JP2013177570A - Fluorine-containing polymer and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new fluorine-containing polymer that is easily cured while having transparency, low refractive index property, solvent resistance and heat resistance.SOLUTION: A fluorine-containing polymer comprises a polymerizable unit based on a fluorine-containing monomer, a polymerizable unit based on vinyl alcohol as an arbitrary polymerizable unit and a polymerizable unit represented by general formula (1): -CH-CH(-O-(L)-R)- (wherein Rb is an organic group containing at least one terminal double bond; L is a divalent organic group; and l is 0 or 1).

Description

The present invention relates to a fluoropolymer and a method for producing the same.

Polyvinyl alcohol and ethylene-vinyl alcohol copolymer have hydrophilic properties, have a property of being difficult to permeate gases such as oxygen and nitrogen, and excellent in fuel barrier properties.

In Patent Document 1, the copolymer film having excellent water resistance is composed of a copolymer of tetrafluoroethylene and vinyl acetate or a copolymer obtained by saponifying at least a part of an acetate group contained in the copolymer. There has been proposed a fluorine-containing copolymer film having a tetrafluoroethylene content of 1 to 70 mol% contained in the copolymer.

In Patent Document 2, it is pointed out that the copolymer proposed in Patent Document 1 is inferior in productivity and heat resistance, and the quality is deteriorated due to coloring. After copolymerization with a vinyl ether in which a hydrogen atom of a hydroxyl group is substituted with a deprotectable protecting group, the protecting group is substituted with a hydrogen atom by a deprotection reaction to form a hydroxyl group, thereby producing a fluorine-containing olefin / A method for producing a vinyl alcohol copolymer has been proposed.

JP-A-5-261256 International Publication No. 2011/126056 Pamphlet

The conventional fluorine-containing olefin / vinyl alcohol copolymer does not have a curing site suitable for the curing reaction and cannot be easily cured.

The present invention provides a novel fluoropolymer that can be easily cured while having transparency, low refractive index property, solvent resistance and heat resistance.

The present invention can also easily produce a polymer that can be easily cured while having transparency, low refractive index property, solvent resistance and heat resistance, and the resulting polymer has a cured product. Provided is a novel fluoropolymer production method capable of easily adjusting the amount of sites.

The present invention is a polymerized unit based on a fluorine-containing monomer,
Polymer units based on vinyl alcohol as optional polymer units, and
Formula (1): —CH ₂ —CH (—O— (L) ₁ —R ^b ) —
(Wherein R ^b is an organic group having at least one terminal double bond, L is a divalent organic group, and l is 0 or 1),
It is a fluorine-containing polymer characterized by including.

R ^b represents the general formula (2):

(In the formula, M is H, Cl, F or CH ₃ , j is an integer of 1 to 20, k is an integer of 1 to 10, and 2j + 1−k is an integer of 0 or more). A group represented by formula (3):

In the formula, R is preferably at least one substituent selected from the group consisting of groups represented by H, Cl, F, CH ₃ or CF ₃ .

L represents the general formula (4):
− (C═O) _s − (N−H) _p −
(Wherein s is 0 or 1 and p is 0 or 1).

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

The present invention is a production method for producing the above-mentioned fluorine-containing polymer, wherein a fluorine-containing monomer / vinyl ester copolymer is obtained by copolymerizing a fluorine-containing monomer and a vinyl ester monomer. A step of obtaining a fluorine-containing monomer / vinyl alcohol copolymer by hydrolyzing the fluorine-containing monomer / vinyl ester copolymer, and the fluorine-containing monomer / vinyl alcohol copolymer. And general formula (5):
O = C = N-R ^b
(Wherein R ^b is an organic group having at least one terminal double bond), and a step of obtaining a fluoropolymer by reacting with the compound represented by But there is.

The present invention is a production method for producing the above-mentioned fluorine-containing polymer, wherein a fluorine-containing monomer / vinyl ester copolymer is obtained by copolymerizing a fluorine-containing monomer and a vinyl ester monomer. A step of obtaining a fluorine-containing monomer / vinyl alcohol copolymer by hydrolyzing the fluorine-containing monomer / vinyl ester copolymer, and the fluorine-containing monomer / vinyl alcohol copolymer. And general formula (7):
^{X b -C (= O) -R} b
(Wherein, ^{X b} is ^HO-, R 10 O-, a F- or Cl @ ^{-, R 10} is an alkyl group or a fluorinated alkyl group, ^{R b} is an organic group having at least one terminal double bond And a step of obtaining a fluorine-containing polymer by reacting with the compound represented by formula (1)).

The present invention is a production method for producing the above-mentioned fluoropolymer, comprising a fluoromonomer and a general formula (9):
CH ₂ = CH-OR
(Wherein R is a protecting group that can be converted to vinyl alcohol by a deprotection reaction) to obtain a fluorine-containing monomer / vinyl ether copolymer by copolymerizing with a vinyl ether monomer represented by: A step of obtaining the fluorine-containing monomer / vinyl alcohol copolymer by deprotecting the fluorine-containing monomer / vinyl ether copolymer, and the fluorine-containing monomer / vinyl alcohol copolymer and the general formula ( 5):
O = C = N-R ^b
(Wherein R ^b is an organic group having at least one terminal double bond), and a step of obtaining a fluoropolymer by reacting with the compound represented by But there is.

The compound represented by the general formula (5) is represented by the general formula (6):

(In the formula, M is H, Cl, F or CH ₃ , j is an integer of 1 to 20, k is an integer of 1 to 10, and 2j + 1−k is an integer of 0 or more). It is preferable that it is a compound represented.

The present invention is a production method for producing the above-mentioned fluoropolymer, comprising a fluoromonomer and a general formula (9):
CH ₂ = CH-OR
(Wherein R is a protecting group that can be converted to vinyl alcohol by a deprotection reaction) to obtain a fluorine-containing monomer / vinyl ether copolymer by copolymerizing with a vinyl ether monomer represented by: A step of obtaining the fluorine-containing monomer / vinyl alcohol copolymer by deprotecting the fluorine-containing monomer / vinyl ether copolymer, and the fluorine-containing monomer / vinyl alcohol copolymer and the general formula ( 7):
^{X b -C (= O) -R} b
(Wherein, ^{X b} is ^HO-, R 10 O-, a F- or Cl @ ^{-, R 10} is an alkyl group or a fluorinated alkyl group, ^{R b} is an organic group having at least one terminal double bond And a step of obtaining a fluorine-containing polymer by reacting with the compound represented by formula (1)).

The compound represented by the general formula (7) is represented by the general formula (8):

(In the formula, R is H, Cl, F, CH ₃ or CF ₃ , X ^b is HO—, R ¹⁰ O—, F— or Cl—, and R ¹⁰ is an alkyl group or a fluorine-containing alkyl group. It is preferable that it is a compound represented by.

This invention is also a curable composition containing the above-mentioned fluoropolymer.

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

The present invention is also an antireflection film obtained by curing the above-described curable composition.

The fluoropolymer of the present invention can be easily cured. The cured product obtained by curing the fluoropolymer of the present invention has transparency, low refractive index, solvent resistance and heat resistance.
The production method of the present invention has a transparency, a low refractive index property, a solvent resistance and a heat resistance, and can easily produce a fluorinated polymer that can be easily cured. It is also easy to adjust the amount of the cured site that the has.

19 is an IR chart of the polymer (A1-96) obtained in Synthesis Example 13. 2 is an IR chart of the polymer (A1-96-AOI) obtained in Example 1.

Hereinafter, the present invention will be specifically described.

The fluorine-containing polymer of the present invention includes a polymer unit based on a fluorine-containing monomer, a polymer unit based on vinyl alcohol as an arbitrary polymer unit, and a polymer unit represented by the general formula (1). To do.

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

Examples of the fluorine-containing monomer include tetrafluoroethylene [TFE], vinylidene fluoride [VdF], chlorotrifluoroethylene [CTFE], vinyl fluoride, hexafluoropropylene [HFP], hexafluoroisobutene, and CH _2. = CZ ¹ (CF ₂ ) _n1 Z ² (wherein Z ¹ is H, F or Cl, Z ² is H, F or Cl, and n1 is an integer of 1 to 10), Perfluoro (alkyl vinyl ether) [PAVE] represented by CF ₂ = CF—ORf ¹ (wherein Rf ¹ represents a perfluoroalkyl group having 1 to 8 carbon atoms), and CF ₂ = CF— OCH ₂ -Rf ² (wherein, Rf ² is a perfluoroalkyl group having 1 to 5 carbon atoms) is selected from the group consisting of alkyl perfluorovinyl ether derivative represented by the At least one fluorine-containing monomer is preferred.

As monomer represented by ^{_{CH 2 = CZ 1 (CF 2}} ) n1 Z 2, 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], perfluoro (butyl vinyl ether), etc. Among them, PMVE PEVE or PPVE is more preferable.

As the alkyl perfluorovinyl ether derivative, those in which Rf ² is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF ₂ = CF—OCH ₂ —CF ₂ CF ₃ is more preferable.

The fluorine-containing monomer is preferably at least one selected from the group consisting of TFE, CTFE and HFP, and more preferably TFE.

The fluoropolymer of the present invention has a general formula (1): —CH ₂ —CH (—O— (L) ₁ —R ^b ) —.
(Wherein R ^b is an organic group having at least one terminal double bond, L is a divalent organic group, and l is 0 or 1). The fluoropolymer of the present invention is a polymer having a double bond as a cured site, and the number of cured sites can be easily adjusted when the fluoropolymer is produced.
Further, the polymerization unit represented by the general formula (1) has the general formula:
_{CH 2 = CH-O- (L} ) l -R b
(Wherein R ^b is an organic group having at least one terminal double bond, L is a divalent organic group, and l is 0 or 1). Unit.

Specific examples of R ^b include general formula (2):

(In the formula, M is H, Cl, F or CH ₃ , j is an integer of 1 to 20, k is an integer of 1 to 10, and 2j + 1−k is an integer of 0 or more.)
The group represented by these is mentioned.

In the general formula representing R ^b , j is preferably an integer of 1 to 10, and more preferably an integer of 1 to 6. k is preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.

Among these substituents, ^Rb has the general formula:

(Where j, k and 2j + 1-k are the same as above)
Is preferable from the viewpoint of reactivity.

Moreover, as a specific example of ^Rb , general formula (3):

(Wherein R is H, CH ₃ , F, CF ₃ or Cl.)
The group represented by these is also mentioned.

Among these, the following formula:

The group represented by these is preferable.

（式中、ＭはＨ、Ｃｌ、Ｆ又はＣＨ_３であり、ｊは１〜２０の整数であり、ｋは１〜１０の整数であり、２ｊ＋１−ｋは０以上の整数である。）で表される基、及び、一般式（３）：

（式中、ＲはＨ、Ｃｌ、Ｆ、ＣＨ_３又はＣＦ_３である）
で表される基からなる群より選択される少なくとも１種の置換基であることが好ましい。 As R ^b , among the groups exemplified above, in particular, the general formula (2):

(In the formula, M is H, Cl, F or CH ₃ , j is an integer of 1 to 20, k is an integer of 1 to 10, and 2j + 1−k is an integer of 0 or more). A group represented by formula (3):

Wherein R is H, Cl, F, CH ₃ or CF ₃
It is preferable that it is at least 1 sort (s) of substituents selected from the group which consists of group represented by these.

L represents the general formula (4):
− (C═O) _s − (N−H) _p −
(Wherein s is 0 or 1 and p is 0 or 1). When both s and p are 1, R ^b is bonded to the main chain of the fluoropolymer via a urethane bond. When s is 1 and p is 0, R ^b is bonded via an ester bond. When bonded to the main chain of the fluoropolymer, when both s and p are 0, L represents a single bond, and ^Rb is bonded to the main chain of the fluoropolymer via an ether bond. become.

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

The fluoropolymer of the present invention may contain a polymer unit based on a vinyl ester monomer or a vinyl ether monomer in addition to the above three polymer units. The fluoropolymer of the present invention includes a polymer unit based on a fluoromonomer, a polymer unit based on vinyl alcohol, a polymer unit represented by the general formula (1), and a vinyl ester monomer or vinyl ether monomer. Is a molar ratio of polymer units based on (polymer unit based on fluorine-containing monomer) / (polymer unit based on vinyl alcohol) / (polymer unit represented by formula (1)) / (vinyl ester monomer or The polymerization unit based on the vinyl ether monomer) is preferably (30 to 70) / (0 to 69) / (1 to 70) / (0 to 69), (30 to 70) / (0 to 65). / (5-70) / (0-65) is more preferable. More preferably, it is (30-70) / (1-65) / (5-69) / (0-65).

Examples of the vinyl ester monomer include vinyl acetate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, and the like. As the vinyl ester monomer, vinyl acetate and vinyl stearate are preferable. More preferred is vinyl acetate.

Examples of the vinyl ether monomer include t-butyl vinyl ether, 1,1-dimethylpropyl vinyl ether, methoxymethyl vinyl ether, tetrahydrofuryl vinyl ether, tetrahydropyranyl vinyl ether, vinyloxytrimethylsilane, and vinyloxydimethylphenylsilane. As the vinyl ether monomer, t-butyl vinyl ether is preferable.
These vinyl ether monomers may be used individually by 1 type, and may use 2 or more types together.

The fluorine-containing polymer of the present invention may contain a polymer unit based on another monomer copolymerizable with the fluorine-containing monomer. Polymeric units based on the above other monomers are polymerized units based on monomers not containing fluorine atoms (however, polymerized units based on vinyl alcohol, polymerized units represented by general formula (1) and vinyl ester monomer) (Excluding polymer-based polymerized units).

Examples of the other monomer include at least selected from the group consisting of ethylene, propylene, 1-butene, 2-butene, vinyl chloride, vinylidene chloride, a hydroxyl group-containing vinyl ether monomer, and an unsaturated carboxylic acid. One fluorine-free ethylenic monomer 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 preferably has a weight average molecular weight of 1,000 to 3,000,000, more preferably 5,000 to 1,000,000, and still more preferably 10,000 to 600,000.

First production method The fluorine-containing polymer of the present invention is a step of copolymerizing a fluorine-containing monomer and a vinyl ester monomer to obtain a fluorine-containing monomer / vinyl ester copolymer. A step of hydrolyzing the fluorine-containing monomer / vinyl ester copolymer to obtain a fluorine-containing monomer / vinyl alcohol copolymer, the fluorine-containing monomer / vinyl alcohol copolymer and the general formula (5 ):
O = C = N-R ^b
(Wherein R ^b is an organic group having at least one terminal double bond), and is preferably produced by a production method comprising a step of obtaining a fluoropolymer by reacting with a compound represented by be able to. This manufacturing method may be referred to as the first manufacturing method of the present invention.

A method for copolymerizing a fluorinated monomer and a vinyl ester monomer and a method for hydrolyzing a fluorinated monomer / vinyl ester copolymer have been well known in the art. Can also be performed in the present invention. By hydrolyzing the fluorinated monomer / vinyl ester copolymer, the acetate group is converted to a hydroxyl group, and a fluorinated 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 has a molar ratio of the fluorine-containing monomer to the vinyl ester monomer ( The fluorine-containing monomer / (vinyl ester monomer) is preferably (30 to 70) / (70 to 30), and more preferably (40 to 60) / (60 to 40). When the molar ratio is in the above range and the degree of saponification is in the range described later, a fluoropolymer in which the molar ratio of each polymerized unit is in the above range can be produced.

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

The degree of saponification is determined by ¹ H-NMR, the integrated value of protons derived from acetyl groups (CH ₃ C (═O) —) near 2.1 ppm before and after saponification, and 2.2 to 2.7 ppm. It can be measured by quantifying the integral value of protons derived from the main chain methylene group (—CH ₂ —CH—).
¹ H-NMR: GEMINI-300 manufactured by Varian

Vinyl ester monomers do not contain fluorine atoms. Examples of the vinyl ester monomer include vinyl acetate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, and the like. As the vinyl ester monomer, vinyl acetate and vinyl stearate are preferable. More preferred is vinyl acetate.

As the compound represented by the general formula (5) used in the step of obtaining the fluoropolymer, the general formula (6):

(In the formula, M is H, Cl, F or CH ₃ , j is an integer of 1 to 20, k is an integer of 1 to 10, and 2j + 1−k is an integer of 0 or more.)
The compound represented by these is preferable.

In General formula (6), it is preferable that j is an integer of 1-10, and it is more preferable that it is an integer of 1-6. k is preferably an integer of 1 to 6, and more preferably an integer of 1 to 3. M is preferably H or CH ₃ .

In the first production method of the present invention, the amount of the compound represented by the general formula (5) varies depending on the number of hydroxyl groups in the molecule of the fluorine-containing monomer / vinyl alcohol copolymer. What is necessary is just to use the quantity sufficient for one compound represented by General formula (5) to react with respect to one hydroxyl group.

The compound represented by the general formula (5) is usually used in an amount of 0.5 to 100 moles per mole of hydroxyl groups in the molecule of the fluorine-containing monomer / vinyl alcohol copolymer. , Preferably 0.67 to 10 mol, more preferably 0.83 to 2 mol.

In the first production method of the present invention, the hydroxyl group in the molecule of the fluorine-containing monomer / vinyl alcohol copolymer and the isocyanate group of the compound represented by the general formula (5) are subjected to a urethanation reaction (addition). Reaction) to form urethane bonds. On the other hand, the terminal double bond present in the compound represented by the general formula (5) does not substantially react and becomes a curing site of the fluoropolymer of the present invention.

When an unreacted OH group is present in the fluoropolymer obtained by the first production method of the present invention, the unreacted OH group is a site for improving the compatibility and solubility of the fluoropolymer of the present invention. Acts as

The urethanization reaction easily proceeds by mixing the fluorine-containing monomer / vinyl alcohol copolymer and the compound represented by the general formula (5) or heating the mixture.

The heating temperature (reaction temperature) of the 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 (5) may be reacted in the presence of a catalyst. It does not specifically limit as said catalyst, What is necessary is just to use the conventionally well-known thing used for a urethanation reaction, and a commercial item can be obtained easily.

Examples of the catalyst include organic titanium compounds such as tetraethyl titanate and tetrabutyl titanate, organotin compounds such as tin octylate, dibutyltin oxide, and dibutyltin dilaurate, and halogen compounds such as stannous chloride and stannous bromide. Examples include stannous.

Examples of the catalyst also include amine catalysts such as ethanolamine, N-methylethanolamine, triethanolamine, N, N-dimethylethanolamine, n-butylamine, diethylamine, triethylamine, tetramethylenediamine, and cyclohexylamine. .

In the first production method of the present invention, by using a catalyst, the urethanization reaction proceeds in a shorter time, and the intended fluoropolymer is obtained.

Although the usage-amount of the catalyst used for a urethanation reaction is not specifically limited, What is necessary is just to adjust suitably, For example, it is 0.00001-3 mass normally with respect to 100 mass parts of compounds represented by General formula (5). Part, preferably about 0.0001 to 1 part by mass.

In the first production method of the present invention, a solvent may be further used. As the solvent, a solvent that does not interfere with the progress of the urethanization reaction and that is generally used may be used.

Examples of the solvent include ketone solvents such as methyl isobutyl ketone (MIBK) and methyl ethyl ketone (MEK); ester solvents such as ethyl acetate and butyl acetate; ether solvents such as tetrahydrofuran (THF); N, N-dimethylformamide An amide solvent such as (DMF); a fluorine solvent such as HCFC225 (CF ₃ CF ₂ CHCl ₂ / CClF ₂ CF ₂ CHClF mixture) may be used. An alcohol solvent having an OH group is not preferable because it prevents the urethanization reaction from proceeding. In addition, even if water is present in the system, the progress of the urethanization reaction is hindered, so that each solvent is more preferably dehydrated before use.

Second production method The fluorine-containing polymer of the present invention is obtained by copolymerizing a fluorine-containing monomer and a vinyl ester monomer to obtain 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 the fluorine-containing monomer / vinyl alcohol copolymer General formula (7):
^{X b -C (= O) -R} b
(Wherein, ^{X b} is ^HO-, R 10 O-, a F- or Cl @ ^{-, R 10} is an alkyl group or a fluorinated alkyl group, ^{R b} is an organic group having at least one terminal double bond It can also be produced by a production method comprising a step of obtaining a fluorine-containing polymer by reacting with a compound represented by: This manufacturing method is sometimes referred to as a second manufacturing method of the present invention.

The method described in detail in the first production method is used for the method of copolymerizing the fluorine-containing monomer and the vinyl ester monomer and the method of hydrolyzing the fluorine-containing monomer / vinyl ester copolymer. it can.

Vinyl ester monomers do not contain fluorine atoms. Examples of the vinyl ester monomer include vinyl acetate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, and the like. As the vinyl ester monomer, vinyl acetate and vinyl stearate are preferable. More preferred is vinyl acetate.

In the general formula (7), R ¹⁰ is an alkyl group or a fluorine-containing alkyl group. As said alkyl group, a linear, branched or cyclic C1-C12 alkyl group is mentioned, for example. Examples thereof include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl and cyclodecyl. . As said fluorine-containing alkyl group, a C1-C12 linear, branched or cyclic fluorine-containing alkyl group is mentioned. For _{example, -CF 3, -CH 2 CF 3} , CH 2 CF 2 CF 3, etc. -CF 2 _CF 2 _{CF 3} and the like.

In the general formula (7), R ^b is the same “organic group having at least one terminal double bond” as in the general formula (1).

As the compound represented by the general formula (7), the general formula (8):

(Wherein R is H, CH ₃ , F, CF ₃ or Cl, and X ^b is the same as above).
It is preferable that it is a compound represented by these.

Among these, a general formula that is an α, β-unsaturated carboxylic acid halide:

(Wherein R is the same as above)
The compound represented by these is more preferable.

Furthermore, among these, the following formula:

Is more preferable.

In the second production method of the present invention, the amount of the compound represented by the general formula (7) varies depending on the number of hydroxyl groups in the molecule of the fluorine-containing monomer / vinyl alcohol copolymer. What is necessary is just to use the quantity sufficient for one compound represented by General formula (7) to react with respect to one hydroxyl group.

The compound represented by the general formula (7) is usually used in an amount of 0.5 to 100 moles per mole of hydroxyl groups in the molecule of the fluorine-containing monomer / vinyl alcohol copolymer. , Preferably 0.67 to 10 mol, more preferably 0.83 to 2 mol.

In the second production method of the present invention, the hydroxyl group of the fluorine-containing monomer / vinyl alcohol copolymer and the X ^b —C (═O) — group of the compound represented by the general formula (7) are esters. Reaction to form an ester bond. On the other hand, the terminal double bond present in the compound represented by the general formula (7) does not substantially react and becomes a curing site of the fluoropolymer of the present invention.

When an unreacted OH group is present in the fluoropolymer obtained by the second production method of the present invention, the unreacted OH group is a site for improving the compatibility and solubility of the fluoropolymer of the present invention. Acts as

The esterification reaction proceeds easily by mixing the fluorine-containing monomer / vinyl alcohol copolymer and the compound represented by the general formula (7) or heating the mixture. The reaction temperature of the esterification reaction is usually about -20 to 40 ° C.

In the second production method of the present invention, HCl and HF are by-produced by the reaction, but it is desirable to add an appropriate base for the purpose of capturing them. Examples of the base include tertiary amines such as pyridine, N, N-dimethylaniline, tetramethylurea and triethylamine, and metallic magnesium.

In addition, the compound represented by the general formula (7) as a raw material during the reaction and an inhibitor for inhibiting the carbon-carbon double bond of the fluoropolymer obtained by the reaction from causing a polymerization reaction coexist. You may let them. Examples of the inhibitor include hydroquinone, t-butyl hydroquinone, hydroquinone monomethyl ether and the like.

In the second production method of the present invention, a solvent may be further used. When a solvent is used, a conventionally known solvent that is generally used and does not hinder the progress of the esterification reaction may be used as the solvent.

Examples of the solvent include ether solvents such as diethyl ether and tetrahydrofuran, ketone solvents such as 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone, and methyl isobutyl ketone (MIBK), propylene glycol monomethyl ether, propylene glycol. Propylene glycol solvents such as monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, CH ₃ CCl ₂ F (HCFC-141b), _{CF 3 CF 2 CHCl 2 / CClF} 2 CF 2 CHClF mixture (HCFC 25), fluorine-containing solvents such as perfluorohexane, perfluoro (2-butyltetrahydrofuran), methoxy-nonafluorobutane, and 1,3-bistrifluoromethylbenzene, aromatic hydrocarbons such as toluene, xylene, chlorobenzene, and chlorotoluene Or a mixed solvent of two or more of these. An alcohol solvent having an OH group is not preferable because it prevents the esterification reaction from proceeding. Further, since the progress of the esterification reaction is hindered even if water is present in the system, each solvent is more preferably dehydrated before use.

Third production method The fluorine-containing polymer of the present invention also contains a fluorine-containing monomer and a general formula (9):
CH ₂ = CH-OR
(Wherein R is a protecting group that can be converted to vinyl alcohol by a deprotection reaction) to obtain a fluorine-containing monomer / vinyl ether copolymer by copolymerizing with a vinyl ether monomer represented by: Deprotecting the fluorine-containing monomer / vinyl ether copolymer to obtain a fluorine-containing monomer / vinyl alcohol copolymer, the fluorine-containing monomer / vinyl alcohol copolymer and the general formula (5) :
O = C = N-R ^b
(Wherein R ^b is an organic group having at least one terminal double bond), and is preferably produced by a production method comprising a step of obtaining a fluoropolymer by reacting with a compound represented by be able to. This manufacturing method is sometimes referred to as a third manufacturing method of the present invention.

A method for copolymerizing a fluorinated monomer and a vinyl ether monomer and a method for deprotecting a fluorinated monomer / vinyl ether copolymer have been well known in the past. The invention can also be performed. By deprotecting the fluorine-containing monomer / vinyl ether copolymer, -OR is converted to a hydroxyl group, and a fluorine-containing monomer / vinyl alcohol copolymer is obtained.

The fluorine-containing monomer / vinyl ether copolymer obtained by copolymerizing a fluorine-containing monomer and a vinyl ether monomer has a molar ratio of the fluorine-containing monomer to the vinyl ether monomer (fluorine-containing monomer). (Mer) / (vinyl ether monomer) is preferably (40-60) / (60-40), more preferably (45-55) / (55-45). When the molar ratio is in the above range and the degree of deprotection is in the range described later, a fluoropolymer in which the molar ratio of each polymerized unit is in the above-described range can be produced.

The deprotection of the fluorinated monomer / vinyl ether copolymer is preferably performed so that the degree of deprotection is 1 to 100%, and more preferably 30 to 100%.

The degree of deprotection is determined by ¹ H-NMR, the integral value of protons derived from a tertiary butyl group (—C (C H ₃ ) ₃ ) around 1.0 to 1.3 ppm before and after the deprotection reaction, and 2 backbone methylene groups .2~2.7ppm _(-C H 2 -CH-) can be measured by quantifying the integral value from the protons.
¹ H-NMR: GEMINI-300 manufactured by Varian

R in the general formula (9) is not particularly limited as long as it is deprotected, but —CR ¹ R ² R ³ (R ¹ , R ² and R ³ are each independently a group having 1 to 3 carbon atoms. An alkyl group.), An alkoxymethyl group having 1 to 6 carbon atoms, a tetrahidrfuryl group, a tetrahydrolpyranyl group, or a trialkylsilyl group (—Si (R ⁴ ) ₃ , R ⁴ has 1 carbon atom. Is an alkyl group or an aryl group of ˜6), and —CR ¹ R ² R ³ is more preferable. As the vinyl ether monomer, tertiary butyl vinyl ether (t-butyl vinyl ether) is preferable because of its availability.

The preferable details of the compound represented by the general formula (5), the preferable addition amount, and the like can apply the contents detailed in the first production method.

Fourth production method The fluoropolymer of the present invention also contains a fluoromonomer and a general formula (9):
CH ₂ = CH-OR
(Wherein R is a protecting group that can be converted to vinyl alcohol by a deprotection reaction) to obtain a fluorine-containing monomer / vinyl ether copolymer by copolymerizing with a vinyl ether monomer represented by: A step of obtaining the fluorine-containing monomer / vinyl alcohol copolymer by deprotecting the fluorine-containing monomer / vinyl ether copolymer, and the fluorine-containing monomer / vinyl alcohol copolymer and the general formula ( 7):
^{X b -C (= O) -R} b
(Wherein, ^{X b} is ^HO-, R 10 O-, a F- or Cl @ ^{-, R 10} is an alkyl group or a fluorinated alkyl group, ^{R b} is an organic group having at least one terminal double bond It can also be produced by a production method comprising a step of obtaining a fluorine-containing polymer by reacting with a compound represented by: This manufacturing method may be referred to as a fourth manufacturing method of the present invention.

As the method for copolymerizing the fluorinated monomer and the vinyl ether monomer and the method for deprotecting the fluorinated monomer / vinyl ether copolymer, the methods detailed in the third production method can be used. As a method of reacting the fluorine-containing monomer / vinyl alcohol copolymer with the compound represented by the general formula (7), the method described in detail in the second production method can be used.

The preferable details of the compound represented by the general formula (7), the preferable addition amount, and the like can apply the contents described in detail in the second production method. The preferable details of the vinyl ether monomer represented by the general formula (9), the preferable addition amount, and the like can apply the contents detailed in the third production method.

Curable composition and hardened | cured material The curable composition containing the fluoropolymer (a) of this invention is also one of this invention.

As an aspect of the curable composition of this invention, the aspect which uses a solvent is mentioned, for example. Various substrates can be coated by dissolving or dispersing the curable composition of the present invention in a solvent to form a coating film, and after coating film formation, it can be efficiently cured by irradiation with active energy rays, It is preferable at the point from which a cured film is obtained.

It is preferable that the curable composition of this invention contains an active energy ray hardening initiator (b).

The active energy ray curing initiator (b), for example, generates radicals and cations only when irradiated with electromagnetic waves in a wavelength region of 350 nm or less, that is, ultraviolet rays, electron beams, X-rays, γ rays, and the like. It functions as a catalyst for initiating the curing (crosslinking reaction) of the carbon-carbon double bond of the polymer, and usually one that generates radicals and cations with ultraviolet light, particularly one that generates radicals. For example, the following can be exemplified.

Acetophenone series : acetophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, α-aminoacetophenone, hydroxypropiophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinepropan-1-one, and the like.

Benzoin series : benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, and the like.

Benzophenone series : benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propylbenzophenone, acrylated benzophenone, Michler's ketone and the like.

Chi Oki Sanson type: thioxanthone, chloro thioxanthone, methyl cyclohexane Son, diethyl thioxanthone, dimethyl thioxanthone and the like.

Others : benzyl, α-acyl oxime ester, acyl phosphine oxide, glyoxy ester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, anthraquinone, etc.

The curable composition of the present invention preferably contains a solvent (c). In the solvent (c), the fluorine-containing polymer (a), the active energy ray curing initiator (b), and additives such as a curing agent, a leveling agent, and a light stabilizer that are added as necessary are uniformly dissolved or dispersed. There is no particular limitation as long as it is a material, but a material that uniformly dissolves the fluoropolymer (a) is particularly preferable. The mode of using this solvent is particularly preferable in that it is highly transparent in a field where a thin layer coating (about 0.1 μm) is required, such as an antireflection coating, and a uniform coating can be obtained with high productivity.

Examples of the solvent (c) include cellosolv solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate; diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, butyl acetate Ester solvents such as amyl acetate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate; propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Propylene glycol solvents such as tate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether; ketone solvents such as 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone; alcohols such as methanol, ethanol, propanol, isopropanol, butanol Examples of the solvent include aromatic hydrocarbons such as toluene and xylene, or a mixed solvent of two or more of these.

Furthermore, in order to improve the solubility of the fluoropolymer (a), a fluorine-based solvent may be used as necessary. Examples of the fluorine-based solvent include CH ₃ CCl ₂ F (HCFC-141b), CF ₃ CF ₂ CHCl ₂ / CClF ₂ CF ₂ CHClF mixture (HCFC-225), perfluorohexane, perfluoro (2-butyltetrahydrofuran). , Methoxy-nonafluorobutane, 1,3-bistrifluoromethylbenzene, and the like, as well as H— (CF ₂ CF ₂ ) _n2 — (CH ₂ ) _n3 —OH (wherein n2 is an integer of 1 to 3, n3 is a compound represented by a is) an integer from 1 to _{6, F- (CF 2) n2 -} (CH 2) in n3 -OH (wherein, n2 represents an integer of 1 to 5, n3 is 1-6 compound represented by the integer which _{is), (CF} 3) fluorine-based alcohols such as compounds represented by 2 -CH-OH, benzotrifluoride, perfluoro Ben Emissions, perfluoro _{(tributylamine),} include ClCF ₂ CFClCF 2 CFCl 2 and the like.

These fluorinated solvents may be used singly or as a mixed solvent of fluorinated solvents or one or more of non-fluorinated and fluorinated solvents. Of these, ketone solvents, acetate solvents, alcohol solvents, aromatic solvents, and the like are preferable in terms of paintability, coating productivity, and the like. Moreover, when dissolving a fluoropolymer, you may mix a fluoroalcohol-type solvent with these general purpose solvents. The fluorine-containing alcohol to be added may be any one having a boiling point of 50 ° C. or higher, preferably 80 ° C. or higher and capable of dissolving the fluorine-containing polymer. For example, a compound represented by H— (CF ₂ CF ₂ ) _n2 — (CH ₂ ) _n3 —OH (wherein n2 is an integer of 1 to 3 and n3 is an integer of 1 to 6), F— _{(CF 2) n2 - (CH} 2) n3 -OH ( wherein, n2 represents an integer of 1 to 5, n3 is an is an integer from 1 to 6), a compound represented _{by, (CF} 3) 2 -CH- A compound represented by OH is a preferred specific example.

The fluorinated alcohol may be used as a solvent by itself, but it is also effective when used in addition to general-purpose solvents such as the above-mentioned ketone solvents, acetate ester solvents, non-fluorine alcohol solvents, and aromatic solvents. It is. When used in combination, the addition amount is 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and particularly preferably 10 to 30% by weight, based on the whole solvent.

The curable composition of the present invention may further contain a curing agent as necessary. As the curing agent, those having at least one carbon-carbon unsaturated bond and capable of being polymerized with radicals or acids are preferable. Specifically, radically polymerizable monomers such as acrylic monomers, vinyl ether monomers, and the like. And cationically polymerizable monomers such as monomers. These monomers may be monofunctional having one carbon-carbon double bond or polyfunctional monomers having two or more carbon-carbon double bonds. Preferably it is a polyfunctional monomer

These so-called curing agents having carbon-carbon unsaturated bonds react with radicals and cations generated by the reaction of the active energy ray curing initiator (b) in the composition of the present invention with active energy rays such as light, The fluorine-containing polymer (a) in the composition of the present invention can be cross-linked by copolymerization with a carbon-carbon double bond in the side chain.

Monofunctional acrylic monomers include acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, α-fluoroacrylic acid, α-fluoroacrylic esters, maleic acid, maleic anhydride, maleic acid In addition to esters, (meth) acrylic acid esters having an epoxy group, a hydroxyl group, a carboxyl group, and the like are exemplified. Among these, in order to keep the refractive index of the cured product low, an acrylate monomer having a fluoroalkyl group is preferable.

(Wherein, the ^{X c} H, CH ₃ or F, Rf ^b is a fluorine-containing alkyl group having ether bond of the fluorine-containing alkyl group, or 2 to 100 carbon atoms having 2 to 40 carbon atoms.)
The compound represented by these is preferable. Specifically, the general formula:

(In the formula, ^Xc is the same as above.)
The compound etc. which are represented by these are mentioned.

As polyfunctional acrylic monomers, compounds in which the hydroxyl groups of polyhydric alcohols such as diols, triols, and tetraols are replaced with acrylate groups, methacrylate groups, or α-fluoroacrylate groups are generally known. . Specifically, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, tripropylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. Examples thereof include compounds in which two or more hydroxyl groups of polyhydric alcohols are replaced with any one of an acrylate group, a methacrylate group, and an α-fluoroacrylate group. In addition, two or more hydroxyl groups of a polyhydric alcohol having a fluorine-containing alkyl group, a fluorine-containing alkyl group containing an ether bond, a fluorine-containing alkylene group or a fluorine-containing alkylene group containing an ether bond are converted into an acrylate group, a methacrylate group, α A polyfunctional acrylic monomer substituted with a fluoroacrylate group can also be used, and is particularly preferable in that the refractive index of the cured product can be kept low. As a specific example,

(In the formula, Rf ^d is a fluorine-containing alkyl group having 1 to 40 carbon atoms.)

(Wherein, Rf ^e is the fluorine-containing alkyl group having ether bond of the fluorine-containing alkyl group, or 2 to 100 carbon atoms 40 carbon atoms, ^{and R c} is H or an alkyl group having 1 to 3 carbon atoms .)

In the formula, Rf ′ is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms, and R ^c is the same as above. Preferred are those having a structure in which two or more hydroxyl groups of the fluorine-containing polyhydric alcohols shown are replaced with acrylate groups, methacrylate groups or α-fluoroacrylate groups. In addition, when these exemplified monofunctional and polyfunctional acrylic monomers are used in the composition of the present invention as a curing agent, an α-fluoroacrylate compound is particularly preferable in terms of good curing reactivity.

In the curable composition of the present invention, the addition amount of the active energy ray curing initiator (b) is the content of the carbon-carbon double bond in the fluoropolymer (a), whether or not the curing agent is used, Depending on the amount of the curing agent used, the initiator used, the type of active energy rays, and the amount of irradiation energy (strength and time, etc.) are appropriately selected. In the case where no curing agent is used, the fluoropolymer (a ) 0.01 to 30 parts by mass, further 0.05 to 20 parts by mass, and most preferably 0.1 to 10 parts by mass with respect to 100 parts by mass. Specifically, it is 0.05 to 50 mol%, preferably 0.1 to 20 mol%, most preferably based on the content (number of moles) of the carbon-carbon double bond contained in the fluoropolymer (a). Is 0.5 to 10 mol%.

When a curing agent is used, the amount of curing agent used is appropriately selected depending on the target hardness and refractive index, the type of curing agent, the content of the curable group of the fluoropolymer used, etc. 1 to 99% by weight, preferably 5 to 95% by weight, more preferably 10 to 90% by weight, based on the coalescence. If the addition amount of the curing agent is too large, the refractive index tends to increase, which is not preferable.

The content of the solvent (c) in the curable composition of the present invention is appropriately determined depending on the type of solid content to be dissolved, the presence or absence and use ratio of a curing agent, the type of substrate to be applied, the target film thickness, and the like. Although selected, the total solid content in the composition is preferably 0.5 to 70% by weight, preferably 1 to 50% by weight. Moreover, what does not contain a solvent at all is also preferable depending on a use.

The curable composition of this invention may mix | blend various additives as needed other than the above-mentioned compound.

Examples of such additives include leveling agents, viscosity modifiers, light stabilizers, moisture absorbers, pigments, dyes, reinforcing agents, and the like. Moreover, the curable composition of this invention can also mix | blend the fine particle of an inorganic compound in order to raise the hardness of hardened | cured material. The inorganic compound fine particles are not particularly limited, but compounds having a refractive index of 1.5 or less are preferable. Specifically, magnesium fluoride (refractive index 1.38), silicon oxide (refractive index 1.46), aluminum fluoride (refractive index 1.33-1.39), calcium fluoride (refractive index 1.44) Fine particles such as lithium fluoride (refractive index 1.36 to 1.37), sodium fluoride (refractive index 1.32 to 1.34), thorium fluoride (refractive index 1.45 to 1.50) are desirable. . The particle diameter of the fine particles is desirably sufficiently smaller than the wavelength of visible light in order to ensure the transparency of the low refractive index material. Specifically, it is preferably 100 nm or less, particularly 50 nm or less.

When using inorganic compound fine particles, use in the form of an organic sol dispersed in advance in an organic dispersion medium in order not to lower the dispersion stability in the curable composition, the adhesion in the low refractive index material, etc. It is desirable to do. Further, in the composition, in order to improve the dispersion stability of the inorganic compound fine particles, the adhesion in the low refractive index material, etc., the surface of the inorganic compound fine particles is previously modified with various coupling agents and the like. Can do. Examples of various coupling agents include organically substituted silicon compounds; metal alkoxides such as aluminum, titanium, zirconium, antimony or mixtures thereof; salts of organic acids; coordination compounds bonded to coordination compounds, and the like. .

In the curable composition of the present invention, the fluoropolymer (a) or additive may be in the form of dispersion or solution with respect to the solvent (c), but in order to form a uniform thin film, Moreover, it is preferable that it is a uniform solution at the point which can form into a film at comparatively low temperature. As the coating method, a known coating method can be adopted as long as the film thickness can be controlled. For example, roll coating method, gravure coating method, micro gravure coating method, flow coating method, bar coating method, spray coating method, die coating method, spin coating method, dip coating method, etc. can be adopted, and the type, shape and production of the substrate Can be selected in consideration of the controllability and controllability of the film thickness.

A cured product obtained by curing the curable composition of the present invention is also one aspect of the present invention. For example, a film obtained by applying the curable composition of the present invention to a substrate and then drying can be photocured by irradiating active energy rays such as ultraviolet rays, electron beams or radiation. When photocured, the carbon-carbon double bond in the fluoropolymer (a) of the present invention is polymerized between molecules, and the carbon-carbon double bond in the fluoropolymer (a) is reduced or eliminated. As a result, the resin hardness is increased, the mechanical strength is improved, the wear resistance, the scratch resistance is improved, and further, the resin becomes insoluble in the solvent dissolved before curing, It becomes insoluble in many other types of solvents.

The curable composition of the present invention may be used for film formation, but is particularly useful as a molding material for various molded products. As the molding method, extrusion molding, injection molding, compression molding, blow molding, transfer molding, stereolithography, nanoimprinting, vacuum molding and the like can be adopted.

As a use of the curable composition of this invention, it can use as a material of a sealing member, an optical member, a photoelectronic imaging tube, various sensors, an antireflection film, for example. Moreover, since the hardened | cured material obtained from the curable composition of this invention is excellent in transparency, it can utilize suitably as an optical material which forms an optical member. In addition, it can also be used as a sealing member material for electronic semiconductors, a water and moisture resistant adhesive, and an adhesive for optical components and elements.

As usage forms of the cured product of the present invention, for example, a package (encapsulation) of an optical functional element such as a light emitting element such as a light emitting diode (LED), an EL element or a nonlinear optical element, or a light receiving element such as a CCD, CMOS or PD, An example of this is mounting. Moreover, sealing members (or fillers) for optical members such as lenses for deep ultraviolet microscopes are also included.

Since the cured product of the present invention is excellent in transparency, it can be suitably used as a sealing material for optical elements. The sealed optical element is used in various places. Although it does not specifically limit as an optical element, For example, in addition to light emitting elements, such as a light emitting diode (LED), EL element, and a nonlinear optical element, light receiving elements, such as CCD, CMOS, and PD, a high mount stop lamp and a meter Light emitting elements such as a panel, a backlight of a mobile phone, a light source of a remote control device of various electric products; a camera autofocus, a light receiving element for an optical pickup for CD / DVD, and the like.

The curable composition of this invention is suitable as a material which forms an optical member. Since the curable composition of the present invention contains fluorine, the obtained cured product becomes an optical member having a low refractive index, and is useful as an optical transmission medium, for example. The curable composition of the present invention includes, in particular, a plastic clad material whose core material is quartz or optical glass, an optical fiber clad material, an all plastic optical fiber clad material whose core material is plastic, an antireflection coating material, and a lens. It can be used for materials, optical waveguide materials, prism materials, optical window materials, optical storage disk materials, nonlinear optical element materials, hologram materials, photolithographic materials, light emitting element sealing materials, and the like.

It can also be used as a material for optical devices. As optical devices, optical devices such as optical waveguides, OADMs, optical switches, optical filters, optical connectors, multiplexers / demultiplexers, and other optical devices are known and useful for forming these devices. Material. In addition, various functional compounds (non-linear optical materials, fluorescent light-emitting functional dyes, photorefractive materials, etc.) are contained and used for functional devices for optical devices such as modulators, wavelength conversion elements, and optical amplifiers. Is suitable. As a sensor application, there is an effect such as an improvement in sensitivity of an optical sensor or a pressure sensor, and protection of the sensor by water / oil repellency characteristics.

In particular, since the cured product obtained by curing the curable composition of the present invention has a very low refractive index, the curable composition of the present invention is suitable as a material for an antireflection film. The antireflection film obtained by curing the curable composition of the present invention is also one aspect of the present invention.

The antireflection film of the present invention may be formed by directly applying the above-described curable composition to a substrate, irradiating with light, and forming a cured film having a thickness of about 0.1 μm. One or a plurality of layers may be formed as an undercoat, and an antireflection film may be formed thereon as a topcoat.

The refractive index of the antireflection film of the present invention is preferably 1.49 or less, more preferably 1.45 or less, further preferably 1.40 or less, and 1.38 or less. Is particularly preferable, and more preferably 1.22 or more.

The preferred film thickness of the antireflection film of the present invention varies depending on the refractive index of the film and the refractive index of the base, but is 0.03 μm or more, preferably 0.07 μm or more, more preferably 0.08 μm or more, and 0.5 μm or less. The thickness is preferably 0.2 μm or less, more preferably 0.12 μm or less. If the film thickness is too low, the reduction in reflectance due to light interference in visible light will be insufficient, and if it is too high, the reflectance will depend only on the reflection at the interface between the air and the film. There is a tendency that the reduction of the reflectance due to is insufficient. In particular, the appropriate film thickness is such that the wavelength that indicates the minimum value of the reflectance of the article after the application of the antireflection film is usually 420 nm or more, preferably 520 nm or more, and 720 nm or less, preferably 620 nm or less. Is preferably set.

The article to which the antireflection film of the present invention is applied, that is, the type of the substrate is not particularly limited. For example, inorganic materials such as glass, stone, concrete, tile; cellulose resins such as vinyl chloride resin, polyethylene terephthalate, triacetyl cellulose, polycarbonate resin, polyolefin resin, acrylic resin, phenol resin, xylene resin, urea resin, melamine Synthetic resins such as resin, diallyl phthalate resin, furan resin, amino resin, alkyd resin, urethane resin, vinyl ester resin, polyimide resin; metal such as iron, aluminum, copper; wood, paper, printed matter, photographic paper, painting, etc. I can give you. In addition, the decorativeness of the article can be improved by applying an antireflection film to a part other than the specific part of the article and causing the shape of the specific part to be raised by reflected light.

Among the base materials, it is preferably applied to a transparent resin base material such as acrylic resin, polycarbonate, cellulose resin, polyethylene terephthalate, and polyolefin resin, and can effectively exhibit an antireflection effect.

Next, the present invention will be described with reference to synthesis examples and examples, but the present invention is not limited to such synthesis examples and examples.

The measurement methods employed in this specification are summarized below.

(1) Fluorine content 10 mg of sample was burned by the oxygen flask combustion method, the decomposition gas was absorbed in 20 ml of deionized water, and the fluorine ion concentration in the absorption liquid was determined by the fluorine selective electrode method (fluorine ion meter, model 901 manufactured by Orion). ) To obtain (mass%).

(2) ¹⁹ F-NMR measurement NMR measurement apparatus: Varian GEMINI-300
¹⁹ F-NMR measurement conditions: 376 MHz (trichlorofluoromethane = 0 ppm)

(3) ¹ H-NMR measurement NMR measurement apparatus: VEMIRAN-made GEMINI-300
¹ H-NMR measurement conditions: 400 MHz (tetramethylsilane = 0 ppm)

(4) Molecular weight and molecular weight distribution GPC HLC-8020 manufactured by Tosoh Corporation using gel permeation chromatography (GPC), one column manufactured by Shodex (one GPC KF-801 and one GPC KF-802) From the data measured by using tetrahydrofuran (THF) as a solvent at a flow rate of 1 ml / min, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are calculated using the following GPC KF-806M in series. calculate.

(5) Glass transition temperature (Tg)
Using DSC (Differential Scanning Calorimeter: RTG220, manufactured by SEIKO), the temperature range from −50 ° C. to 200 ° C. was raised at a rate of 10 ° C./min (first run) -temperature fall-temperature rise (second run) The intermediate point of the endothermic curve in the second run was defined as Tg (° C.).

(6) Melting point (Tm)
Using DSC (differential scanning calorimeter: RTG220, manufactured by SEIKO), the temperature corresponding to the maximum value in the heat of fusion curve when the temperature was raised at 10 ° C./min was defined as Tm (° C.).

(7) IR analysis Measured at room temperature with a Fourier transform infrared spectrophotometer 1760X manufactured by Perkin Elmer.

Synthesis example 1
Into a 3 L stainless steel autoclave, 1200 g of butyl acetate as a solvent and 140 g of vinyl acetate as a vinyl ester monomer were added, 7.2 g of perbutyl PV (product name, manufactured by NOF Corporation) was added as a polymerization initiator, and the flange was tightened. The autoclave was replaced with vacuum, tetrafluoroethylene was enclosed as a fluorine olefin gas, and the reaction was started by placing it in a shaking thermostat at 60 ° C. Since the polymerization pressure was lowered, the consumption of the gas monomer was confirmed, the shaking was stopped in 6 hours, and the remaining gas was blown to complete the reaction.

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

The composition of the polymer A1 was determined from elemental analysis of fluorine, the alternating ratio of fluorine olefin and vinyl ester was calculated from ¹ H-NMR, and the weight average molecular weight and molecular weight distribution (Mw / Mn) were determined from GPC. The glass transition temperature was measured from DSC. The results are shown in Table 2.

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

Synthesis example 3
A 3 L stainless steel autoclave was charged with 1000 g of pure water, 23.2 g of vinyl acetate, Neocor P (76.4 mass% isopropyl alcohol solution of sodium dioctylsulfosuccinate: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), nitrogen-substituted, and tetrafluoro Ethylene 37g was added and the inside of a tank was heated up to 80 degreeC. Thereafter, 30 g of tetrafluoroethylene was added. At this time, the pressure in the tank was 0.809 MPa. Under stirring, 22 g of a 1% by mass aqueous solution of ammonium persulfate (APS) was added to initiate the reaction. The addition of vinyl acetate was started at the start of the reaction, and 283 g of vinyl acetate was added over 6 hours. During the reaction, tetrafluoroethylene was continuously supplied using a solenoid valve so that the ratio of vinyl acetate / tetrafluoroethylene was constant. The stirring speed was 500 rpm.

Specifically, when tetrafluoroethylene is consumed and the inside of the tank reaches 0.800 MPa, the solenoid valve is automatically opened to supply tetrafluoroethylene, and when 0.775 MPa is reached, the solenoid valve is automatically closed and tetrafluoroethylene is closed. While controlling the supply and pressure of tetrafluoroethylene in a cycle in which the supply of ethylene was stopped, vinyl acetate was added in accordance with the consumption of tetrafluoroethylene.

Six hours after the start of the reaction, the supply of tetrafluoroethylene and vinyl acetate was stopped. Then, after reacting for 1 hour, the inside of the tank was returned to room temperature and normal pressure to stop the polymerization, thereby obtaining 1661 g of a vinyl acetate / tetrafluoroethylene copolymer emulsion (solid content concentration 38.5% by mass).

The resulting vinyl acetate / tetrafluoroethylene copolymer had a glass transition temperature of 40 ° C. and a particle size of 116 nm.

Synthesis example 4
A 300 mL stainless steel autoclave is charged with 50 g of butyl acetate solvent and 10 g of vinyl stearate monomer, 0.4 g of perbutyl PV (product name, manufactured by NOF Corporation) is added as a polymerization initiator, the flange is tightened, and the autoclave is vacuum-substituted. Then, 8.0 g of tetrafluoroethylene was encapsulated as a fluorine olefin gas, and 2.6 g of hexafluoropropylene was subsequently encapsulated, and the mixture was placed in a shaking thermostat at 60 ° C. to initiate the reaction. Since the polymerization pressure was lowered, the consumption of the gas monomer was confirmed, the shaking was stopped in 15 hours, and the remaining gas was blown to complete the reaction.

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

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

Synthesis Examples 5-7
Polymers A5, B1, and B2 were obtained in the same manner as in Synthesis Example 1 except that the type of monomer and the charging ratio, scale, reaction time, and the like were changed. The reaction conditions are summarized in Table 1, and the physical properties of the obtained polymer are summarized in Table 2.

Synthesis Example 8
In a 300 ml stainless steel autoclave, 150.0 g of t-butanol, 26.7 g of t-butyl vinyl ether, and 0.48 g of potassium carbonate were added, 0.46 g of a 70% isooctane solution of perbutyl PV was added as a polymerization initiator, and the flange was tightened. The autoclave was vacuum-replaced, 26.7 g of tetrafluoroethylene was sealed as a fluorine olefin gas, and the reaction was started by placing it in a shaking thermostat at 60 ° C. Since the polymerization pressure was lowered, the consumption of the gas monomer was confirmed, the shaking was stopped in 3 hours, and the remaining gas was blown to complete the reaction.

After completion of the reaction, the polymer solution was reprecipitated in a large amount of methanol solution, and the polymer was purified to obtain polymer C1.
The reaction conditions are summarized in Table 1, and the physical properties of the obtained polymer are summarized in Table 2.

Synthesis Example 9 (Saponification heterogeneous system)
4 g of TFE / vinyl acetate polymer A2 obtained in Synthesis Example 2 was stirred in 136 g of MeOH solvent, and a catalytic amount of NaOH particles (about 0.4 g) was added and gradually reacted to uniformly dissolve the polymer. Stirring was continued until The solution colored yellow with the reaction, and when the solution was stirred at room temperature for 3 days, the polymer was uniformly dissolved, so the reaction was terminated. The reaction solution was concentrated with an evaporator and dropped into water to purify the polymer by reprecipitation. After washing with 1N HCl, it was thoroughly washed with ion-exchanged water, and the reprecipitated polymer was suction filtered and dried at 80 ° C. for 2 hours with a dryer. As a result of calculating the hydrolysis rate (degree of saponification) from the relative intensity of the carbonyl peak observed by IR, TFE / vinyl alcohol polymer A2-100, which was almost 100%, was obtained.

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

Synthesis Examples 11 to 13 (saponification uniform system)
AFE-vinyl alcohol / vinyl acetate polymers A1-45, A1-86, and A1-96 were obtained by changing the saponification time of Synthesis Example 10. The results are summarized in Table 3.

Synthesis Examples 14 to 18 (saponification homogeneous system)
A saponification polymer was obtained in the same manner as in Synthesis Example 10 except that the saponification time of Synthesis Example 10 was 1 day and the polymers obtained in Synthesis Examples 3 to 7 were used. The results are summarized in Table 3.

Synthesis example 19 (deprotection process)
In a 100 ml eggplant flask, 2.63 g of TFE / t-butyl vinyl ether polymer C1 obtained in Synthesis Example 8 (TFE / t-butyl vinyl ether = 48/52 (molar ratio)), 1,4-dioxane 1.2 ml, 4N An aqueous HCl solution (50 ml) was added and the mixture was heated and stirred at 80 ° C. After 2 hours, heating was stopped and the mixture was allowed to cool, and the precipitated polymer was washed 3 times with pure water. The polymer was dissolved in tetrahydrofuran (THF), reprecipitated into a solution of ethanol / water (50/50% by volume) and dried in vacuo. ^{According to 1} H-NMR, the integral value of protons derived from a tertiary butyl group (—C (C H ₃ ) ₃ ) around 1.0 to 1.3 ppm before and after the deprotection reaction, and 2.2 to 2.7 ppm. As a result of calculating the degree of deprotection by quantifying the integral value of protons derived from the main chain methylene group (—C H ₂ —CH—) of the TFE / vinyl alcohol / t-butyl vinyl ether polymer C1- 97 was obtained. The results are summarized in Table 3.

Example 1
2.1 g of polymer A1-96 was uniformly dissolved in 20 g of DMF (N, N-dimethylformamide) solvent. After adding 2.3 g of Karenz AOI (CH ₂ = CHCOOCH ₂ CH ₂ NCO) manufactured by Showa Denko KK and 89 μL of dibutyltin dilaurate as a catalyst, the mixture was stirred at room temperature for 24 hours.

The DMF solution after the reaction was placed in a separatory funnel, ion exchanged water and butyl acetate were added to extract the polymer, water washing was repeated, the organic layer was separated, and dried over anhydrous magnesium sulfate.

Thereafter, the reaction solution was concentrated with a rotary evaporator, the solvent was removed by a casting method, and the precipitated solid was dissolved again in a small amount of acetone. The polymer was purified by reprecipitation of this solution in a sufficiently large amount of n-hexane. This purification operation was repeated a total of 3 times to obtain 3.7 g of a polymer.

IR analysis results are shown in FIGS. Apparently, the OH groups of the polymer were greatly reduced, and new urethane bonds (N—H and C═O) and carbon-carbon double bond peaks were observed. This polymer is referred to as A1-96-AOI.

Examples 2-11
Reaction with Karenz AOI was carried out in the same manner as in Example 1 except that the polymers listed in Table 4 were used. The blending ratio is summarized in Table 4. As a result of IR analysis of these polymers, the OH groups of the polymers were greatly reduced, and new peaks of urethane bonds (N—H and C═O) and carbon-carbon double bonds were observed. It was. The abbreviations for each polymer are also shown in Table 4.

Examples 12 and 13
The reaction was carried out in the same manner as in Example 1 except that Karenz MOI (CH ₂ = CCH ₃ COOCH ₂ CH ₂ NCO) manufactured by Showa Denko KK and Karenz BEI manufactured by Showa Denko KK were used instead of Karenz AOI. The blending ratio is summarized in Table 4. Karenz BEI is represented by the following chemical formula.

As a result of IR analysis of the obtained polymer, the OH group of the polymer was greatly reduced, and a new peak of urethane bond (N—H and C═O) and carbon-carbon double bond was observed. It was done. The abbreviations for each polymer are also shown in Table 4.

Example 14
2.2 g of polymer A1-96 was weighed and dissolved in 40 g of methyl isobutyl ketone (MIBK) previously dehydrated with molecular sieves 4A, and charged into a 100 ml glass four-necked flask equipped with a stirrer and a thermometer. Thereafter, 1.9 g of triethylamine was added, and then 1.6 g of ₂ -fluoroacrylic acid fluoride (CH ₂ = CFCOF) was added dropwise from an addition funnel in an ice bath, and the mixture was sufficiently stirred and homogenized. After stirring for 2 hours, the temperature was returned to room temperature. Stirring was continued for another 4 hours.

The MIBK solution after the reaction was placed in a separatory funnel, washed with water, washed with 2% hydrochloric acid, washed with 5% NaCl, and further washed with water. The organic layer was separated and dried over anhydrous magnesium sulfate.

Thereafter, the reaction solution was concentrated with a rotary evaporator, the solvent was removed by a casting method, and the precipitated solid was dissolved again in a small amount of acetone. The polymer was purified by reprecipitation of this solution in a sufficiently large amount of n-hexane. This purification operation was repeated a total of 3 times to obtain 2.2 g of a viscous polymer.

All of these post-treatment operations were performed so as not to exceed 60 ° C. The same applies to the subsequent embodiments.

When this polymer was examined by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis, the following formula (10):

The polymer was m: n = 10: 90. This polymer is referred to as A1-96-F-100.

Example 15
In Example 14, the reaction was carried out in the same manner except that 2.1 g of the polymer (A1-96), 0.92 g of triethylamine, and 0.77 g of 2-fluoroacrylic acid fluoride were used. ), 1.8 g of an unsaturated group-containing polymer having m: n = 55: 45 was obtained. This polymer is referred to as A1-96-F-50.

Example 16
2.1 g of polymer (A1-96) was weighed and dissolved in 40 g of methyl isobutyl ketone (MIBK) previously dehydrated with molecular sieves 4A, and charged into a 200 ml glass four-necked flask equipped with a stirrer and a thermometer. . Thereafter, 0.92 g of triethylamine was added, and then 0.87 g of methallylic acid chloride (CH ₂ ═C (CH ₃ ) COCl) was added dropwise in an ice bath from a dropping funnel, and the mixture was sufficiently stirred and homogenized. . After stirring for 2 hours, the temperature was returned to room temperature. After completion of the dropwise addition, the temperature was raised to room temperature and stirring was continued for 4 hours.

The MIBK solution after the reaction was placed in a separatory funnel, washed with water, washed with 2% hydrochloric acid, washed with 5% NaCl, and further washed with water. The organic layer was separated and dried over anhydrous magnesium sulfate.

Thereafter, the reaction solution was concentrated with a rotary evaporator, the solvent was removed by a casting method, and the precipitated solid was dissolved again in a small amount of acetone. The polymer was purified by reprecipitation of this solution in a sufficiently large amount of n-hexane. This purification operation was repeated a total of 3 times to obtain 1.5 g of a viscous polymer. When this polymer was examined by ¹⁹ F-NMR, ¹ H-NMR analysis, and IR analysis, the following formula (11):

The polymer was m: n = 53: 47. This polymer is referred to as A1-96-M-50.

Example 17
In Example 16, the reaction was conducted in the same manner except that 0.75 g of acrylic acid chloride was used instead of methallylic acid chloride, and the following formula (12):

1.5 g of an unsaturated group-containing polymer (m: n = 56: 44) shown in FIG. This polymer is referred to as A1-96-A-50.

Example 18
In Example 14, the reaction was carried out in the same manner except that the polymer (C1-97) was 2.2 g, the amount of triethylamine was 0.95 g, and the amount of 2-fluoroacrylic acid fluoride was 0.78 g. ), 1.5 g of an unsaturated group-containing polymer of m: n = 54: 46 was obtained. This polymer is referred to as C1-97-F-50.

The results of Examples 14-18 are summarized in Table 5.

Example 19 (Preparation of curable composition)
A curable composition was prepared according to the following formulation. Table 6 shows the amount of each composition.
Polymer (A1-96-AOI) 50 parts by mass 4FA (CH ₂ = CHCOOCH ₂ C ₂ F ₄ H) 30 parts by mass Trimethylolpropane triacrylate (TMPA) 20 parts by mass Darocur MBF (manufactured by Ciba Specialty Chemicals) 4 parts by mass MIBK 200 parts by mass

Next, the appearance of the liquid composition at 25 ° C. of the prepared composition before curing was visually evaluated. The results are shown in Table 7. The evaluation criteria are as follows.

○: Transparent and uniform.
Δ: Partly cloudy (gel-like material) is observed.
X: Opaque and cloudy.

Next, the appearance, refractive index (n), solvent resistance (butyl acetate) and heat resistance (150 ° C.) of the cured film prepared by curing in the following manner were examined. The results are shown in Table 7.

(Production of cured film)
A curable composition is spin-coated on a silicon wafer, applied to a film thickness of about 0.1 μm, air-dried, dried for 10 minutes in a 200 ° C. blower dryer, and then a belt conveyor type UV. It was cured by irradiating ultraviolet rays with an intensity of 1500 mJ / cm ² U from the top using an exposure machine.

The evaluation criteria for appearance, solvent resistance and heat resistance are shown below.

(appearance)
The cured product obtained by UV curing was visually evaluated.
○: Transparent and uniform.
Δ: Some cloudiness is observed.
X: Opaque and cloudy.

(Solvent resistance)
At room temperature, a few drops of butyl acetate were applied to the surface of the UV-cured sample, wiped off with Kimwipe after 1 minute, and visually observed.
○: No swelling is visually observed.
Δ: Swelling is visually observed.
X: Dissolve.

(Heat-resistant)
With respect to heat resistance, each sample was held at 150 ° C. for 1 hour, and the change in appearance was visually observed.
○: No change is visually observed.
Δ: Slight discoloration and turbidity are observed visually.
X: Discoloration, white turbidity, deformation, etc. that are clearly visible are observed.

For the refractive index, the value of the refractive index at 550 nm was calculated by a spectroscopic ellipsometer.

Examples 20-26
A curable composition was prepared according to the formulation shown in Table 6, and various physical properties were measured in the same manner as in Example 19. The results are shown in Table 7.

Comparative Example 1
A curable composition was prepared in the same manner as in Example 19 except that A1 having no terminal double bond was used as the polymer, and various physical properties were measured in the same manner as in Example 19. The results are shown in Table 7.

Comparative Example 2
A curable composition was prepared in the same manner as in Example 19 except that A1-96 having no terminal double bond was used as the polymer, and various physical properties were measured in the same manner as in Example 19. The results are shown in Table 7.

Since the fluoropolymer of the present invention can be easily cured, it can be suitably used as an optical material such as an antireflection film, a raw material for paint, a sealing material for solar cells, an antifouling agent, a repellent and the like.

Claims (15)

Polymerized units based on fluorine-containing monomers,
Polymer units based on vinyl alcohol as optional polymer units, and
Formula (1): —CH ₂ —CH (—O— (L) ₁ —R ^b ) —
(Wherein R ^b is an organic group having at least one terminal double bond, L is a divalent organic group, and l is 0 or 1),
A fluorine-containing polymer comprising: R ^b represents the general formula (2):

(In the formula, M is H, Cl, F or CH ₃ , j is an integer of 1 to 20, k is an integer of 1 to 10, and 2j + 1−k is an integer of 0 or more). A group represented by formula (3):

(Wherein, R H, Cl, F, CH ₃ or CF ₃ and is) fluorine-containing polymer of the at least one substituent which claim 1 is selected from the group consisting of groups represented by. L represents the general formula (4):
− (C═O) _s − (N−H) _p −
The fluorine-containing polymer according to claim 1 or 2, which is an organic group represented by the formula (wherein s is 0 or 1 and p is 0 or 1). The molar ratio of the polymer unit based on the fluorine-containing monomer, the polymer unit based on vinyl alcohol, and the polymer unit represented by the general formula (1) is (30 to 70) / (0 to 69) / (1 to 70). The fluorine-containing polymer according to claim 1, 2 or 3. A production method for producing the fluoropolymer according to claim 1, 2, 3 or 4,
A step of copolymerizing a fluorine-containing monomer and a vinyl ester monomer to obtain a fluorine-containing monomer / vinyl ester copolymer;
Obtaining a fluorine-containing monomer / vinyl alcohol copolymer by hydrolyzing the fluorine-containing monomer / vinyl ester copolymer; and
The fluorine-containing monomer / vinyl alcohol copolymer and the general formula (5):
O = C = N-R ^b
(Wherein R ^b is an organic group having at least one terminal double bond), and a step of obtaining a fluoropolymer by reacting with the compound represented by:
The manufacturing method characterized by including. The compound represented by the general formula (5) is represented by the general formula (6):

(In the formula, M is H, Cl, F or CH ₃ , j is an integer of 1 to 20, k is an integer of 1 to 10, and 2j + 1−k is an integer of 0 or more). The production method according to claim 5, which is a compound represented. A production method for producing the fluoropolymer according to claim 1, 2, 3 or 4,
A step of copolymerizing a fluorine-containing monomer and a vinyl ester monomer to obtain a fluorine-containing monomer / vinyl ester copolymer;
Obtaining a fluorine-containing monomer / vinyl alcohol copolymer by hydrolyzing the fluorine-containing monomer / vinyl ester copolymer; and
The fluorine-containing monomer / vinyl alcohol copolymer and the general formula (7):
^{X b -C (= O) -R} b
(Wherein, ^{X b} is ^HO-, R 10 O-, a F- or Cl @ ^{-, R 10} is an alkyl group or a fluorinated alkyl group, ^{R b} is an organic group having at least one terminal double bond A step of obtaining a fluoropolymer by reacting with a compound represented by:
The manufacturing method characterized by including. The compound represented by the general formula (7) is represented by the general formula (8):

(In the formula, R is H, Cl, F, CH ₃ or CF ₃ , X ^b is HO—, R ¹⁰ O—, F— or Cl—, and R ¹⁰ is an alkyl group or a fluorine-containing alkyl group. The production method according to claim 7, which is a compound represented by: A production method for producing the fluoropolymer according to claim 1, 2, 3 or 4,
Fluorine-containing monomer and general formula (9):
CH ₂ = CH-OR
(Wherein R is a protecting group that can be converted to vinyl alcohol by a deprotection reaction) to obtain a fluorine-containing monomer / vinyl ether copolymer by copolymerizing with a vinyl ether monomer represented by:
Obtaining a fluorine-containing monomer / vinyl alcohol copolymer by deprotecting the fluorine-containing monomer / vinyl ether copolymer; and
The fluorine-containing monomer / vinyl alcohol copolymer and the general formula (5):
O = C = N-R ^b
(Wherein R ^b is an organic group having at least one terminal double bond), and a step of obtaining a fluoropolymer by reacting with the compound represented by:
The manufacturing method characterized by including. The compound represented by the general formula (5) is represented by the general formula (6):

(In the formula, M is H, Cl, F or CH ₃ , j is an integer of 1 to 20, k is an integer of 1 to 10, and 2j + 1−k is an integer of 0 or more). The production method according to claim 9, which is a compound represented. A production method for producing the fluoropolymer according to claim 1, 2, 3 or 4,
Fluorine-containing monomer and general formula (9):
CH ₂ = CH-OR
(Wherein R is a protecting group that can be converted to vinyl alcohol by a deprotection reaction) to obtain a fluorine-containing monomer / vinyl ether copolymer by copolymerizing with a vinyl ether monomer represented by:
Obtaining a fluorinated monomer / vinyl alcohol copolymer by deprotecting the fluorinated monomer / alkyl vinyl ether copolymer; and
The fluorine-containing monomer / vinyl alcohol copolymer and the general formula (7):
^{X b -C (= O) -R} b
(Wherein, ^{X b} is ^HO-, R 10 O-, a F- or Cl @ ^{-, R 10} is an alkyl group or a fluorinated alkyl group, ^{R b} is an organic group having at least one terminal double bond A step of obtaining a fluoropolymer by reacting with a compound represented by:
The manufacturing method characterized by including. The compound represented by the general formula (7) is represented by the general formula (8):

(In the formula, R is H, Cl, F, CH ₃ or CF ₃ , X ^b is HO—, R ¹⁰ O—, F— or Cl—, and R ¹⁰ is an alkyl group or a fluorine-containing alkyl group. The production method according to claim 11, which is a compound represented by: A curable composition comprising the fluoropolymer according to claim 1, 2, 3 or 4. A cured product obtained by curing the curable composition according to claim 13. An antireflection film obtained by curing the curable composition according to claim 13.

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