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WO2013115267A1 - Polymère contenant du fluor et son procédé de production - Google Patents

Polymère contenant du fluor et son procédé de production Download PDF

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Publication number
WO2013115267A1
WO2013115267A1 PCT/JP2013/052081 JP2013052081W WO2013115267A1 WO 2013115267 A1 WO2013115267 A1 WO 2013115267A1 JP 2013052081 W JP2013052081 W JP 2013052081W WO 2013115267 A1 WO2013115267 A1 WO 2013115267A1
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Prior art keywords
fluorine
general formula
containing monomer
vinyl
monomer
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PCT/JP2013/052081
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English (en)
Japanese (ja)
Inventor
田中　義人
剣吾 伊藤
三木　淳
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ダイキン工業株式会社
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Publication of WO2013115267A1 publication Critical patent/WO2013115267A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/186—Monomers containing fluorine with non-fluorinated comonomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups

Definitions

  • the present invention relates to a fluoropolymer and a method for producing the same.
  • Polyvinyl alcohol and ethylene-vinyl alcohol copolymer are hydrophilic, have a property of being difficult to permeate gases such as oxygen and nitrogen, and excellent in fuel barrier properties.
  • 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.
  • a fluorine-containing copolymer film having a tetrafluoroethylene content of 1 to 70 mol% contained in the copolymer has been proposed.
  • 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.
  • 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.
  • 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.
  • 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):
  • R is H, Cl, F, CH 3 or CF 3
  • R is preferably at least one substituent selected from the group consisting of groups represented by:
  • 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.
  • 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.
  • 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:
  • M is H, Cl, F or CH 3
  • j is an integer from 1 to 20
  • k is an integer from 1 to 10
  • 2j + 1 ⁇ k is an integer of 0 or more. It is preferable that it is a compound represented.
  • R is H, Cl, F, CH 3 or CF 3
  • X b is HO—, R 10 O—, F— or Cl—
  • 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.
  • 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.
  • fluorine-containing monomer examples include tetrafluoroethylene [TFE], vinylidene fluoride [VdF], chlorotrifluoroethylene [CTFE], vinyl fluoride, hexafluoropropylene [HFP], hexafluoroisobutene, and CH 2.
  • PAVE perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], perfluoro (butyl vinyl ether), among others, PMVE. PEVE or PPVE is more preferable.
  • 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 fluorine-containing polymer 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.
  • the polymerization unit represented by the general formula (1) has the general formula: 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). Unit.
  • R b include general formula (2):
  • M is H, Cl, F or CH 3
  • j is an integer of 1 to 20
  • k is an integer of 1 to 10
  • 2j + 1 ⁇ k is an integer of 0 or more.
  • 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, more preferably an integer of 1 to 3.
  • Rb has the general formula:
  • R is H, CH 3 , F, CF 3 or Cl.
  • R b among the groups exemplified above, in particular, the general formula (2): (Wherein M is H, Cl, F or CH 3 , j is an integer from 1 to 20, k is an integer from 1 to 10, and 2j + 1 ⁇ k is an integer of 0 or more).
  • R b is bonded to the main chain of the fluoropolymer via a urethane bond.
  • R b is bonded via an ester bond.
  • 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 (polymerized unit) / (polymerized unit based on vinyl alcohol) / (polymerized unit represented by 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.
  • the polymerization units based on vinyl ether monomers) are 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 to 70) / (1 to 65) / (5 to 69) / (0 to 65).
  • vinyl ester monomer examples include vinyl acetate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl cyclohexylcarboxylate, and the like.
  • vinyl ester monomer vinyl acetate and vinyl stearate are preferable. More preferred is vinyl acetate.
  • vinyl ether monomer examples include t-butyl vinyl ether, 1,1-dimethylpropyl vinyl ether, methoxymethyl vinyl ether, tetrahydrofuryl vinyl ether, tetrahydropyranyl vinyl ether, vinyloxytrimethylsilane, and vinyloxydimethylphenylsilane.
  • 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.
  • 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.
  • 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 (fluorinated monomer) / (vinyl ester monomer) is preferably (30 to 70) / (70 to 30), more preferably (40 to 60) / (60 to 40).
  • Hydrolysis of the fluorinated monomer / vinyl ester copolymer is preferably carried out so that the degree of saponification is 1 to 100%, more preferably 30 to 100%.
  • the degree of saponification is determined by 1 H-NMR, the integral 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.
  • vinyl ester monomer vinyl acetate and vinyl stearate are preferable. More preferred is vinyl acetate.
  • M is H, Cl, F or CH 3
  • j is an integer of 1 to 20
  • k is an integer of 1 to 10
  • 2j + 1 ⁇ k is an integer of 0 or more.
  • 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, more preferably an integer of 1 to 3.
  • M is preferably H or CH 3 .
  • 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 amount of the compound represented by the general formula (5) is usually 0.5 to 100 moles with respect to 1 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 may be used.
  • 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.
  • 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.
  • 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.
  • 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.
  • the catalyst examples 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.
  • the catalyst also include amine catalysts such as ethanolamine, N-methylethanolamine, triethanolamine, N, N-dimethylethanolamine, n-butylamine, diethylamine, triethylamine, tetramethylenediamine, and cyclohexylamine. .
  • amine catalysts such as ethanolamine, N-methylethanolamine, triethanolamine, N, N-dimethylethanolamine, n-butylamine, diethylamine, triethylamine, tetramethylenediamine, and cyclohexylamine.
  • the urethanization reaction proceeds in a shorter time, and the intended fluoropolymer is obtained.
  • the amount of the catalyst used for the urethanization reaction is not particularly limited and may be appropriately adjusted.
  • the amount is usually 0.00001-3 mass per 100 mass parts of the compound represented by the general formula (5). Part, preferably about 0.0001 to 1 part by mass.
  • a solvent may be further used.
  • a solvent that does not interfere with the progress of the urethanization reaction and that is generally used may be used.
  • the solvent examples 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
  • 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 urethan
  • 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 (In the formula, X b is HO—, R 10 O—, F— or Cl—, R 10 is an alkyl group or a fluorine-containing alkyl group, and 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
  • 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.
  • vinyl ester monomer vinyl acetate and vinyl stearate are preferable. More preferred is vinyl acetate.
  • R 10 is an alkyl group or a fluorine-containing alkyl group.
  • the alkyl group include linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms. 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, cyclodecyl and the like. .
  • fluorine-containing alkyl group examples include linear, branched or cyclic fluorine-containing alkyl groups having 1 to 12 carbon atoms.
  • fluorine-containing alkyl group examples include linear, branched or cyclic fluorine-containing alkyl groups having 1 to 12 carbon atoms.
  • —CF 3 , —CH 2 CF 3 , CH 2 CF 2 CF 3 , —CF 2 CF 2 CF 3 and the like can be mentioned.
  • R b is the same “organic group having at least one terminal double bond” as in the general formula (1).
  • 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.
  • 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 amount of the compound represented by the general formula (7) is usually 0.5 to 100 moles with respect to 1 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 may be used.
  • 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.
  • 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.
  • 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 for the esterification reaction is usually about ⁇ 20 to 40 ° C.
  • HCl and HF are by-produced by the reaction, but it is desirable to add an appropriate base for the purpose of capturing them.
  • the base include tertiary amines such as pyridine, N, N-dimethylaniline, tetramethylurea and triethylamine, and metallic magnesium.
  • a 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.
  • the inhibitor include hydroquinone, t-butyl hydroquinone, hydroquinone monomethyl ether and the like.
  • a solvent may be further used.
  • a solvent a conventionally known solvent that is generally used and does not hinder the progress of the esterification reaction may be used as the solvent.
  • the solvent examples 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.
  • ether solvents such as diethyl ether and tetrahydrofuran
  • ketone solvents such as 2-hexanone, cyclohexanone, methylaminoketone, 2-heptanone and methyl isobutyl ketone (MIBK)
  • MIBK methyl isobutyl ketone
  • 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), fluorinated solvents such as perfluorohexane, perfluoro (2-butyltetrahydrofuran), methoxy-nonafluorobutane, 1,3-bistrifluoromethylbenzene, aromatic hydrocarbons such as toluene, xylene, chlorobenzene, 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
  • 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 to 60) / (60 to 40), more preferably (45 to 55) / (55 to 45).
  • the deprotection of the fluorine-containing 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 It can be measured by quantifying the integral value of protons derived from a main chain methylene group (—C H 2 —CH—) of 0.2 to 2.7 ppm.
  • 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 each independently has 1 to 3 carbon atoms) An alkyl group), an alkoxymethyl group having 1 to 6 carbon atoms, a tetrahydrolfuryl group, a tetrahydrolpyranyl group, or a trialkylsilyl group (—Si (R 4 ) 3 , R 4 has 1 carbon atom) An alkyl group or an aryl group of ⁇ 6), and —CR 1 R 2 R 3 is more preferable.
  • 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.
  • the methods detailed in the third production method can be used.
  • 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.
  • cured material The curable composition containing the fluoropolymer (a) of this invention is also one 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.
  • 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, ⁇ 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, ⁇ -aminoacetophenone, hydroxypropiophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinepropan-1-one, etc.
  • 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, etc.
  • the curable composition of the present invention preferably contains a solvent (c).
  • a solvent 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.
  • 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 ⁇ m) is required, such as an antireflection coating, and a uniform coating can be obtained with high productivity.
  • solvent (c) examples include cellosolv solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate; diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, butyl acetate.
  • cellosolv solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, 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
  • a fluorine-based solvent may be used as necessary.
  • 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 an integer of 1 to 6), F— (CF 2 ) n2 — (CH 2 ) n3 —OH (wherein n2 is an integer of 1 to 5 and n3 is 1 to 6) compound represented by the integer which is),
  • fluorinated solvents may be used singly or as a mixed solvent of fluorinated solvents or one or more of non-fluorinated and fluorinated solvents.
  • ketone solvents, acetate solvents, alcohol solvents, aromatic solvents, and the like are preferable in terms of paintability, coating productivity, and the like.
  • 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.
  • 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— A compound represented by (CF 2 ) n2 — (CH 2 ) n3 —OH (where n2 is an integer of 1 to 5 and n3 is an integer of 1 to 6)
  • 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.
  • a curing agent those having at least one carbon-carbon unsaturated bond and capable of being polymerized with radicals or acids are preferable.
  • radically polymerizable monomers such as acrylic monomers, vinyl ether-based monomers, and the like.
  • 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.
  • it is a polyfunctional monomer
  • 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, ⁇ -fluoroacrylic acid, ⁇ -fluoroacrylic esters, maleic acid, maleic anhydride, maleic acid
  • esters (meth) acrylic acid esters having an epoxy group, a hydroxyl group, a carboxyl group, and the like are exemplified.
  • an acrylate monomer having a fluoroalkyl group is preferable.
  • polyfunctional acrylic monomers compounds in which hydroxyl groups of polyhydric alcohols such as diols, triols, and tetraols are replaced with acrylate groups, methacrylate groups, or ⁇ -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 acrylate groups, methacrylate groups, or ⁇ -fluoroacrylate groups.
  • 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, ⁇ -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.
  • a specific example
  • Rf d is a fluorine-containing alkyl group having 1 to 40 carbon atoms.
  • Rf e is the fluorine-containing alkyl group having ether bond of the fluorine-containing alkyl group or a 2 to 100 carbon atoms having 1 to 40 carbon atoms
  • R c is H or an alkyl group having 1 to 3 carbon atoms .
  • 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 ⁇ -fluoroacrylate groups.
  • an ⁇ -fluoroacrylate compound is particularly preferred from the viewpoint of good curing reactivity.
  • the amount of the active energy ray curing initiator (b) added is the content of the carbon-carbon double bond in the fluoropolymer (a), the presence or absence of the use of the curing agent, 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.
  • the fluoropolymer (a ) 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight, and most preferably 0.1 to 10 parts by weight with respect to 100 parts by weight.
  • it is 0.05 to 50 mol%, preferably 0.1 to 20 mol%, most preferably based on the content (number of moles) of carbon-carbon double bonds contained in the fluoropolymer (a). Is 0.5 to 10 mol%.
  • 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. It is 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.
  • 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
  • the curable composition of this invention can also mix
  • the inorganic compound fine particles are not particularly limited, but compounds having a refractive index of 1.5 or less are preferable.
  • 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.
  • inorganic compound fine particles 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. .
  • 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.
  • 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.
  • 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.
  • active energy rays such as ultraviolet rays, electron beams or radiation.
  • 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.
  • 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.
  • the curable composition of this invention can use as a material of a sealing member, an optical member, a photoelectronic imaging tube, various sensors, an antireflection film, for example.
  • 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.
  • 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.
  • a package 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.
  • 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
  • sealing members or fillers for optical members such as lenses for deep ultraviolet microscopes are also included.
  • 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, an autofocus of a camera, 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.
  • 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 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, which is useful.
  • 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 ⁇ m.
  • 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 ⁇ m or more, preferably 0.07 ⁇ m or more, more preferably 0.08 ⁇ m or more, and 0.5 ⁇ m or less.
  • the thickness is preferably 0.2 ⁇ m or less, more preferably 0.12 ⁇ m 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.
  • 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 is not particularly limited.
  • 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.
  • 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.
  • a transparent resin base material such as acrylic resin, polycarbonate, cellulose resin, polyethylene terephthalate, and polyolefin resin, and can effectively exhibit an antireflection effect.
  • GPC HLC-8020 manufactured by Tosoh Corporation was used, one column manufactured by Shodex (one GPC KF-801 and one GPC KF-802 were used). 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) were calculated using the following GPC KF-806M in series. calculate.
  • THF tetrahydrofuran
  • Tg Glass transition temperature
  • Tm Melting point
  • 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.
  • perbutyl PV product name, manufactured by NOF Corporation
  • 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.
  • APS ammonium persulfate
  • the solenoid valve 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.
  • 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.
  • perbutyl PV product name, manufactured by NOF Corporation
  • 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.
  • 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.
  • 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) By changing the saponification time in Synthesis Example 10, TFE / vinyl alcohol / vinyl acetate polymers A1-45, A1-86, and A1-96 were obtained. Table 3 summarizes.
  • Synthesis Examples 14 to 18 (saponification homogeneous system) A saponified 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.
  • DMF N, N-dimethylformamide
  • 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.
  • Examples 2 to 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.
  • the abbreviations for each polymer are also shown in Table 4.
  • the blending ratio is summarized in Table 4.
  • Karenz BEI is represented by the following chemical formula.
  • MIBK methyl isobutyl ketone
  • 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.
  • 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.
  • 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.
  • MIBK methyl isobutyl ketone
  • 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.
  • 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):
  • ⁇ Transparent and uniform. ⁇ : Partly cloudy (gel-like material) is observed. X: Opaque and cloudy.
  • a curable composition is spin-coated on a silicon wafer, applied to a film thickness of about 0.1 ⁇ m, air-dried, dried for 10 minutes in a 200 ° C. blower dryer, and then a belt conveyor type UV. It was cured by irradiating with ultraviolet rays at an intensity of 1500 mJ / cm 2 U from above using an exposure machine.
  • 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.
  • 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.

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Abstract

L'objectif de la présente invention est de fournir un nouveau polymère contenant du fluor qui présente une transparence, un indice de réfraction faible, une résistance aux solvants et une résistance à la chaleur et qui peut être facilement durci. Ce polymère contenant du fluor est caractérisé par le fait qu'il comprend des unités polymérisées dérivées d'un monomère contenant du fluor, des unités polymérisées dérivées d'alcool vinylique en tant qu'unités polymérisées optionnelles et des unités polymérisées représentées par la formule générale (1) :-CH2-CH (-O- (L) l-Rb)- (Dans la formule, Rb est un groupe organique qui a au moins une double liaison terminale, L est un groupe organique divalent et l est 0 ou 1).
PCT/JP2013/052081 2012-01-31 2013-01-30 Polymère contenant du fluor et son procédé de production WO2013115267A1 (fr)

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