol copolymer by hydrolyzing the above fluorine-containing monomer/vinyl ester copolymer, and by using the above fluorine-containing monomer/vinyl alcohol copolymer with the general formula (6): X ^b -R ^c (6)

a step of reacting a compound represented by (wherein X ^b is Cl, Br or I, R ^c is an organic group having at least one olefin) to obtain an olefin-containing fluoropolymer, and the above-mentioned olefin-containing fluorine-containing compound The polymer is subjected to a hydrogenation oximation reaction with trichloromethane or a trialkoxy decane, and when trichloromethane is used, it is further subjected to alkoxylation with an aliphatic alcohol to obtain a fluoropolymer containing a hydrolyzable metal alkoxide. step. This manufacturing method is referred to as the second manufacturing method of the present invention.

The method of copolymerizing a fluorine-containing monomer with a vinyl ester monomer, and the method of hydrolyzing the fluorine-containing monomer/vinyl ester copolymer, can be used in the method detailed in the first production method.

The vinyl ester single system does not contain fluorine atoms. Examples of the vinyl ester monomer include vinyl acetate, vinyl versatate, vinyl laurate, vinyl stearate, and vinyl cyclohexyl carboxylic acid. In terms of the vinyl ester monomer, vinyl acetate or vinyl stearate is preferred.

More preferred is vinyl acetate.

In the general formula (6), R ^c is "an organic group having at least one olefin".

The compound represented by the general formula (6) is represented by the following general formula (7): X ^b -R ¹³ -(R ¹⁴ -CH=CH ₂ ) _c (7)

(wherein X ^b is Cl, Br or I, R ¹³ may be the same or different, and is a hydrocarbon group having a carbon number of 1 to 20 (c+1), and R ¹⁴ may be the same or different, and is -O-, Preferably, the compound represented by -OC(=O)-, a single bond, and the c-number is an integer of 1 to 10).

In the above general formula (7), X ^b is preferably Br if it is easy to control the reaction.

In the aspect of the compound represented by the general formula (6), the following general formula (7-1): X-(CH ₂ ) _m -CH=CH ₂ (7-1)

The compound represented by the formula (X-type Cl, Br or I, m is an integer of 1 to 10) is more preferable.

In the case of the compound represented by the general formula (6), among the specific compounds, for example, the following chemical formula: Br-CH ₂ CH=CH ₂

Cl-CH ₂ CH=CH ₂

I-CH ₂ CH=CH ₂

The compound shown is preferred, the following chemical formula: Br-CH ₂ CH=CH ₂

Cl-CH ₂ CH=CH ₂

The compounds shown are preferred.

In the second production method of the present invention, the hydroxyl group of the fluorine-containing monomer/vinyl alcohol copolymer undergoes etherification reaction with the X ^b - group of the compound represented by the general formula (6) to form an ether bond. On the other hand, the olefin which is present in the compound represented by the general formula (6) is not substantially reacted, but becomes a reaction point of the subsequent hydrogenation reaction, and finally becomes a point of introduction of the hydrolyzable metal alkoxide. The hardened portion of the fluoropolymer of the present invention.

In the fluoropolymer obtained by the second production method of the present invention, when an unreacted OH group is present, the unreacted OH group acts as a compatibility and solubility improving portion of the fluoropolymer of the present invention. .

The above etherification reaction can be carried out by reacting the above fluorine-containing monomer/vinyl alcohol copolymer with a compound represented by the general formula (6) under basic conditions. It is preferably carried out under the conditions of pH 8-12. The hydroxyl group 1 mole in the molecule of the above fluorine-containing monomer/vinyl alcohol copolymer is preferably 1.0 to 1.1 moles of the compound represented by the general formula (6). The above etherification reaction can be carried out at a temperature from room temperature to reflux of the solvent for 1 to 24 hours. As the solvent, an aromatic hydrocarbon such as benzene or toluene, tetrahydrofuran, N,N-dimethylformamide or dimethylhydrazine can be used.

In the second production method, after the fluoromonomer/vinyl alcohol copolymer is reacted with a compound represented by the general formula (6) to obtain an olefin-containing fluoropolymer, in order to obtain a hydrolyzable metal alkoxide And continuing to hydrogenate the chlorobenzene or the trialkoxy decane with the olefin-containing fluoropolymer olefin, and using trichloromethane, followed by alkoxylation with the aliphatic alcohol. A fluorine-containing copolymer containing a hydrolyzable metal alkoxide for the purpose can be obtained. If one of the processes is chemically reacted When expressed by the formula, the following formula can be displayed.

In the formula, x and y are the number of repetitions of the polymerization unit. X ^b , R ¹³ , R ¹⁴ and c are the same as the general formula (7).

The above-mentioned trialkoxy decane may, for example, be trimethoxy decane, triethoxy decane or tripropoxy decane. Among them, trimethoxydecane and triethoxydecane are preferred. When such a trialkoxy decane is used, although the advantage of one step can be shortened compared with the case of using chloroformane, on the other hand, when the base used in the etherification reaction of the preceding stage remains, it is hydrolyzed. In the case of a de-alkali step. The alkali removal step can be used in general The ion exchange resin or the like is carried out.

The above hydrogenation sulfonation reaction can be carried out by reacting the above olefin-containing fluoropolymer with trichloromethane or trialkoxy decane. The olefin 1 mole in the molecule of the olefin-containing fluoropolymer is preferably 1.05 to 10 moles using trichlorodecane or trialkoxy decane.

The aliphatic alcohol may, for example, be an alcohol having 1 to 12 carbon atoms. From the viewpoint of reactivity, a preferred tertiary alcohol, a secondary alcohol or even a tertiary alcohol is preferred. Further, the carbon number is preferably from 1 to 4, more preferably 1 or 2. Examples of such examples include methanol or ethanol.

The alkoxylation reaction can be carried out by reacting the polymer obtained by the above-described hydrogenation reaction with trichlorosilane with a fatty alcohol. Further, even when the above hydrogenation oximation reaction is carried out with a trialkoxysilane, the alkoxylation reaction can be carried out, and at this time, the hydrolyzable metal alkane obtained by the hydrazine alkylation reaction with a trialkoxysilane is hydrogenated. The carbon chain length of the alkoxide portion of the substance can be changed.

The amount of the aliphatic alcohol used in the alkoxylation reaction is preferably in the range of the intramolecular decyl group 1 mole of the polymer obtained by the above alkylation reaction, preferably using an aliphatic alcohol of 1 to 2 moles. .

In the alkoxylation reaction, an aprotic solvent such as diethyl ether, toluene, tetrahydrofuran or acetonitrile is preferably used as the solvent. In the case of a solvent, it is also possible to use only the third-order amine which is used as a catalyst to be described later.

Further, in the alkoxylation reaction, a catalyst may be used, and in the case of the catalyst, a third-order amine is preferred. Examples of the third-order amine include triethyl Amine, pyridine, tri-n-butylamine, di-n-butyloctylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-octylamine, and the like.

In order to increase the amount of the above-mentioned catalyst, in order to carry out the reaction more efficiently, it is preferable to use a catalyst of 1 to 2 moles for the alkylene group. The reaction temperature is not less than the boiling point of the solvent, but it is preferably carried out in the range of 40 to 70 °C. It is preferred to reflux it at the boiling point of the solvent.

Third manufacturing method

The fluoropolymer of the present invention can be further preferably produced by a production process comprising the steps of: formulating a fluoromonomer with a general formula (8): CH ₂ =CH-OR (8)

a step of obtaining a fluoromonomer/vinyl ether copolymer by copolymerizing a vinyl ether monomer represented by R (a protecting group which can be converted into a vinyl alcohol by a deprotection reaction), by using the above The step of deprotecting the fluoromonomer/vinyl ether copolymer to obtain a fluoromonomer/vinyl alcohol copolymer, and by reacting the above fluoromonomer/vinyl alcohol copolymer with the general formula (4): O=C=NR ^b (4)

A step of reacting a compound represented by the formula (wherein R ^b is an organic group having at least one hydrolyzable metal alkoxide) to obtain a fluorine-containing polymer. This manufacturing method is referred to as the third manufacturing method of the present invention.

A method of copolymerizing a fluorine-containing monomer with a vinyl ether monomer, and a method of deprotecting a fluorine-containing monomer/vinyl ether copolymer It is known from the past, and the present invention can also be carried out by a conventionally known method. By subjecting the fluorine-containing monomer/vinyl ether copolymer to a deprotection reaction, -OR is converted into a hydroxyl group, and a fluorine-containing monomer/vinyl alcohol copolymer can be obtained.

The fluorine-containing monomer/vinyl ether copolymer obtained by copolymerizing a fluorine-containing monomer and a vinyl ether monomer is a molar ratio of a fluorine-containing monomer to a vinyl ether monomer (fluorinated monomer) / (ethylene) The base ether monomer is preferably (40 to 60) / (60 to 40), and more preferably (45 to 55) / (55 to 45). By setting the molar ratio within the above range and the degree of deprotection falling within the range described later, it is possible to produce a fluoropolymer having a molar ratio of each of the polymerization units falling within the above range.

The deprotection of the fluorine-containing monomer/vinyl ether copolymer is preferably carried out with a degree of deprotection of from 1 to 100%, preferably from 30 to 100%.

The above degree of deprotection can be quantified by ¹ H-NMR to quantify the integral value of the proton from the third butyl group (-C(CH ₃ ) ₃ ) in the vicinity of 1.0 to 1.3 ppm before and after the deprotection reaction. The integral value of the proton from 2.2 to 2.7 ppm of the main chain methylene group (-CH ₂ -CH-) was measured.

¹ H-NMR: GEMINI-300 manufactured by VARIAN

The R aspect of the general formula (8) is not particularly limited as long as it is deprotectable, but -CR ¹ R ² R ³ (R ¹ , R ² and R ³ are each independently a carbon number of 1 to 3). Alkyl), alkoxymethyl group having 1 to 6 carbon atoms, tetrahydrofuranyl group, tetrahydropyranyl group or trialkyldecyl group (-Si(R ⁴ ) ₃ , R ⁴ is an alkane having 1 to 6 carbon atoms More preferably, -CR ¹ R ² R ^{3 is} preferred. In terms of the ease of obtaining the vinyl ether monomer, a third butyl vinyl ether (t-butyl vinyl ether) is preferred.

The preferred type, preferred addition amount, and the like of the compound represented by the general formula (4) can be applied to the details of the first production method.

Fourth manufacturing method

The fluoropolymer of the present invention can be produced by a production method comprising the following steps, and the fluoromonomer and the general formula (8): CH ₂ =CH-OR (8)

a step of obtaining a fluoromonomer/vinyl ether copolymer by copolymerizing a vinyl ether monomer represented by R (a protecting group which can be converted into a vinyl alcohol by a deprotection reaction), by using the above The step of deprotecting the fluoromonomer/vinyl ether copolymer to obtain a fluoromonomer/vinyl alcohol copolymer by using the above fluoromonomer/vinyl alcohol copolymer with the general formula (6): X ^b -R ^c (6)

a step of reacting a compound represented by (wherein X ^b is Cl, Br or I, R ^c is an organic group having at least one olefin) to obtain an olefin-containing fluoropolymer, and the above-mentioned olefin-containing fluorine-containing compound The polymer is subjected to a hydrogenation oximation reaction with trichloromethane or a trialkoxy decane, and when trichloromethane is used, a fluorine-containing metal alkoxide-containing fluorine is further obtained by alkoxylation with an aliphatic alcohol. The step of the polymer. This manufacturing method is referred to as the fourth manufacturing method of the present invention.

The method of copolymerizing a fluorine-containing monomer with a vinyl ether monomer, and the method of deprotecting a fluorine-containing monomer/vinyl ether copolymer can be carried out by the method detailed in the third manufacturing method.

The preferred type, preferred addition amount, and the like of the compound represented by the general formula (6) can be applied to the details of the second production method. The preferred type, preferred addition amount, and the like of the vinyl ether monomer represented by the general formula (8) can be applied to the details of the third production method.

Hardening composition and hardened material

The curable composition containing the fluoropolymer of the present invention is also one of the inventions.

The aspect of the curable composition of the present invention may be, for example, a solvent. The curable film can be obtained by dissolving or dispersing the curable composition of the present invention in a solvent, applying it to various substrates to form a coating film, and then forming a coating film, and then curing it more efficiently by heating. The point is better.

Examples of the solvent include fluorine-containing organic solvents such as perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, and HCFC225; and alcohols having a carbon number of 1 to 8 Or an alcohol such as a glycol such as ethylene glycol or glycerin; a ketone such as methyl isobutyl ketone (MIBK); a halogenated hydrocarbon other than an ester or fluorine; Among these, HCFC225, alcohols, and ketones are preferred because the fluoropolymer can be easily dissolved and easily obtained. Among the alcohols, an alcohol having a carbon number of 1 to 4 is more preferable, and an isopropanol is more preferable.

The curable composition of the present invention may also contain a decane compound.

In the above decane compound, for example, the following general formula (9): Si(OR ^l ) ₄ (9)

(wherein R ^l represents an aliphatic hydrocarbon group, and the carbon number thereof is not particularly limited), the alkoxide compound represented by the oxime, the partial hydrolysis condensation product of the compound represented by the general formula (9), and the like.

As for the decane compound, among them, tetraethoxy decane is preferred from the viewpoint of easy availability.

The curable composition of the present invention is preferably a compound (a decane coupling agent) containing a hydrolyzable metal alkoxide other than the fluoropolymer of the present invention.

In the above decane coupling agent, the following general formula (10) is used: ESi(R ^II ) _3-r D _r (10)

(In the formula, the decane-based compound represented by the organic residue of the E-based organic compound, the D-based halogen atom or the alkoxy group, the R ^II- based alkyl group, and the r-based 1-3 integer) is preferably. .

Specific examples of the above decane coupling agent include tetraalkoxy decanes (for example, tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, tetraisopropoxy decane, tetrabutoxy). a decane or the like, a trialkoxy decane (for example, methyltrimethoxydecane, methyltriethoxydecane, methyltripropoxydecane, methyltributoxydecane, ethyltrimethoxy) Decane, ethyltriethoxydecane, n-propyltrimethoxydecane, n-propyltriethoxydecane, isopropyltrimethoxydecane, isopropyltriethoxydecane,vinyltrimethoxy Base decane, vinyl triethoxy decane, 3-glycidoxy propyl trimethoxy decane, 3-glycidoxy propyl triethoxy decane, 3-mercaptopropyl trimethoxy decane, 3-mercaptopropyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, 3,4-epoxycyclohexylethyltrimethoxydecane, 3,4-epoxy ring Hexylethyltrimethoxy Based on decane, etc.). Further, one type of these decane coupling agents or a mixture of two or more types may be used. These may act as a crosslinking agent for the curable composition and impart an increase in strength or heat resistance of the cured product.

Preferred among them, tetramethoxy decane, methyl trimethoxy decane, phenyl trimethoxy decane, tetraethoxy decane, methyl triethoxy decane, phenyl triethoxy decane, and , such condensates.

The blending amount of the decane coupling agent in the curable composition of the present invention can be adjusted in the range of 0 to 99% by mass based on 100% by mass of the fluoropolymer of the present invention.

The curable composition of the present invention may contain a filler as a constituent component as needed. For the above-mentioned filler, for example, a metal oxide, a metal, a polymer, a mineral, or the like may be used. These may be used alone or in combination of two or more. The filler is a function of functioning and functioning of the cured film obtained from the curable composition of the present invention. Specific functions include surface hardness, anti-blocking property, heat resistance, barrier properties, electrical conductivity, antistatic property, electromagnetic wave absorption, ultraviolet ray resistance, toughening resistance, impact resistance, and low heat line expansion.

Examples of the metal oxide include cerium oxide, titanium oxide, zirconium oxide, zinc oxide, tin oxide, indium oxide, aluminum oxide, cerium oxide, cerium oxide, magnesium oxide, iron oxide, and tin-doped indium oxide (ITO). , antimony doped tin oxide, fluorine doped tin oxide, and the like.

Examples of the metal include gold, silver, copper, aluminum, nickel, iron, zinc, stainless steel, and the like.

Examples of the polymer include a fluororesin, a liquid crystal polymer, an acrylic resin, a styrene resin, a polyurethane resin, an epoxy resin, a polycarbonate resin, a melamine resin, a polyolefin resin, a rubber, and the like.

Examples of the minerals include clay minerals such as montmorillonite, talc, mica, gibbsite, kaolin, bentonite, chert, vermiculite, and sericite. Other examples include carbon compounds such as carbon fibers, carbon black, acetylene black, ketjen black, and carbon nanotubes; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; glass fibers, glass beads, glass sheets, and glass. Various glasses such as balloons; etc.

The size of the above-mentioned filler is not particularly limited. For example, it may be any one of a spherical shape, a needle shape, a plate shape, a fiber shape, a balloon shape, a hollow shape, or the like, in a size of about 1 nm to 10 μm. As the above polymer, a powder, crosslinked particles, beads, or the like can be used.

Further, the filler may be used as it is, or it may be used as a solvent dispersed in a sol or a colloid.

In the above-mentioned filler, for the purpose of improving the dispersibility or the interface affinity, a surface-treated filler such as a coupling agent may be used.

The curable composition of the present invention may contain other components in addition to the above components insofar as the effects of the present invention are not impaired. Examples of the other component include a hardness adjuster, a bulking agent, a release agent, a surface treatment agent, a flame retardant, an antibacterial agent, a leveling agent, an antifoaming agent, a shaker, a heat stabilizer, and a light stabilizer. , UV absorbers, colorants, coupling agents, metal alkoxides, etc.

The curable composition of the present invention is not by the above In any one of the first to fourth manufacturing methods, the step of obtaining the fluoropolymer of the present invention is carried out by reprecipitating the fluoropolymer to be purified, and the decane coupling agent and the filler as a crosslinking agent may be directly added. , hardness modifier, extender or other additives, and in combination with the final state to adjust the viscosity by adding solvent to adjust.

The hardening of the curable composition of the present invention is basically carried out by a sol-gel reaction, a hydrolysis followed by a condensation reaction. The sol-gel hardening reaction can be carried out under known reaction conditions, but it can also be carried out, for example, by the following method.

First, the solvent-containing curable composition of the present invention is poured into a container, and then heated to carry out distillation of the solvent and sol-gel hardening. Next, the temperature is further raised to completely distill off the solvent, and by hardening the sol-gel, the desired blended hardened material can be obtained. In the distillation of the solvent and the sol-gel hardening step, it is preferred to carry out the foaming or hardening shrinkage caused by the rapid scattering of the volatile matter of the solvent or the like, and it is preferable to carry out the stage of the above two stages or more. . When it is hardened in two stages, the first stage is partially hardened and dried in order to remove the surface viscosity of the cured product, and it is usually preferably about 20 to 150 ° C for about 1 minute to 2 hours. The second stage is about 130 ° C ~ 280 ° C, preferably 200 ° C or more and less than 250 ° C, heating for 1 minute ~ 6 hours, completely remove the residual solvent, while the alkoxy decyl alcohol decoholization condensation reaction It’s over. The cured product (cured film) thus obtained is characterized by excellent heat resistance, mechanical properties, chemical resistance, water resistance, and durability due to the effect of the composite.

The curable composition of the present invention varies depending on its use, and examples thereof For example, for the use of sealing, etc., due to the viscosity at 30 ° C, if the viscosity is too low, there are many droplets, and on the contrary, the operability is lowered, which is 1 mPa. The above is better, from the viewpoint of good film formation, it is 5mPa. s or more is better, from the viewpoint of hardening and shrinkage at the time of hardening, it is 10 mPa. More is better than s. Also, from the point of view of good operability, 20000 mPa. The following is preferable, from the viewpoint of the forming process to the hardening composition, at 5000 mPa. s is more preferable, from the viewpoint of leveling (smooth surface smoothness) when forming a film, 2000 mPa. s is better than below.

The curable composition of the present invention is cured to form a cured film, and can be used in various applications. In terms of the method of forming the film, a suitable and well-known method can be employed for the purpose of use. For example, when it is necessary to control the film thickness, a roll coating method, a gravure coating method, a micro gravure coating method, a shower coating method, a bar coating method, a spray coating method, a slit coating method, a spin coating method, or a dipping method may be employed. Coating method, etc.

Although the curable composition of the present invention can be used for film formation, it is particularly useful as a molding material for various molded articles. Examples of the molding method include extrusion molding, injection molding, compression molding, blow molding, transfer molding, light molding, nanoimprinting, and vacuum molding.

The use of the curable composition of the present invention can be used as a material such as a sealing member, an optical member, a photoelectron tube, various inductors, and an antireflection film. Moreover, since the cured product obtained from the curable composition of the present invention is excellent in transparency, it is suitably used as an optical material for forming an optical member. Others may be used as a material for a sealing member for an electronic semiconductor, a water- and moisture-resistant adhesive, an adhesive for an optical component or a component, or a coating material.

In the form of use of the cured product of the present invention, a light-emitting element such as a light-emitting diode (LED), an EL element, or a nonlinear optical element, or a light-emitting element such as a CCD, CMOS, or PD light-receiving element may be exemplified (enclosed) ), installation, etc. Further, a sealing member (or a filler) for an optical member such as a lens of a deep ultraviolet microscope may be used.

The cured product of the present invention is excellent in transparency and is suitable as a sealing material for optical elements. The sealed optical element can be used in a variety of locations. The optical element is not particularly limited, and examples thereof include a light-emitting element such as a light-emitting diode (LED), an EL element, and a nonlinear optical element, or a light-receiving element such as a CCD, a CMOS or a PD, and a high-position brake lamp. Or a light-emitting element such as an instrument panel, a backlight for a mobile phone, a light source of a remote control device for various electrical products, an autofocus for a camera, a light-receiving element for optical pickup for CD/DVD, and the like.

The curable composition of the present invention is suitable for forming a material for an optical member. The curable composition of the present invention contains fluorine, and the obtained cured product can be an optical member having a low refractive index, and can be used, for example, as a medium for optical transmission. The curable composition of the present invention can be especially used for a plastic facing material of quartz or optical glass, a protective material for optical fibers, a protective material for all plastic optical fibers of a plastic material, and an anti-reflective coating. Materials, lens materials, optical waveguide materials, triterpenoid materials, optical window materials, optical memory disc materials, non-linear optical element materials, holographic optical materials, photolithographic materials, sealing materials for light-emitting elements, and the like.

Further, a material for an optical device can also be used. In terms of optical devices, optical waveguides, OADMs, optical converters, filters, and light are known. Optical components such as connectors, multiplexers, and optical components, etc., are useful materials for forming such devices. It also contains various functional compounds (non-linear optical materials, fluorescent functional dyes, photorefractive materials, etc.), and is also suitable for functional devices for optical devices such as regulators, wavelength conversion elements, and optical amplifiers. In terms of the use of the sensor, in particular, the sensitivity of the optical sensor or the pressure sensor is improved or the protection of the sensor due to the water-repellent property.

The cured product obtained by curing the curable composition is suitably used as an optical member in terms of excellent transparency. The cured product of the present invention preferably has a light transmittance of 80% or more. More preferably, it is 85% or more, and even more preferably 90% or more. The light transmittance of the cured product can be measured by a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.) at a wavelength of 550 nm. The cured product of the present invention is not only excellent in transparency, but also has a special performance as a sealing member, and is particularly suitable as a sealing member for an optical element.

Further, the curable composition of the present invention is excellent in adhesion to glass or metal, and is also applicable to a coating agent such as a glass or a metal surface, an antifouling agent, or the like. That is, the curable composition as a coating agent or an antifouling agent is also one of the preferred embodiments of the present invention.

When the curable composition of the present invention is used as a coating agent or an antifouling agent, a method of applying the curable composition of the present invention to the surface of a substrate can be employed. Examples of the coating method include brush coating, spray coating, spin coating, dip coating, roll coating, gravure coating, curtain coating, and the like.

Examples of the substrate include decorations such as tie clips, necklaces, and earrings; metal or plated products such as water pipes, brass instruments, woodwind instruments, golf clubs, door handles, dumbbells, and blades; and insulators and tiles. Ceramic materials such as sanitary ware, tableware, roof tiles, stone materials such as tombstones, chess stones, marble, etc.; paper products such as wallpapers, window papers, books, posters, photographs, etc.; wallets, boots, purses, straps, baseball Leather products such as gloves; fan blades, microwave oven doors, surface of refrigerators, etc.; contact glass for photocopiers, mirrors for OHP bodies, OHP sheets, keyboards, telephones, office machines, etc.; Household items such as cups, cupboards, mirrors, windowpanes, lampshades, chandeliers, etc.; building materials for windows, telephone booths, glass for sinks, vehicle parts such as vehicle glass and painted surface of vehicle body; Frames, glass of frog mirrors, goggles, hard hats, accessories for cover glass of clocks, etc.; glass of Pachinko pinball, playing cards, mahjong tiles, etc. Game console; furniture, pianos, etc. painted surfaces and so on.

[Examples]

Next, the present invention will be described by way of Synthesis Examples and Examples, but the present invention is not limited to the Synthesis Examples and Examples.

The measurement methods used in this specification are organized as follows.

(1) Fluorine content

The sample was burned by an oxygen flask to burn 10 mg of the sample to absorb the decomposition gas. In 20 ml of deionized water, the fluorine ion concentration in the absorption liquid was measured by a fluorine selective electrode method (fluoride ion meter, model 901 manufactured by ORION Co., Ltd.) to determine (% by mass).

(2) ¹⁹ F-NMR measurement

NMR measuring device: GEMINI-300 manufactured by VARIAN

¹⁹ F-NMR measurement conditions: 376 MHz (trichlorofluoromethane = 0 ppm)

(3) ¹ H-NMR measurement

NMR measuring device: GEMINI-300 manufactured by VARIAN

¹ H-NMR measurement conditions: 400 MHz (tetramethyl decane = 0 ppm)

(4) Molecular weight and molecular weight distribution

By colloidal permeation chromatography (GPC), GPC HLC-8020 manufactured by TOSOH Co., Ltd., pipe column manufactured by Shodex Co., Ltd. (GPC KF-801 1 GPC KF-802 1 GPC KF-806 M 2 inline column) Next, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were calculated from the data obtained by flowing tetrahydrofuran (THF) as a solvent at a flow rate of 1 ml/min.

(5) Glass transition temperature (Tg)

Using a DSC (differential scanning calorimeter: manufactured by SEIKO Co., Ltd., RTG220), the temperature range from -50 ° C to 200 ° C was raised at 10 ° C / min (first round) - cooling - warming (second round), In the second round The intermediate point of the endothermic curve is Tg (°C).

(6) Melting point (Tm)

When the temperature was raised at 10 ° C /min using DSC (differential scanning calorimeter: manufactured by SEIKO Co., Ltd., RTG220), the temperature corresponding to the maximum value in the heat of fusion curve was taken as Tm (° C.).

(7) IR analysis

The measurement was carried out at room temperature using a Fourier transform infrared spectrophotometer 1760X manufactured by Perkin Elmer.

Synthesis Example 1

1200 g of butyl acetate as a solvent and 140 g of vinyl acetate as a vinyl ester monomer were placed in a 3 L stainless steel high-pressure reactor, and per-butyl PV (product name, Nippon Oil Co., Ltd.) as a polymerization initiator was added. The company made 7.2 g, screwed the flange, replaced the high-pressure reactor with a vacuum, sealed 200 g of tetrafluoroethylene as a fluoroolefin gas, and placed the reactor at 60 ° C to start the reaction. The consumption of the gas monomer was confirmed by the decrease in the polymerization pressure, and the vibration was stopped after 6 hours, and the residual gas was blown off to terminate the reaction.

After completion of the reaction, the polymer solution was reprecipitated in a large amount of methanol solution to purify the polymer to obtain a polymer A1.

The composition of the polymer A1 is determined by elemental analysis of fluorine, and the interaction ratio of the fluoroolefin to the vinyl ester is calculated from ¹ H-NMR, and the weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) are determined from GPC. Got it. The glass transition temperature was also determined from DSC. The results are shown in Table 2.

Synthesis Example 2

The polymer A2 was obtained in the same manner as in Synthesis Example 1 except that the monomer implantation ratio, the scale, the reaction time, and the like were changed. The reaction conditions are shown in Table 1, and the physical properties of the obtained polymer were summarized in Table 2.

Synthesis Example 3

In a 3L stainless steel high-pressure reactor, 1000 g of pure water, 23.2 g of vinyl acetate, and NEOCAL P (76.4% by mass of sodium octylsulfosuccinate) in isopropyl alcohol solution: First Industrial Pharmaceutical Co., Ltd. After replacing with nitrogen, 37 g of tetrafluoroethylene was added, and the temperature in the tank was raised to 80 °C. Thereafter, 30 g of tetrafluoroethylene was added. At this time, the pressure in the tank was 0.809 MPa. Thereto, 22 g of a 1% by mass aqueous solution of ammonium persulfate (APS) was added under stirring to start the reaction. At the beginning of the reaction, vinyl acetate was added, and 283 g of vinyl acetate was added over 6 hours. In the reaction, a ratio of vinyl acetate/tetrafluoroethylene was made constant, and a solenoid valve was used to continuously supply tetrafluoroethylene. The stirring speed was 500 rpm.

Specifically, when tetrafluoroethylene is consumed to make the inside of the tank 0.800 MPa, the electromagnetic valve is automatically opened to supply tetrafluoroethylene, and when it is 0.775 MPa, the electromagnetic valve is automatically closed to stop the supply of tetrafluoroethylene, so that The cycle is used to control the supply and pressure of tetrafluoroethylene, and vinyl acetate is added in combination with the consumption of tetrafluoroethylene.

Stopping tetrafluoroethylene and acetic acid 6 hours after the start of the reaction The supply of vinyl esters. After the reaction was carried out for 1 hour, the inside of the vessel was returned to normal temperature and normal pressure to terminate the polymerization, and 1661 g of a vinyl acetate/tetrafluoroethylene copolymer emulsion (solid content concentration: 38.5 mass%) was obtained.

The glass transition temperature of the obtained vinyl acetate/tetrafluoroethylene copolymer was 40 ° C and the particle diameter was 116 nm. The reaction conditions are shown in Table 1, and the physical properties of the obtained polymer were summarized in Table 2.

Synthesis Example 4

Into a 300 mL stainless steel high-pressure reactor, 50 g of a butyl acetate solvent and 10 g of a vinyl stearate monomer were placed, and 0.4 g of per-butyl PV (product name, manufactured by Nippon Oil Co., Ltd.) as a polymerization initiator was added. The flange was screwed, the high pressure reactor was replaced by a vacuum, 8.0 g of tetrafluoroethylene as a fluoroolefin gas was sealed, and then 2.6 g of hexafluoropropylene was sealed, and the reaction was started by placing it in a vibrating thermostat at 60 °C. The consumption of the gas monomer was confirmed by the decrease in the polymerization pressure, the vibration was stopped for 15 hours, and the residual gas was blown off to terminate the reaction.

After completion of the reaction, the polymer solution was reprecipitated in a large amount of methanol solution to purify the polymer to obtain a polymer A4.

The same analysis as in Synthesis Example 1 was carried out except that the melting point was measured instead of the glass transition temperature. The results are shown in Table 2.

Synthesis Example 5~7

Polymers A5, B1, and B2 were obtained in the same manner as in Synthesis Example 1, except that the type of the monomer, the implantation ratio, the scale, and the reaction time were changed. The reaction conditions are listed in Table 1, and the physical properties of the obtained polymer are summarized in the table. 2.

Synthesis Example 8

Into a 300 mL stainless steel high-pressure reactor, 150.0 g of t-butanol, 26.7 g of t-butyl vinyl ether, and 0.48 g of potassium carbonate were added, and a 70% isooctane solution of per-butyl PV as a polymerization initiator was added. 0.46 g, the flange was screwed, the high pressure reactor was replaced by a vacuum, and 26.7 g of tetrafluoroethylene (TFE) as a fluoroolefin gas was sealed, and the reaction was started by placing it in a vibrating thermostat at 60 °C. The consumption of the gas monomer was confirmed by the decrease in the polymerization pressure, the vibration was stopped for 3 hours, and the residual gas was blown off to terminate the reaction.

After completion of the reaction, the polymer solution was reprecipitated in a large amount of methanol solution to purify the polymer to obtain a polymer C1.

The reaction conditions are shown in Table 1, and the physical properties of the obtained polymer were summarized in Table 2.

Synthesis Example 9 (saponification heterogeneous system)

4 g of the TFE/vinyl acetate polymer A2 obtained in Synthesis Example 2 was placed in 136 g of a MeOH solvent and stirred, and a catalyst amount of NaOH pellets (about 0.4 g) was added thereto to slowly react, and stirring was continued until the polymer was uniformly Soaked up. At the same time as the reaction, the solution turned yellow and colored, and as a result of stirring at room temperature for 3 days, the reaction was stopped because the polymer was uniformly dissolved. The reaction liquid was concentrated by an evaporator, and the mixture was poured into water to reprecipitate the polymer to be purified. After washing with 1 N HCl, the mixture was sufficiently washed with ion-exchanged water, and the reprecipitated polymer was vacuum-filtered, and dried in a dryer at 80 ° C for 2 hr. The hydrolysis rate (saponification degree) was calculated from the relative intensity of the carbonyl peak by IR, and as a result, almost 100% of TFE/vinyl alcohol polymer A2-100 was obtained.

Synthesis Example 10 (saponification uniformity)

10 g of the TFE/vinyl acetate polymer A1 obtained in Synthesis Example 1 was uniformly dissolved in a THF solvent to have a concentration of 10% by mass. Thereafter, a 0.6 N NaOH solution was added to make a vinyl acetate equivalent in the polymer, and after 30 minutes, the polymer was reprecipitated in a large amount of water. After washing with 1 N HCl, the mixture was sufficiently washed with ion-exchanged water, and the reprecipitated polymer was vacuum-filtered, and dried in a dryer at 80 ° C for 2 hr. The hydrolysis rate (saponification degree) was calculated from the relative intensity of the carbonyl peak by IR, and as a result, 34% of TFE/vinyl alcohol/vinyl acetate polymer A1-34 was obtained.

Synthesis Examples 11 to 13 (saponification uniformity)

By changing the saponification time of Synthesis Example 10, A1-45, A1-86, and A1-96 of a TFE/vinyl alcohol/vinyl acetate polymer were obtained. The saponification time and the degree of saponification were summarized in Table 3.

Synthesis Examples 14 to 18 (saponification uniformity)

The saponified polymer was obtained in the same manner as in Synthesis Example 10 except that the saponification time of Synthesis Example 10 was one day and the polymers obtained in Synthesis Examples 3 to 7 were used. The results are summarized in Table 3.

Synthesis Example 19 (deprotection step)

The TFE/t-butyl vinyl ether polymer C1 (TFE/t-butyl vinyl ether = 48/52 (mole ratio)) obtained in Synthesis Example 8 was placed in a 100 mL eggplant-shaped flask, 2.63 g, 1, 1.2 ml of 4-dioxanthine and 50 ml of a 4N aqueous HCl solution were stirred and heated at 80 °C. After 2 hours, the heating was stopped and left to cool, and the precipitated polymer was washed 3 times with pure water. The polymer was dissolved in tetrahydrofuran (THF), reprecipitated in a solution of ethanol/water (50/50% by volume), and dried under vacuum. The integral value of the proton from the third butyl group (-C(CH ₃ ) ₃ ) in the vicinity of 1.0 to 1.3 ppm and the main chain methylene group from 2.2 to 2.7 ppm before and after the deprotection reaction were quantified by ¹ H-NMR ( The integral value of the proton of -CH ₂ -CH-), and the result of calculating the degree of deprotection showed that 97% of TFE/vinyl alcohol/t-butyl vinyl ether polymer C1-97 was obtained. The results are summarized in Table 3.

Example 1

1.5 g of polymer A1-96 was uniformly dissolved in 20 g of N,N-dimethylformamide (DMF) solvent. Add 3-isocyanate propyl triethoxy decane ((C ₂ H ₅ O) ₃ SiC ₃ H ₆ NCO) (KBE-9007) 0.59 g (corresponding to 10 mM % denaturation of OH groups in the polymer) and as After 42 μL of the catalyst dibutyltin dilaurate, it was stirred at room temperature for 24 hours.

From the analysis results of IR, it was found that the OH group of the polymer was greatly reduced, and the peak of the urethane bond (N-H and C=O) was newly observed. This polymer is referred to as A1-96-KBE20.

Example 2~11

The reaction was carried out in the same manner as in Example 1 except that the polymer described in Table 4 was used, and it was reacted with 3-isocyanatepropyltriethoxysilane. The blend ratios are summarized in Table 4. As a result of performing IR analysis of these polymers, it was found that the OH group of the polymer was greatly reduced, and the peak of the urethane bond (N-H and C=O) was newly observed. Abbreviations for each polymer are also shown in Table 4.

Example 12

1.5 g of polymer A1-96 was uniformly dissolved in 15 g of THF solvent. After that, 0.4 g of sodium hydroxide was added, and after it was uniformly dissolved, it leaked from the drip. 0.54 g of allyl bromide was added dropwise at room temperature, and stirred at room temperature for 13 hours. After the obtained reaction solution was further submerged in water and dried under vacuum, it was dissolved in a DMSO solution and analyzed by H-NMR to confirm the allyl group. The amount of introduction of the allyl group calculated from NMR was 100 mol%. The obtained polymer was 0.8 g, and the yield was 53%.

If this process is represented by a chemical reaction formula, it can be expressed as follows.

The polymer A1-96 and the obtained polymer were analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis, and in the above formula, each was m:n:p=43:55:2, m:a : p=43:55:2 polymer.

Next, 5 g of THF was added to 0.5 g of the obtained polymer, and it was dissolved at room temperature. 0.1 ml of 1,3-divinyl-1,1,3,3-tetramethyldioxane platinum complex and 0.54 g (0.004 mol) of trichloromethane were added thereto, and stirred at room temperature for 24 hours. , hydrogenation oximation reaction. The completion of the reaction was confirmed by IR (infrared absorption analysis) with the disappearance of the specific absorption (2130 cm ^-1 ) on Si-H. Further, 0.65 g (0.014 mol) of ethanol and 1.2 g of pyridine were added, and the mixture was stirred for 24 hours. The obtained solution was reprecipitated and purified to obtain 0.2 g of a polymer (yield: 40%).

The polymer was analyzed by ¹⁹ F-NMR, ¹ H-NMR analysis and IR analysis as a polymer of m:a:p=43:55:2 in the following formula.

Example 13 Production of hardenable composition

1.1 g of the A1-96-KBE20 synthesized in Example 1 was dissolved in MIBK to a concentration of 10% by mass. Next, a spin coater was used on the wafer at 300 rpm. 5 seconds, 3000rpm. After 25 seconds of spin coating, heating The film was heated on a table at 250 ° C for 5 minutes. The physical properties of the coating film after film formation were evaluated. The results are summarized in Table 5. The appearance after film formation was evaluated by visual observation. The evaluation results are represented by ○ (homogeneous), Δ (turbidity), and × (white turbidity). Solvent Resistance A drop of butyl acetate solution was applied to the coating film, and after 1 minute, it was wiped with a mirror paper to visually evaluate the appearance. The evaluation results are indicated by ○ (no change), Δ (partial change), and × (peel). Heat resistance The enamel wafer after film formation was placed in an electric furnace at 100 ° C, and the appearance was visually evaluated after 100 hours. The evaluation results are indicated by ○ (no change), Δ (partial change), and × (peel). The value of the refractive index after film formation was measured by an ellipsometer.

Examples 14, 15

A curable composition was produced in the same manner as in Example 13, and the physical properties of the coating film were evaluated. The types, amounts, and evaluation results of the polymers to be used are shown in Table 5.

Comparative example 1, 2

Using the polymer A1 (Comparative Example 1) and A1-96 (Comparative Example 2), a curable composition was produced in the same manner as in Example 13, and the coating film properties were evaluated. The evaluation results are shown in Table 5.

Claims (16)

A fluoropolymer comprising a polymerization unit based on a fluorine-containing monomer, a vinyl alcohol-based polymerization unit as an arbitrary polymerization unit, and a polymerization unit represented by the general formula (1): -CH ₂ -CH (- O-(L) _l -R ^b )- (1) (wherein R ^b is an organic group having at least one hydrolyzable metal alkoxide, L is a divalent organic group, and l is 0 or 1). The fluoropolymer according to claim 1, wherein R ^b is a group represented by the following general formula (2): -R ¹¹ _a (R ¹² O) _b M{O-MR ¹¹ _g (OR ¹² ) _h } _f -R ¹¹ _d (OR ¹² ) _e (2) (wherein the M-based metal and R ¹¹ may be the same or different, and are a hydrocarbon group having 1 to 20 carbon atoms; R ¹² may be the same or different, and is an alkyl group; Alkoxyalkyl or aryl, a-line 1-3 integer, b-system 0-4 integer, a+b=2~5, d-system 0 or 1, e-system 0 or 1, d+e= 1. f is an integer from 0 to 10, g is an integer from 0 to 3, h is an integer from 0 to 3, g + h = 1 to 3, and at least one of b, e, and h is 1 or more. The fluoropolymer according to claim 1 or 2, wherein L is an organic group represented by the general formula (3): -(C=O) _s -(NH) _p - (3) (wherein s is 0 Or 1, p is 0 or 1). A fluoropolymer as claimed in claim 1, 2 or 3, wherein the L is a single key. The fluoropolymer according to claim 1, 2, 3 or 4, wherein the molar ratio based on the polymerization unit of the fluorine-containing monomer, the polymerization unit based on the vinyl alcohol, and the polymerization unit represented by the general formula (1) (30~70)/(0~69)/(1~70). A manufacturing method for producing a fluoropolymer according to claim 1, 2, 3, 4 or 5, characterized by comprising the step of copolymerizing a fluoromonomer with a vinyl ester monomer a step of obtaining a fluorine-containing monomer/vinyl ester copolymer, a step of obtaining a fluorine-containing monomer/vinyl alcohol copolymer by hydrolyzing the fluorine-containing monomer/vinyl ester copolymer, and by subjecting the fluorine-containing monomer a step of reacting a body/vinyl alcohol copolymer with a compound represented by the general formula (4) to obtain a fluoropolymer: O = C = NR ^b (4) (wherein R ^{b has} at least one hydrolyzable metal The organic group of the alkoxide). The production method according to claim 6, wherein the compound represented by the general formula (4) is a compound represented by the following general formula (5): O = C = NR ¹¹ _a (R ¹² O) _b M{O-MR ¹¹ _g (OR ¹² ) _h } _f -R ¹¹ _d (OR ¹² ) _e (5) (wherein the M-based metal and R ¹¹ may be the same or different, and are a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² may be the same Or different, an alkyl group, an alkoxyalkyl group, or an aryl group, an integer of a to 1 to 3, an integer of b to 0 to 4, a+b=2 to 5, d system 0 or 1, e system 0 or 1, d + e = 1, f is an integer from 0 to 10, g is an integer from 0 to 3, h is an integer from 0 to 3, g + h = 1 to 3, b, e, and h are at least 1 Those are more than 1). A manufacturing method for producing a fluoropolymer according to claim 1, 2, 3, 4 or 5, characterized by comprising the step of copolymerizing a fluoromonomer with a vinyl ester monomer a step of obtaining a fluorine-containing monomer/vinyl ester copolymer, a step of obtaining a fluorine-containing monomer/vinyl alcohol copolymer by hydrolyzing the fluorine-containing monomer/vinyl ester copolymer, by subjecting the fluorine-containing monomer a step of reacting a monomer/vinyl alcohol copolymer with a compound represented by the general formula (6) to obtain an olefin-containing fluoropolymer: X ^b -R ^c (6) (wherein X ^b is Cl, Br or I, R ^c is an organic group having at least one olefin), and further by alkylating the olefin-containing fluoropolymer with trichlorodecane or trialkoxy decane, and using trichloromethane, further The step of alkoxylation with an aliphatic alcohol to obtain a fluoropolymer containing a hydrolyzable metal alkoxide is carried out. The production method of claim 8, wherein the compound represented by the general formula (6) is a compound represented by the following general formula (7): X ^b -R ¹³ -(R ¹⁴ -CH=CH ₂ ) _c (7) (wherein X ^b is Cl, Br or I, R ¹³ may be the same or different, and is a hydrocarbon group having a carbon number of 1 to 20 (c+1), and R ¹⁴ may be the same or different, and is -O- , -OC(=O)-, single bond, c is an integer from 1 to 10). A manufacturing method for producing a fluoropolymer according to claim 1, 2, 3, 4 or 5, characterized by comprising the steps of: fluorinating a monomer and formula (8) The step of copolymerizing a vinyl ether monomer to obtain a fluorine-containing monomer/vinyl ether copolymer: CH ₂ =CH-OR (8) (wherein R can be converted into a vinyl alcohol by a deprotection reaction a protecting group), a step of obtaining a fluorine-containing monomer/vinyl alcohol copolymer by deprotecting the aforementioned fluorine-containing monomer/vinyl ether copolymer, and by subjecting the aforementioned fluorine-containing monomer/vinyl alcohol copolymer a step of reacting a compound represented by the general formula (4) to obtain a fluoropolymer: O = C = NR ^b (4) (wherein R ^b is an organic group having at least one hydrolyzable metal alkoxide) . The method of claim 10, wherein the compound represented by the general formula (4) is a compound represented by the following general formula (5): O=C=NR ¹¹ _a (R ¹² O) _b M{O-MR ¹¹ _g (OR ¹² ) _h } _f -R ¹¹ _d (OR ¹² ) _e (5) (wherein the M-based metal and R ¹¹ may be the same or different, and are a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² may be the same Or different, an alkyl group, an alkoxyalkyl group, or an aryl group, an integer of a to 1 to 3, an integer of b to 0 to 4, a+b=2 to 5, d system 0 or 1, e system 0 or 1, d + e = 1, f is an integer from 0 to 10, g is an integer from 0 to 3, h is an integer from 0 to 3, g + h = 1 to 3, b, e, and h are at least 1 Those are more than 1). A manufacturing method for producing a fluoropolymer according to claim 1, 2, 3, 4 or 5, characterized by comprising the steps of: fluorinating a monomer and formula (8) The step of copolymerizing a vinyl ether monomer to obtain a fluorine-containing monomer/vinyl ether copolymer: CH ₂ =CH-OR (8) (wherein R can be converted into a vinyl alcohol by a deprotection reaction a protecting group), wherein the fluoromonomer/vinyl alcohol copolymer is obtained by deprotecting the fluoromonomer/vinyl ether copolymer, by using the fluoromonomer/vinyl alcohol copolymer The step of reacting a compound represented by the formula (6) to obtain an olefin-containing fluoropolymer: X ^b -R ^c (6) (wherein the X ^b system Cl, Br or I, R ^c system has at least one An organic group of an olefin, and further alkoxylation of the olefin-containing fluoropolymer with a trichloro decane or a trialkoxy decane, and using trichloromethane The reaction is carried out to obtain a fluoropolymer containing a hydrolyzable metal alkoxide. The method of claim 12, wherein the compound represented by the general formula (6) is a compound represented by the following general formula (7): X ^b -R ¹³ -(R ¹⁴ -CH=CH ₂ ) _c (7) (wherein X ^b is Cl, Br or I, R ¹³ may be the same or different, and is a hydrocarbon group having a carbon number of 1 to 20 (c+1), and R ¹⁴ may be the same or different, and is -O- , -OC(=O)-, single bond, c is an integer from 1 to 10). A hardenable composition comprising the fluoropolymer of claim 1, 2, 3, 4 or 5. A sclerosing composition according to claim 14, which is a coating agent or an antifouling agent. A cured product obtained by hardening a hardenable composition as claimed in claim 14.