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WO2009123013A1 - Composé contenant du fluor polyfonctionnel et son procédé de fabrication - Google Patents

Composé contenant du fluor polyfonctionnel et son procédé de fabrication Download PDF

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Publication number
WO2009123013A1
WO2009123013A1 PCT/JP2009/056131 JP2009056131W WO2009123013A1 WO 2009123013 A1 WO2009123013 A1 WO 2009123013A1 JP 2009056131 W JP2009056131 W JP 2009056131W WO 2009123013 A1 WO2009123013 A1 WO 2009123013A1
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Prior art keywords
group
compound
fluorine
alkyl group
represented
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English (en)
Japanese (ja)
Inventor
義人 田中
卓司 石川
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority to JP2010505774A priority Critical patent/JP5338809B2/ja
Publication of WO2009123013A1 publication Critical patent/WO2009123013A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons

Definitions

  • the present invention relates to a polyfunctional fluorine-containing compound, a method for producing the compound, a crosslinking agent comprising the compound, a curable composition containing the compound, and a cured product obtained by curing the composition.
  • Fluorine-containing compounds having fluorine atoms in the molecule are excellent in light transmission and light durability.
  • Materials containing fluorine-containing compounds are used as cross-linking agents for paints, sealing materials for optical devices, etc. in use.
  • the fluorine-containing compound used for these applications is desired to have a plurality of functional groups in the molecule that react with other components.
  • the synthesis of the fluorine-containing compound requires a special raw material having a fluorine atom.
  • the reactivity of the fluorine-containing compound is often different from that of a general organic compound, it is difficult to obtain a target compound by a general organic synthesis method.
  • polyfunctional fluorine-containing compounds having a plurality of functional groups in the molecule are not easily synthesized, and there are no commercially available polyfunctional fluorine-containing compounds having three or more functional groups.
  • An object of the present invention is to provide a polyfunctional fluorine-containing compound, a method for producing the compound, a crosslinking agent comprising the compound, a curable composition containing the compound, and a cured product obtained by curing the composition.
  • the present inventors have conducted an enethiol reaction between a polyfunctional thiol compound and a fluorine-containing allyl compound having a hydroxyl group, or a fluorine-containing vinyl ether compound having a polyfunctional thiol compound and a hydroxyl group.
  • a polyfunctional fluorine-containing compound having at least one hydroxyl group is synthesized by an enethiol reaction, and a polyfunctional fluorine-containing compound having two or more carbon-carbon double bonds at the terminal by an esterification reaction or urethanization reaction with the hydroxyl group. It has been found that a functional fluorine-containing compound can be synthesized.
  • the obtained polyfunctional fluorine-containing compound has a plurality of curable sites in the molecule, it can be suitably used as a crosslinking agent for paints. Further, the polyfunctional fluorine-containing compound of the present invention having a plurality of carbon-carbon double bonds in the molecule can be mixed with other components to form a curable composition, which can be cured to produce a cured product. .
  • the present invention has been completed based on such findings and further studies.
  • the present invention relates to a novel polyfunctional fluorine-containing compound described in the following items 1 to 12, a method for producing the compound, a crosslinking agent comprising the compound, a curable composition containing the compound, and a cured product obtained by curing the composition I will provide a.
  • Item 1 a novel polyfunctional fluorine-containing compound described in the following items 1 to 12, a method for producing the compound, a crosslinking agent comprising the compound, a curable composition containing the compound, and a cured product obtained by curing the composition I will provide a.
  • T is a hydrocarbon which may have at least one heteroatom selected from the group consisting of O, N and S, p is an integer of 2 or more, and X, Z and Rf are each Same or different and the same.
  • R 4 is the same or different and is a single bond, —C a H 2a —, —C b H 2b —B—C c H 2c — or —S—C d H 2d —, a, b, c and d are the same or different and are an integer of 1 or more, B is —S—, —C ( ⁇ O) O—, —OC ( ⁇ O) — or —O—, and A is —C e H 2e ⁇ or —C f H 2f —E—C g H 2g —, e, f and g are the same or different and are an integer of 1 or more, and E is —S—, —C ( ⁇ O) O—.
  • Q has an optionally substituted aliphatic ring, an optionally substituted heteroaliphatic ring, an optionally substituted aromatic ring or a substituted group.
  • substituents may be an alkyl group having 1 to 12 carbon atoms, —OH, —COOR 7 , —CONR 8 R 9 , —NH 2 , —COCl, —SO 2 F, respectively.
  • Rf is a linear or branched fluorinated alkyl group having 1 to 20 carbon atoms and having at least one group represented by the formula: —O—C ( ⁇ O) —X a —R b , or at least one formula Any one of Items 1 to 6, which is a linear or branched fluorinated alkyl group having an ether bond having 2 to 50 carbon atoms and having a group represented by —O—C ( ⁇ O) —X a —R b A compound according to claim 1. Item 8.
  • Rf 1 is at least one of the formulas —O—C ( ⁇ O) —NH—R b A fluorine-containing alkyl group having 1 to 40 carbon atoms having the group represented by the formula, or an ether having 2 to 100 carbon atoms having at least one group represented by the formula: —O—C ( ⁇ O) —NH—R b A fluorine-containing alkyl group having a bond, and R b is an organic group having at least one terminal double bond.
  • the manufacturing method characterized by making it react with the compound represented by these. Item 9.
  • Two or more general formulas (1-2) in the molecule S—CX 2 CHF—Z—O—Rf 2 (1-2)
  • X is the same or different and is H or F
  • Z is —CF 2 — or a single bond
  • Rf 2 is represented by at least one formula: —O—C ( ⁇ O) —R b
  • Rfa is a fluorine-containing alkyl group having 1 to 40 carbon atoms having at least one hydroxyl group, or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms and having at least one hydroxyl group; Z is the same as above.
  • the manufacturing method characterized by making it react with the compound represented by these.
  • Item 8. A coating crosslinking agent comprising the compound according to any one of Items 1 to 7.
  • the polyfunctional fluorine-containing compound of the present invention has the following general formula (1).
  • X is the same or different and is H or F; Z is —CF 2 — or a single bond, Rf represents at least one fluorine-containing alkyl group having 1 to 40 carbon atoms having a group represented by the formula: —O—C ( ⁇ O) —X a —R b , or at least one formula: —O—C ( ⁇ O) -X a —R b is a fluorine-containing alkyl group having a C 2-100 ether bond and a group represented by X a is —NH— or a single bond, R b is an organic group having at least one terminal double bond.
  • It is a compound characterized by having 2 or more groups represented by these.
  • the alkyl group is preferably a fluorinated alkyl group having 1 to 20 carbon atoms, more preferably a fluorinated alkyl group having 1 to 12 carbon atoms.
  • the fluorine-containing alkyl group may be linear, branched or cyclic.
  • a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms and having a group represented by at least one formula: —O—C ( ⁇ O) —X a —R b” Is preferably a fluorine-containing alkyl group having an ether bond having 2 to 50 carbon atoms, and more preferably a fluorine-containing alkyl group having an ether bond having 2 to 25 carbon atoms.
  • the fluorine-containing alkyl group may be linear, branched or cyclic.
  • R b is an organic group having at least one terminal double bond. Specific examples of R b include the following general 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.
  • 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 is represented by the following general formula:
  • an unreacted isocyanate group (O ⁇ C ⁇ ) present in the compound is obtained from a compound obtained by urethanation reaction of a polyvalent isocyanate compound and a monoalcohol having a terminal double bond.
  • N-) A group (part) excluding one is also included.
  • polyvalent isocyanate compound examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, mixed isocyanate of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, P, P ′ -Diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, paraphenylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate and the like.
  • Examples of the monoalcohol having a terminal double bond include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl.
  • Examples include monoalcohols having an acryloyl group or methacryloyl group such as methacrylate; monoalcohols having an allyl group such as allyl alcohol, allyl cellosolve, and trimethylpropane diallyl ether.
  • R b include the following general formula:
  • R is H, CH 3 , F, CF 3 or Cl.
  • the group represented by these is also mentioned.
  • the group represented by is preferable.
  • Rf of the general formula (1) at least one group represented by the formula: —O—C ( ⁇ O) —X a —R b suffices to be present in Rf.
  • the number is usually about 1 to 10, preferably about 1 to 6, and more preferably about 1 to 3.
  • the polyfunctional fluorine-containing compound of the present invention having at least two of these terminal double bonds can be used as a crosslinking agent for paints because the substituent is a functional group.
  • “at least one fluorine-containing alkyl group having 1 to 40 carbon atoms having a group represented by the formula: —O—C ( ⁇ O) —X a —R b ” and “at least Specific structural formulas of “one formula: —O—C ( ⁇ O) —X a —R b and a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms” include, for example, Can be represented by the following structural formula.
  • each repeating unit is not limited to this order, and may be a block or random.
  • Rf is preferably represented by the following structural formula.
  • n, n1, X a and R b are as defined above.
  • n, n1, n2, X a and R b are as defined above.
  • T is a hydrocarbon optionally having at least one heteroatom selected from the group consisting of O, N and S; p is an integer of 2 or more.
  • the compound represented by these is preferable.
  • X, Z and Rf are the same or different and are the same as those of the compound represented by the general formula (1).
  • p groups (p is an integer of 2 or more) represented by the formula: — (S—CX 2 CHF—Z—O—Rf), Each is the same or different.
  • p is usually an integer of 2 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6.
  • R 4 is the same or different and is a single bond, —C a H 2a —, —C b H 2b —B—C c H 2c — or —S—C d H 2d —, a, b, c and d are the same or different and are an integer of 1 or more
  • B is —S—, —C ( ⁇ O) O—, —OC ( ⁇ O) — or —O—
  • A is —C e H 2e — or —C f H 2f —E—C g H 2g —, e, f and g are the same or different and are integers of 1 or more
  • E is —S—, —C ( ⁇ O) O—, —OC ( ⁇ O) — or —O—
  • R 5 is H, an optionally substituted alkyl group, or a group represented by the formula: —R 4 —S—CX 2 CHF—Z—O—Rf, R
  • R 4 is the same or different and is a single bond, —C a H 2a —, —C b H 2b —B—C c H 2c —, or —S—C d H 2d —.
  • a, b, c and d are the same or different and are an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10.
  • R 4 In the group in which R 4 is represented by —C b H 2b —B—C c H 2c —, B represents —S—, —C ( ⁇ O) O—, —OC ( ⁇ O) — or —O—. It is. However, in R 4 , —C a H 2a —, —C b H 2b —B—C c H 2c —, and —S—C d H 2d — are each represented by the right side bond on the paper in the formula (1b) Bonded to the S atom of —S—CX 2 CHF—Z—O—Rf. Among these, B is preferably —OC ( ⁇ O) —.
  • A is —C e H 2e — or —C f H 2f —E—C g H 2g —.
  • e, f and g are the same or different and are an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10.
  • E is —S—, —C ( ⁇ O) O—, —OC ( ⁇ O) — or —O—. Among these, E is preferably —O—.
  • R 5 is H, an alkyl group which may have a substituent, or a group represented by the formula: —R 4 —S—CX 2 CHF—Z—O—Rf.
  • alkyl group of the “optionally substituted alkyl group” represented by R 5 examples 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. . More preferably, it is an alkyl group having 1 to 8 carbon atoms.
  • the alkyl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the present invention.
  • the substituent include —OH, —COOH, —COOCH 3 , —NH 2 , —COOCH 2 CH 3 , —COOCH 2 CF 3 and the like.
  • the alkyl group may be substituted with 1 to 3 of at least one selected from these groups.
  • R 6 is H, an alkyl group which may have a substituent, or a group represented by the formula: —R 4 —S—CX 2 CHF—Z—O—Rf.
  • alkyl group of the “optionally substituted alkyl group” represented by R 6 examples 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. . More preferably, it is an alkyl group having 1 to 8 carbon atoms.
  • the alkyl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the present invention.
  • the substituent include —OH, —COOH, —COOCH 3 , —NH 2 , —COOCH 2 CH 3 , —COOCH 2 CF 3 and the like.
  • the alkyl group may be substituted with 1 to 3 of at least one selected from these groups.
  • q is an integer of 0 or more. q is preferably an integer of 0 to 10, more preferably an integer of 0 to 5, and particularly preferably 0 or 1.
  • particularly preferable compounds include compounds represented by the following general formula.
  • R 5 is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms.
  • Q has an optionally substituted aliphatic ring, an optionally substituted heteroaliphatic ring, an optionally substituted aromatic ring or a substituted group.
  • a heteroaromatic ring that may be The substituents are each selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, —OH, —COOR 7 , —CONR 8 R 9 , —NH 2 , —COCl, —SO 2 F, —SO 3 H, and —CN.
  • R 7 is H, an alkyl group or a fluorine-containing alkyl group
  • R 8 and R 9 are the same or different and are H, an alkyl group or a fluorine-containing alkyl group
  • r is an integer greater than or equal to 2
  • X, Z and Rf are the same or different and are the same as above
  • the groups represented by the formula: — (S—CX 2 CHF—Z—O—Rf) are the same or different. ] The compound represented by these is mentioned.
  • X, Z and Rf are the same or different and are the same as those of the compound represented by the general formula (1).
  • the aliphatic ring which may have a substituent may be either a monocyclic ring or a bicyclic ring.
  • each of the substituents is an alkyl group having 1 to 12 carbon atoms, —OH, —COOR 7 , —CONR 8 R 9 , —NH 2 , —COCl, —SO 2 F, —SO 3 It is at least one selected from the group consisting of H and —CN.
  • R 7 is H, an alkyl group, or a fluorine-containing alkyl group.
  • alkyl group include linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms.
  • fluorine-containing alkyl group include linear, branched or cyclic fluorine-containing alkyl groups having 1 to 12 carbon atoms.
  • R 8 and R 9 are the same or different and are H, an alkyl group, or a fluorine-containing alkyl group.
  • alkyl group include linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms.
  • fluorine-containing alkyl group include linear, branched or cyclic fluorine-containing alkyl groups having 1 to 12 carbon atoms.
  • r is an integer of 2 or more, and the group represented by — (S—CX 2 CHF—Z—O—Rf) is represented by the general formula (1c). There are two or more in a given compound. r is usually an integer of 2 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6.
  • the carbon number of the aliphatic ring which may have a substituent is usually about 3 to 100, preferably about 3 to 50, more preferably about 3 to 12.
  • each aliphatic ring may have the same substituent as in general formula (1c), and X, Z and Rf are the same as those in the compound represented by general formula (1). , R are the same as those in the general formula (1c). ]
  • the heteroaliphatic ring which may have a substituent may be either a monocyclic ring or a bicyclic ring.
  • each of the substituents is an alkyl group having 1 to 12 carbon atoms, —OH, —COOR 7 , —CONR 8 R 9 , —NH 2 , —COCl, —SO 2 F, —SO 3 It is at least one selected from the group consisting of H and —CN.
  • R 7 , R 8 and R 9 are the same as those of the aliphatic ring which may have the substituent.
  • the carbon number of the heteroaliphatic ring which may have a substituent is usually about 2 to 100, preferably about 2 to 50, more preferably about 2 to 12.
  • hetero atom contained in the heteroaliphatic ring include at least one selected from the group consisting of O, N, and S.
  • each heteroaliphatic ring may have the same substituent as in general formula (1c), and X, Z and Rf are the same as those in the compound represented by general formula (1). And r is the same as that of the general formula (1c). ]
  • the aromatic ring which may have a substituent may be either a monocyclic ring or a bicyclic ring.
  • each of the substituents is an alkyl group having 1 to 12 carbon atoms, —OH, —COOR 7 , —CONR 8 R 9 , —NH 2 , —COCl, —SO 2 F, —SO 3 It is at least one selected from the group consisting of H and —CN.
  • R 7 , R 8 and R 9 are the same as those of the aliphatic ring which may have the substituent.
  • the carbon number of the aromatic ring which may have a substituent is usually about 6 to 100, preferably about 6 to 50, more preferably about 6 to 20.
  • each aromatic ring may have the same substituent as in the general formula (1c), and X, Z and Rf are the same as those in the compound represented by the general formula (1). , R are the same as those in the general formula (1c). ]
  • the heteroaromatic ring which may have a substituent may be either a monocyclic ring or a bicyclic ring.
  • each of the substituents is an alkyl group having 1 to 12 carbon atoms, —OH, —COOR 7 , —CONR 8 R 9 , —NH 2 , —COCl, —SO 2 F, —SO 3 It is at least one selected from the group consisting of H and —CN.
  • R 7 , R 8 and R 9 are the same as those of the aliphatic ring which may have the substituent.
  • the carbon number of the heteroaromatic ring which may have a substituent is usually about 4 to 100, preferably about 4 to 50, more preferably about 4 to 20.
  • each heteroaromatic ring may have the same substituent as in the general formula (1c), and X, Z and Rf are the same as those in the compound represented by the general formula (1). And r is the same as that of the general formula (1c). ]
  • the 1st manufacturing method of the polyfunctional fluorine-containing compound of this invention is 2 or more following general formula (2) in a molecule
  • Rfa is a fluorine-containing alkyl group having 1 to 40 carbon atoms having at least one hydroxyl group, or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms having at least one hydroxyl group
  • X is the same or different and is H or F;
  • Z is —CF 2 — or a single bond.
  • the “compound having two or more groups represented by the general formula (1-1)” obtained by the first production method of the present invention is the above-mentioned “general formula” which is the polyfunctional fluorine-containing compound of the present invention.
  • X a in Rf of the “compound having two or more groups represented by (1)” is a compound in which —NH— is present.
  • fluorine-containing alkyl group of "at least one fluorinated alkyl group having 1 to 40 carbon atoms having a hydroxyl group” is preferably a fluorine-containing alkyl group having 1 to 20 carbon atoms, carbon atoms 1 to 12 fluorine-containing alkyl groups are more preferred.
  • the fluorine-containing alkyl group may be linear, branched or cyclic.
  • a fluorinated alkyl group of the "at least a fluorinated alkyl group having an ether bond having 2-100 carbon atoms which has one hydroxyl group" is, including having an ether bond 2-50 carbon atoms
  • a fluorine alkyl group is preferable, and a fluorine-containing alkyl group having an ether bond having 2 to 25 carbon atoms is more preferable.
  • the fluorine-containing alkyl group may be linear, branched or cyclic.
  • the carbon at least one existing hydroxyl group (-OH) is directly bonded to the Rf a is primary from the chemical bonding mode, secondary and tertiary three Can be classified as carbon.
  • Rfa of the general formula (2) " a fluorine-containing alkyl group having 1 to 40 carbon atoms having at least one hydroxyl group” and "a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms and having at least one hydroxyl group”
  • a specific structural formula of “” it can be represented by the following structural formula, for example.
  • n is an integer of 0 to 5
  • n1 is an integer of 1 to 10
  • each repeating unit is not limited to this order, But it may be random.
  • Rf a is Of these, preferred are those represented by the following structural formula.
  • Rf a is Of these, preferred are those particularly represented by the following structural formula.
  • n is the same as defined above.
  • R b is the same “organic group having at least one terminal double bond” as in the general formula (1).
  • M is H 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.
  • the “organic group having at least one terminal double bond” of R b is a polyvalent isocyanate similar to the compound represented by the general formula (1).
  • a group (part) obtained by removing one unreacted isocyanate group (O ⁇ C ⁇ N—) present in the compound from a compound obtained by urethanation of a compound and a monoalcohol having a terminal double bond is also obtained. Can be mentioned.
  • polyvalent isocyanate compound examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, mixed isocyanate of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, P, P ′ -Diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, paraphenylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate and the like.
  • Examples of the monoalcohol having a terminal double bond include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate.
  • Monoalcohols having an acryloyl group or a methacryloyl group such as monoalcohols having an allyl group such as allyl alcohol, allyl cellosolve, and trimethylpropane diallyl ether.
  • the amount of the compound having two or more groups represented by the general formula (2) in the molecule varies depending on the number of hydroxyl groups in the molecule.
  • an amount sufficient for one compound represented by the general formula (3) to react may be used.
  • this amount is called equivalent.
  • the equivalent is 1 ⁇ 2 of the molecular weight, and in the same manner, in the compound having three hydroxyl groups in the molecule, the equivalent is 3 of the molecular weight.
  • the amount of the compound having two or more groups represented by the general formula (2) in the molecule is usually about 0.01 to 2 equivalents, preferably about the compound represented by the general formula (3).
  • the amount is about 0.1 to 1.5 equivalents, more preferably about 0.5 to 1.2 equivalents.
  • the compound represented by the general formula (3) is usually used in an amount of 0.5 to 100 per 1 mol of the hydroxyl group in the compound having a group represented by the general formula (2) in the molecule.
  • About mol, preferably about 0.67 to 10 mol, more preferably about 0.83 to 2 mol may be used.
  • a compound having two or more groups represented by the general formula (2) in the molecule and a compound represented by the general formula (3) are subjected to a urethanation reaction (addition reaction). ) To form a urethane bond.
  • the terminal double bond present in the compound represented by the general formula (3) does not substantially react and becomes a reactive functional group of the polyfunctional fluorine-containing compound of the present invention.
  • the polyfunctional fluorine-containing compound of the present invention has a plurality of reactive terminal double bonds derived from the above substituents present in the compound represented by the general formula (3) in the molecule, It can be suitably used as an agent. Moreover, it can be set as the curable composition containing the polyfunctional fluorine-containing compound of this invention, and this can be hardened and a hardened
  • the OH group acts as a curing reaction group when the polyfunctional fluorine-containing compound of the present invention is used as a curable composition.
  • two or more compounds having a group represented by the general formula (2) in the molecule may be used singly or in combination of two or more. May be.
  • the urethanization reaction easily proceeds by mixing a compound having a group represented by two or more general formulas (2) in the molecule with a compound represented by the general formula (3) or heating the mixture. .
  • the heating temperature (reaction temperature) of the urethanization reaction is usually about 5 to 90 ° C., preferably about 10 to 70 ° C., more preferably about 20 to 60 ° C.
  • a catalyst may be further used for the compound having a group represented by two or more general formulas (2) in the molecule and the compound represented by the general formula (3).
  • the catalyst is not particularly limited, and a conventionally known catalyst used for the urethanization reaction may be used, and a commercially available product is easily available.
  • 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 urethanization reaction proceeds in a shorter time, and the target polyfunctional fluorine-containing compound is obtained.
  • the amount of the catalyst used for the urethanization reaction is not particularly limited and may be adjusted as appropriate.
  • the amount is usually 0.0001 to 3 masses per 100 mass parts of the compound represented by the general formula (3). Part by weight, preferably about 0.001 to 1 part by weight, more preferably about 0.01 to 0.5 part by weight.
  • a solvent may be further used.
  • a solvent a conventionally known solvent that is generally used and does not interfere with the progress of the urethanization reaction may be used as the solvent.
  • 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; fluorine solvents such as HCFC225 (dichloropentafluoropropane) do it.
  • MIBK methyl isobutyl ketone
  • MEK methyl ethyl ketone
  • ester solvents such as ethyl acetate and butyl acetate
  • fluorine solvents such as HCFC225 (dichloropentafluoropropane) do it.
  • An alcohol solvent having an OH group is not preferable because it prevents the urethanization reaction from proceeding.
  • the progress of the urethanization reaction is hindered, so that each solvent is more preferably dehydrated before use.
  • other components may be added as necessary.
  • other components include an antioxidant, a leveling agent, an inorganic filler, and an organic filler.
  • the amount used is usually about 0.01 to 10 parts by weight, preferably about 0.1 to 2 parts by weight, based on 100 parts by weight of the compound represented by the general formula (3). More preferably, it is about 0.5 to 1 part by mass.
  • the second production method of the polyfunctional fluorine-containing compound of the present invention comprises two or more of the following general formula (2) in the molecule. —S—CX 2 CHF—Z—O—Rf a (2) [Wherein, Rfa is a fluorine-containing alkyl group having 1 to 40 carbon atoms having at least one hydroxyl group, or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms and having at least one hydroxyl group; Z is the same as above.
  • Rf 2 represents at least one fluorine-containing alkyl group having 1 to 40 carbon atoms having a group represented by the formula: —O—C ( ⁇ O) —R b , or at least one formula: —O— A fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms and having a group represented by C ( ⁇ O) —R b ; R b is an organic group having at least one terminal double bond; X and Z are the same as described above.
  • a production method comprising obtaining a compound having a group represented by the formula:
  • the “compound having a group represented by two or more general formulas (1-2) in the molecule” obtained by the second production method of the present invention refers to the above general formula ( X a in Rf of the compound having a group represented by 1) 2 or more is a compound of a single bond.
  • the compound having two or more groups represented by the general formula (2) is the same as the first production method of the present invention.
  • the compound represented by the general formula (4) is: X b —C ( ⁇ O) —R b (4) [Wherein, X b represents HO—, R 10 O—, F— or Cl—, R 10 represents an alkyl group or a fluorine-containing alkyl group, and R b represents an organic compound having at least one terminal double bond. It is a group. ] It is.
  • 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 General Formula (1).
  • R is H, CH 3 , F, CF 3 or Cl, and X b is the same as above.
  • X b is the same as above.
  • ⁇ , ⁇ -unsaturated cyclic carboxylic acid halide is represented by the following general formula
  • the compound represented by these is preferable.
  • the amount of the compound having a group represented by the general formula (2) in the molecule varies depending on the number of hydroxyl groups in the molecule, as in the first production method.
  • an amount sufficient for one compound represented by the general formula (4) to react with one hydroxyl group may be used.
  • this amount is called equivalent.
  • the equivalent is 1 ⁇ 2 of the molecular weight, and in the same manner, in the compound having three hydroxyl groups in the molecule, the equivalent is 3 of the molecular weight.
  • the amount of the compound having two or more groups represented by the general formula (2) in the molecule is usually about 0.01 to 2 equivalents, preferably about the compound represented by the general formula (4).
  • the amount is about 0.1 to 1.5 equivalents, more preferably about 0.5 to 1.2 equivalents.
  • the compound represented by the general formula (4) is usually used in an amount of 0.5 to 100 per 1 mol of the hydroxyl group in the compound having a group represented by the general formula (2) in the molecule.
  • About mol, preferably about 0.67 to 10 mol, more preferably about 0.83 to 2 mol may be used.
  • the terminal double bond present in the compound represented by the general formula (4) does not substantially react and becomes a reactive functional group of the polyfunctional fluorine-containing compound of the present invention.
  • the polyfunctional fluorine-containing compound of the present invention has a plurality of reactive terminal double bonds derived from the above substituents present in the compound represented by the general formula (4) in the molecule, It can be suitably used as an agent. Moreover, it can be set as the curable composition containing the polyfunctional fluorine-containing compound of this invention, and this can be hardened and a hardened
  • the OH group acts as a curing reaction group when the polyfunctional fluorine-containing compound of the present invention is used as a curable composition.
  • the compound having two or more groups represented by the general formula (2) in the molecule may be used alone or in combination of two or more. May be.
  • the esterification reaction proceeds easily by mixing a compound having a group represented by two or more general formulas (2) in the molecule with a compound represented by the general formula (4) or heating the mixture. .
  • the reaction temperature of 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 supplementing these.
  • the base include tertiary amines such as pyridine, N, N-dimethylaniline, tetramethylurea and triethylamine, and metallic magnesium.
  • a compound represented by the general formula (3) as a raw material or a carbon atom in a compound having two or more groups represented by the general formula (1-2) in the molecule as a product may coexist.
  • 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, and 2-heptanone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono Propylene glycol solvents such as butyl 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-225), perfluorohexane, perfluoro Fluorine-containing solvents such as bromo (2-butyltetrahydrofuran), methoxy-nonafluoro
  • other components may be added as necessary.
  • other components include an antioxidant, a leveling agent, an inorganic filler, and an organic filler.
  • the amount used is usually about 0.01 to 10 parts by weight, preferably about 0.1 to 2 parts by weight, based on 100 parts by weight of the compound represented by the general formula (2). More preferably, it is about 0.5 to 1 part by mass.
  • T is a hydrocarbon which may have at least one heteroatom selected from the group consisting of O, N and S, and p is an integer of 2 or more.
  • p is an integer of 2 or more.
  • T and p are the same as those in general formula (1a).
  • R 5b is H, an alkyl group which may have a substituent, or a group represented by the formula: —R 4 —SH
  • R 6b may be H, which may have a substituent.
  • the compound represented by these is mentioned.
  • R 5b is H, an alkyl group which may have a substituent, or a group represented by the formula: —R 4 —SH.
  • alkyl group of the “optionally substituted alkyl group” represented by R 5b examples 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. . More preferably, it is an alkyl group having 1 to 8 carbon atoms.
  • the alkyl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the present invention.
  • the substituent include —OH, COOH, —COOCH 3 , —NH 2 , —COOCH 2 CH 3 , —COOCH 2 CF 3 and the like.
  • the alkyl group may be substituted with 1 to 3 of at least one selected from these groups.
  • R 6b is H, an alkyl group which may have a substituent, or a group represented by the formula: —R 4 —SH.
  • alkyl group of the “ optionally substituted alkyl group” represented by R 6b examples 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. . More preferably, it is an alkyl group having 1 to 8 carbon atoms.
  • the alkyl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the present invention.
  • the substituent include —OH, COOH, —COOCH 3 , —NH 2 , —COOCH 2 CH 3 , —COOCH 2 CF 3 and the like.
  • the alkyl group may be substituted with 1 to 3 of at least one selected from these groups.
  • particularly preferred compounds include compounds represented by the following general formula.
  • Examples of the compound represented by the general formula (3b) include 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopros Pionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), 1,2-dimercaptoethane, 1,2-dimercaptopropane, 1,3- Dimercaptopropane, dimercaptobutane, dimercaptohexane, tetrakismercaptomethylmethane, dimercaptomethane, trimercaptomethane, 1,2,3-trimercaptopropane, 1,2,3,4-tetramercaptobutane, dimercaptomethane 1,1-dimercapto Tan, 1,2-dimercaptoethan
  • Q has an aliphatic ring which may have the same substituent as in general formula (1c), a heteroaliphatic ring which may have a substituent, and a substituent.
  • the substituent is at least one selected from the group consisting of an alkyl group, —OH, —COOR 7 , —CONR 8 R 9 , —NH 2 , —COCl, —SO 2 F, —SO 3 H, and —CN. is there.
  • the aliphatic ring which may have a substituent may be either a monocyclic ring or a bicyclic ring. Further, when it has a substituent, the substituent consists of an alkyl group, —OH, —COOR 7 , —CONR 8 R 9 , —NH 2 , —COCl, —SO 2 F, —SO 3 H, and —CN, respectively. It is at least one selected from the group.
  • R 7 is H, an alkyl group, or a fluorine-containing alkyl group.
  • alkyl group include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms.
  • fluorine-containing alkyl group include linear, branched or cyclic fluorine-containing alkyl groups having 1 to 10 carbon atoms.
  • R 8 and R 9 are the same or different and are H, an alkyl group, or a fluorine-containing alkyl group.
  • alkyl group include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms.
  • fluorine-containing alkyl group include linear, branched or cyclic fluorine-containing alkyl groups having 1 to 10 carbon atoms.
  • r is an integer of 2 or more, and two or more groups represented by — (SH) are present in the compound represented by the general formula (3c).
  • r is usually an integer of 2 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6.
  • the carbon number of the aliphatic ring which may have a substituent is usually about 3 to 100, preferably about 3 to 50, more preferably about 3 to 12.
  • each aliphatic ring may have the same substituent as in general formula (3c), and the substituent and r are the same as those of the compound represented by general formula (1c). . ]
  • the heteroaliphatic ring which may have a substituent may be a single ring or multiple rings. Further, when it has a substituent, the substituent consists of an alkyl group, —OH, —COOR 7 , —CONR 8 R 9 , —NH 2 , —COCl, —SO 2 F, —SO 3 H, and —CN, respectively. It is at least one selected from the group. R 7 , R 8 and R 9 are the same as those of the aliphatic ring which may have the substituent.
  • the carbon number of the heteroaliphatic ring which may have a substituent is usually about 2 to 100, preferably about 2 to 50, more preferably about 2 to 12.
  • hetero atom contained in the heteroaliphatic ring include at least one selected from the group consisting of O, N, and S.
  • each heteroaliphatic ring may have the same substituent as in the general formula (3c), and the substituent and r are the same as those in the compound represented by the general formula (1c). is there. ]
  • Q in the general formula (3c) is an optionally substituted heteroaliphatic ring
  • Q in the general formula (3c) is an optionally substituted heteroaliphatic ring
  • examples of the compound in which Q in the general formula (3c) is an optionally substituted heteroaliphatic ring include 2,5-dimercaptomethyl-1,4-dithiane, 4,5-dithiane Examples include mercaptomethyl-1,3-dithiane.
  • the aromatic ring which may have a substituent may be a monocyclic ring or a multicyclic ring. Further, when it has a substituent, the substituent consists of an alkyl group, —OH, —COOR 7 , —CONR 8 R 9 , —NH 2 , —COCl, —SO 2 F, —SO 3 H, and —CN, respectively. It is at least one selected from the group. R 7 , R 8 and R 9 are the same as those of the aliphatic ring which may have the substituent.
  • the carbon number of the aromatic ring which may have a substituent is usually about 6 to 100, preferably about 6 to 50, more preferably about 6 to 20.
  • each aromatic ring may have the same substituent as in the general formula (3c), and the substituent and r are the same as those of the compound represented by the general formula (1c). ]
  • Specific examples of the compound in which Q in the general formula (3c) is an aromatic ring which may have a substituent include 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4- Dimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2-dimercaptotoluene, 1,3-dimercaptotoluene, 1,4-dimercaptotoluene, 1,3,5-trimercaptotoluene, 1, Examples include 2-dimercaptoxylene, 1,3-dimercaptoxylene, 1,4-dimercaptoxylene, 1,3-dimercaptotolylene, 1,3,5-trimercaptotolylene, and the like.
  • the heteroaromatic ring which may have a substituent may be a single ring or multiple rings. Further, when it has a substituent, the substituent consists of an alkyl group, —OH, —COOR 7 , —CONR 8 R 9 , —NH 2 , —COCl, —SO 2 F, —SO 3 H, and —CN, respectively. It is at least one selected from the group. R 7 , R 8 and R 9 are the same as those of the aliphatic ring which may have the substituent.
  • the carbon number of the heteroaromatic ring which may have a substituent is usually about 4 to 100, preferably about 4 to 50, more preferably about 4 to 20.
  • hetero atom contained in the heteroaromatic ring include at least one selected from the group consisting of O, N, and S.
  • each heteroaromatic ring may have the same substituent as in general formula (3c), and the substituent and r are the same as those in the compound represented by general formula (1c). . ]
  • the compound having two or more thiol groups (—SH group, mercapto group) in the molecule of the present invention is a compound obtained by a conventionally known production method, and a commercially available product can also be used.
  • the compound having two or more thiol groups in the molecule of the present invention is synthesized, for example, according to the method described in The Chemistry of the thiol group (Chemistry of Functional Groups) By Saul Patai: John Wiley and Sons Ltd. be able to. For example, there is an isothiuronium salt method in which thiourea is reacted, isothiuronium salified and hydrolyzed.
  • n is the same as defined above.
  • n is the same as defined above.
  • n is the same as defined above.
  • n is the same as defined above.
  • the compound represented by the general formula (2-1) of the present invention is a compound obtained by a conventionally known production method, and a commercially available product can also be used.
  • the compounds represented by the general formula (2-1) may be used singly or in combination of two or more.
  • the amount of the compound having two or more thiol groups in the molecule varies depending on the number of thiol groups in the molecule. For example, one compound represented by the general formula (2-1) per one thiol group An amount sufficient to react may be used. In this specification, this amount is called equivalent. In a compound having two thiol groups in the molecule, the equivalent is 1 ⁇ 2 of the molecular weight, and in the same manner, in an compound having three thiol groups in the molecule, the equivalent is 3 of the molecular weight.
  • the amount of the compound having two or more thiol groups in the molecule is usually about 2 to 0.1 equivalent, preferably 1.2 to 0.1, relative to the compound represented by the general formula (2-1).
  • the amount is about 2 equivalents, more preferably about 1 to 0.5 equivalents.
  • the compound represented by the general formula (2-1) is usually about 0.5 to 1 mol, preferably 0, with respect to 1 mol of the thiol group of the compound having two or more thiol groups in the molecule.
  • About 0.8 to 5 mol, more preferably about 1 to 2 mol may be used.
  • the carbon-carbon double bond existing in the compound represented by the general formula (2-1) is added to the thiol group in the compound having two or more thiol groups in the molecule. react.
  • the hydroxyl groups in the Rf a is present in the compounds represented by the general formula (2-1), without substantial reaction, the isocyanate groups in the compound represented by the general formula (3) or
  • the polyfunctional fluorine-containing compound of the present invention is produced by reacting with the X b —C ( ⁇ O) — group in the compound represented by the general formula (4).
  • the unreacted thiol group is an isocyanate group of the compound represented by the general formula (3) or A bond can be formed by reacting with the X b —C ( ⁇ O) — group of the compound represented by the general formula (4), but a thiol group remains in the polyfunctional fluorine-containing compound of the present invention without reacting. Even if used, it acts as a curing reactive group when used as a curable composition.
  • compounds having two or more thiol groups in the molecule may be used alone or in combination of two or more. Good.
  • the enethiol reaction easily proceeds by irradiating a mixture of a compound having two or more thiol groups in the molecule and a compound represented by the general formula (2-1) with ultraviolet rays.
  • the irradiation amount of ultraviolet rays is usually about 0.1 to 10 J / cm 2 , preferably about 0.5 to 8 J / cm 2 , more preferably about 1 to 6 J / cm 2 .
  • the reaction temperature of the enethiol reaction is usually about 5 to 60 ° C., preferably about 10 to 55 ° C., more preferably about 20 to 50 ° C.
  • a photopolymerization initiator may be used in addition to the compound having two or more thiol groups in the molecule and the compound represented by the general formula (2-1). Even if the photopolymerization initiator is not used, the polyfunctional fluorine-containing compound of the present invention can be obtained. However, by using the photopolymerization initiator, the enethiol reaction proceeds in a shorter time, and the desired polyfunctional compound is contained. A fluorine compound is obtained.
  • the type of photopolymerization initiator is not particularly limited, and a conventionally known one may be used, and a commercially available product is easily available.
  • photopolymerization initiator examples include acetophenone compounds such as acetophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, ⁇ -aminoacetophenone; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl Benzoin compounds such as dimethyl ketal; benzophenone compounds such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propylbenzophenone, acrylated benzophenone, Michler ketone; thioxanthone, chlorothioxanthone, Methylthioxanthone, diethylthioxanthone, dimethylthioxone Thioxanthones such as Benson; benzyl, al
  • photopolymerization initiators examples include Irgacure 907, Irgacure 127, Irgacure 369, and Irgacure 819 manufactured by Nagase Sangyo Co., Ltd.
  • a photoinitiator may be used individually by 1 type and may be used in mixture of 2 or more types.
  • a known photoinitiator such as amines, sulfones and sulfines may be added to the photopolymerization initiator as necessary.
  • the amount of the photopolymerization initiator used is not particularly limited and may be adjusted as appropriate.
  • the amount is usually about 0.01 to 10 parts by mass, preferably about 0.5 to 7 parts by mass, more preferably about 1 to 5 parts by mass.
  • a solvent may be further used.
  • a solvent a conventionally known solvent that is generally used and does not hinder the progress of the enethiol reaction may be used as the solvent.
  • the solvent for example, methanol, ethanol, isopropanol, HCFC225 (dichloropentafluoropropane), methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK) or the like may be used.
  • other components may be added as necessary.
  • other components include an antioxidant, a leveling agent, an inorganic filler, and an organic filler.
  • the amount used is usually about 0.01 to 10 parts by weight, preferably 0.1 to 2 parts by weight, with respect to 100 parts by weight of the compound represented by the general formula (2-1). About 0.5, more preferably about 0.5 to 1 part by mass.
  • the enethiol reaction can proceed by generating radicals by an appropriate method without particularly irradiating ultraviolet rays.
  • a method of generating radicals for example, a method of generating radicals by heating using a known radical polymerization initiator is preferable.
  • radical polymerization initiator known peroxides, azo initiators and the like can be used.
  • the amount of the radical polymerization initiator is usually about 0.01 to 10 parts by weight, preferably about 0.05 to 7 parts by weight, more preferably 100 parts by weight of the compound represented by the general formula (2-1). About 0.5 to 3 parts by mass.
  • crosslinking agent and additive for coating material Since the polyfunctional fluorine-containing compound of the present invention has a plurality of unsaturated groups (carbon-carbon double bonds) in the molecule, it can be suitably used as a crosslinking agent and additive for coating material.
  • curable composition and cured product Since the polyfunctional fluorine-containing compound of the present invention has a plurality of unsaturated groups (carbon-carbon double bonds) in the molecule, the curable composition (cured) is mixed with other components. Can be suitably used as a functional fluorine-containing resin composition).
  • Examples of the mode of the curable fluorine-containing resin composition of the present invention include a mode using a solvent.
  • Various base materials can be coated by dissolving or dispersing the curable fluorine-containing resin composition of the present invention in a solvent to form a coating film. After the coating film is formed, it is efficiently irradiated with active energy rays or the like. It is preferable in that it can be cured and a cured film can be obtained.
  • the fluorine-containing resin composition for coating of the present invention is a composition containing (a) a polyfunctional fluorine-containing compound of the present invention, (b) an active energy ray curing initiator, and (c) a solvent.
  • 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, etc. It functions as a catalyst for initiating the curing (crosslinking reaction) of the carbon-carbon double bond of the fluorine-containing compound.
  • radicals and cations with ultraviolet light particularly those that generate radicals are used. 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 polyfunctional fluorine-containing compound (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. If it does, there will be no restriction
  • 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 cetate, 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, etc.
  • fluorinated alcohols such as compounds represented by the formula: benzotrifluoride, perfluorobenzene, perfluoro (tributylamine), ClCF 2 CFClCF 2 CFCl 2 and the like.
  • fluorinated solvents may be used alone or as a mixed solvent of fluorinated solvents with each other, 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.
  • a fluorine-containing alcohol solvent may be mixed together with these general-purpose solvents.
  • the fluorine-containing alcohol to be added may be one having a boiling point of 50 ° C. or higher, preferably 80 ° C. or higher and capable of dissolving the polyfunctional fluorine-containing compound.
  • the fluorinated alcohol may be used as a solvent alone, 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. Necessary for the curable fluorinated resin composition of the polyfunctional fluorinated compound (a) of the present invention and the active energy ray curing initiator (b), and further for the fluorinated resin composition for coating including the solvent (c).
  • 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,
  • a curing agent may be added.
  • the 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 monomers, etc.
  • Cationic polymerizable monomers can be mentioned. These monomers may be monofunctional having one carbon-carbon double bond or polyfunctional monomers having two or more carbon-carbon double bonds.
  • the polyfunctional fluorine-containing compound (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, for example, the following general formula
  • X c is H, CH 3 or F
  • Rf b is a fluorine-containing alkyl group having 2 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms.
  • the compound represented by these is preferable. Specifically, the following general formula
  • 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 ⁇ -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 a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having an ether bond having 2 to 100 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
  • R c is the same as defined above.
  • Preferred are those having a structure in which two or more hydroxyl groups of the fluorine-containing polyhydric alcohols represented by the general formula such as] 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 polyfunctional fluorine-containing compound (a), whether or not the curing agent is used.
  • the polyfunctional fluorine-containing compound is used when no curing agent is used.
  • the total number of moles of the carbon-carbon double bond content (number of moles) contained in the polyfunctional fluorine-containing compound (a) and the number of moles of carbon-carbon unsaturated bonds of the curing agent 0.05 to 50 mol%, preferably 0.1 to 20 mol%, and most preferably 0.5 to 10 mol%.
  • the amount of the 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 polyfunctional fluorine-containing compound to be used, etc. It is 1 to 80% by weight, preferably 5 to 70% by weight, more preferably 10 to 50% by weight, based on the fluorine-containing compound. If the addition amount of the curing agent is too large, the refractive index tends to increase, which is not preferable.
  • the type of solid content to be dissolved As content of the solvent (c) in the fluorine-containing resin composition for coating of the present invention, 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, and the target film thickness It is preferably selected so that the total solid content in the composition is 0.5 to 70% by weight, preferably 1 to 50% by weight.
  • 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. Furthermore, 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 fine particle compound is modified in advance using various coupling agents. Can do. Examples of various coupling agents include organically substituted silicon compounds; metal alkoxides such as aluminum, titanium, zirconium, antimony, and mixtures thereof; salts of organic acids; coordination compounds bonded to coordination compounds, and the like. .
  • the coating fluorine-containing resin composition of the present invention may be a polyfunctional fluorine-containing compound (a) or an additive in the form of a dispersion or a solution with respect to the solvent (c).
  • a uniform solution is preferable.
  • 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. Can be selected in consideration of the controllability and controllability of the film thickness.
  • the curable resin composition containing the polyfunctional fluorine-containing compound (a) of the present invention and the active energy ray curing initiator (b), and the coating fluorine-containing resin composition of the present invention applied to the substrate by the above method 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 polyfunctional fluorine-containing compound (a) of the present invention is polymerized between molecules, and the carbon-carbon double bond in the polyfunctional fluorine-containing compound (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.
  • a polyfunctional compound having at least one hydroxyl group is obtained by an enethiol reaction between a polyfunctional thiol compound and a fluorine-containing allyl compound having a hydroxyl group, or an enethiol reaction between a polyfunctional thiol compound and a fluorine-containing vinyl ether compound having a hydroxyl group.
  • a polyfunctional fluorine-containing compound having two or more carbon-carbon double bonds at the terminal can be synthesized by synthesizing a fluorine-containing compound and further performing an esterification reaction or urethanization reaction with the hydroxyl group.
  • the obtained polyfunctional fluorine-containing compound of the present invention has a plurality of curable sites in the molecule, it can be suitably used as a crosslinking agent for paints. Further, the polyfunctional fluorine-containing compound of the present invention having a plurality of carbon-carbon double bonds in the molecule can be mixed with other components to form a curable composition, which can be cured to produce a cured product. .
  • Synthesis Example 1 ( Synthesis of trifunctional OH group-containing fluorine-containing compound) (1) Preparation of mixed solution (a1) A mixed solution (a1) was prepared according to the following formulation.
  • the viscosity of the solution (a1) after the ultraviolet irradiation was increased to an extent that can be visually confirmed as compared with the mixed solution (a1) before the ultraviolet irradiation.
  • the solution (a1) after ultraviolet irradiation was colorless and transparent.
  • Example 1 26 parts by mass ((a1)) of Karenz AOI (hereinafter also referred to as AOI) manufactured by Showa Denko KK as an unsaturated group-containing isocyanate with respect to 100 parts by mass of the reaction product (a1) obtained in Synthesis Example 1. 1 equivalent to the hydroxyl group) and 0.01 parts by mass of dibutyltin dilaurate was added and reacted at 40 ° C. for 24 hours.
  • the structural formula of AOI is represented by the following general formula.
  • CH 2 CHCOOCH 2 CH 2 NCO
  • Example 2 29 parts by mass ((a1)) of Karenz MOI (hereinafter also referred to as MOI) manufactured by Showa Denko KK as an unsaturated group-containing isocyanate with respect to 100 parts by mass of the reaction product (a1) obtained in Synthesis Example 1. 1 equivalent to the hydroxyl group) and 0.01 parts by mass of dibutyltin dilaurate was added and reacted at 40 ° C. for 24 hours.
  • the structural formula of MOI is represented by the following general formula.
  • CH 2 CCH 3 COOCH 2 CH 2 NCO
  • Example 3 39 parts by mass ((a1)) of Karenz BEI (hereinafter also referred to as BEI) manufactured by Showa Denko KK as an unsaturated group-containing isocyanate with respect to 100 parts by mass of the reaction product (a1) obtained in Synthesis Example 1. 1 equivalent to the hydroxyl group) and 0.01 parts by mass of dibutyltin dilaurate was added and reacted at 40 ° C. for 24 hours.
  • the structural formula of BEI is represented by the following general formula.
  • Synthesis Example 2 ( Synthesis of a bifunctional OH group-containing fluorine-containing compound) (1) Preparation of mixed solution (a2) A mixed solution (a2) was prepared according to the following formulation.
  • Example 4 36 parts by mass of AOI (corresponding to 1 equivalent to the hydroxyl group) was added to 100 parts by mass of the reaction product (a2) obtained in Synthesis Example 2, and 0.01 parts by mass of dibutyltin dilaurate was further added. The reaction was carried out at 24 ° C. for 24 hours.
  • Synthesis example 3 (1) Preparation of mixed solutions (a3) to (a5) Mixed solutions (a3) to (a5) were prepared according to the following formulation.
  • the viscosity of each solution after ultraviolet irradiation increased to a level that can be visually confirmed as compared with each mixed solution before ultraviolet irradiation.
  • Example 5 AOI is 12 parts by mass, 26 parts by mass, and 23 parts by mass with respect to 100 parts by mass of the reaction products (a3) to (a5) obtained in Example 4, respectively (based on the hydroxyl groups of (a3) to (a5)). Each was equivalent to 1 equivalent), and 0.01 parts by mass of dibutyltin dilaurate was further added and reacted at 40 ° C. for 24 hours.
  • Synthesis example 4 (1) Preparation of mixed solutions (a6) and (a7) Mixed solutions (a6) and (a7) were prepared according to the following formulation.
  • the viscosity of each solution after ultraviolet irradiation increased to a level that can be visually confirmed as compared with each mixed solution before ultraviolet irradiation.
  • Example 6 39 parts by mass and 38 parts by mass of AOI with respect to 100 parts by mass of the reaction products (a6) and (a7) obtained in Synthesis Example 4, respectively 1 equivalent to the hydroxyl groups of (a6) and (a7) In addition, 0.01 parts by mass of dibutyltin dilaurate was further added and reacted at 40 ° C. for 24 hours.
  • Synthesis example 5 (1) Preparation of mixed solutions (a8) and (a9) Mixed solutions (a8) and (a9) were prepared according to the following formulation.
  • the viscosity of each solution after ultraviolet irradiation increased to a level that can be visually confirmed as compared with each mixed solution before ultraviolet irradiation.
  • Example 7 10 g of the reaction product (a8) obtained in Synthesis Example 5, 5.9 g (3 equivalents) of triethylamine, and 20 g of dehydrated methyl isobutyl ketone as a solvent were placed in a flask and cooled to 4 ° C. in an ice bath. 1.95 g (1.1 equivalents) of acrylic acid chloride was slowly added dropwise from the dropping funnel to the obtained mixed solution. After 2 hours, 1N HCl was added to the flask to quench and return to room temperature. Thereafter, separation and purification operations (hydrochloric acid ⁇ saturated saline solution ⁇ aqueous sodium bicarbonate solution ⁇ saturated saline solution) were repeated, and finally MgSO 4 was added and dehydrated for 24 hours. By IR analysis of the obtained reaction product, C ⁇ C bond and C ⁇ O bond were confirmed, and it was confirmed that the reaction proceeded.
  • Example 8 10 g of the reaction product (a9) obtained in Synthesis Example 5, 4.5 g (3 equivalents) of triethylamine, and 20 g of dehydrated methyl isobutyl ketone as a solvent were placed in a flask and cooled to 4 ° C. in an ice bath. To the obtained mixed solution, 1.5 g (1.1 equivalents) of acrylic acid chloride was slowly dropped from the dropping funnel. After 2 hours, 1N HCl was added to the flask to quench and return to room temperature. Thereafter, separation and purification operations (hydrochloric acid ⁇ saturated saline solution ⁇ aqueous sodium bicarbonate solution ⁇ saturated saline solution) were repeated, and finally MgSO 4 was added and dehydrated for 24 hours. By IR analysis of the obtained reaction product, C ⁇ C bond and C ⁇ O bond were confirmed, and it was confirmed that the reaction proceeded.
  • Synthesis Example 6 Mixed solution (a10) VEH-0 68 parts by mass TMMP 32 parts by mass Irgacure 907 4 parts by mass HCFC225 100 parts by mass.
  • Example 9 100 parts by mass of dehydrated methyl isobutyl ketone and 33 parts by mass, 39 parts by mass, and 24 parts by mass of AOI with respect to 100 parts by mass of the reaction products (a10) to (a12) obtained in Synthesis Example 6, respectively ((a10) (Corresponding to 1 equivalent each of the hydroxyl groups of (a12)), and 0.01 parts by mass of dibutyltin dilaurate was further added and reacted at 40 ° C. for 24 hours.
  • Example 10 (Preparation of curable composition) Each component was mixed with the following mixing
  • Curable composition (b1) (I) 50 parts by mass of the reaction product of Example 1 (ii) 50 parts by mass of TMPA (iii) 3 parts by mass of Irgacure 907
  • Curable composition (b2) (I) Reaction product of Example 1 90 parts by mass (ii) 10 parts by mass of TMPA (iii) 3 parts by mass of Irgacure 907
  • Curable composition (b3) (I) Reaction product of Example 1 20 parts by mass (ii) 80 parts by mass of TMPA (iii) 3 parts by mass of Irgacure 907
  • Curable composition (b4) (I) Reaction product of Example 2 50 parts by mass (ii) TMPA 50 parts by mass (iii) Irgacure 907 3 parts by mass
  • Curable composition (b5) (I) Reaction product of Example 3 50 parts by mass (ii) TMPA 50 parts by mass (iii) Irgacure 907 3 parts by mass
  • Curable composition (b6) (I) Reaction product of Example 4 50 parts by mass (ii) TMPA 50 parts by mass (iii) Irgacure 907 3 parts by mass
  • Curable composition (b7) (I) Reaction product (a3) of Example 5 50 parts by mass (ii) TMPA 50 parts by mass (iii) Irgacure 907 3 parts by mass
  • Curable composition (b8) (I) Reaction product of Example 5 (a4) 50 parts by mass (ii) TMPA 50 parts by mass (iii) Irgacure 907 3 parts by mass
  • Curable composition (b9) (I) Reaction product of Example 5 (a5) 50 parts by mass (ii) TMPA 50 parts by mass (iii) Irgacure 907 3 parts by mass
  • Curable composition (b10) (I) Reaction product of Example 7 25 parts by mass (ii) TMPA 8 parts by mass (iii) MIBK 50 parts by mass (vi) Irgacure 907 3 parts by mass
  • Curable composition (b11) (I) Reaction product of Example 8 25 parts by mass (ii) TMPA 8 parts by mass (iii) MIBK 50 parts by mass (vi) Irgacure 907 3 parts by mass
  • the obtained curable compositions (b1) to (b11) were all uniform and transparent compositions.
  • the appearance of the obtained curable compositions (b1) to (b11) was evaluated. Evaluation was performed according to the following criteria. The results are shown in Table 7.
  • this reactive organism was analyzed by 19 F-NMR and IR, it was confirmed to be a fluoropolymer having an OH group consisting only of the AEH-1 structural unit in its side chain. Moreover, the number average molecular weight measured by GPC analysis using tetrahydrofuran (THF) as a solvent was 34000, and the weight average molecular weight was 75000.
  • THF tetrahydrofuran
  • Curable composition (c1) (I) Reactive organism of Comparative Synthesis Example 1 50 parts by mass (ii) TMPA 50 parts by mass (iii) Irgacure 907 3 parts by mass
  • Curable composition (c2) (I) 100 parts by mass of TMPA (ii) 3 parts by mass of Irgacure 907
  • the obtained curable compositions (c1) and (c2) were both non-uniform compositions.
  • the appearance of the obtained curable compositions (c1) and (c2) was evaluated. Evaluation was performed according to the following criteria. The results are shown in Table 7.
  • Example 11 (Preparation of coated product) Each of the photocurable compositions (b1) to (b11) obtained in Example 10 was coated on a non-surface-treated acrylic plate by a spin coater at room temperature and vacuum-dried at room temperature for 5 minutes. At this time, the rotation speed of the spin coater was adjusted (500 to 2000 rotations) so that the film thickness after drying was 1 ⁇ m. Moreover, the applicability at the time of application
  • Example 12 Measurement of physical properties of cured film
  • the resulting coating was photocured by irradiating with ultraviolet rays at an intensity of 5000 mJ / cm 2 at room temperature using a high-pressure mercury lamp.
  • a cured film was prepared.
  • the physical properties of the obtained film were evaluated by the following methods. The results are shown in Table 7.
  • Comparative Example 2 The curable composition (c2) obtained in Comparative Example 1 was applied and cured in the same manner as in Examples 11 and 12, and the coating film was evaluated. The results are shown in Table 7.

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  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

L'invention porte sur un composé contenant du fluor polyfonctionnel et sur un procédé de fabrication du composé. L'invention porte également sur un agent de réticulation composé du composé, sur une composition durcissable contenant le composé et sur un produit durci obtenu par durcissement de la composition. Le composé contenant du fluor polyfonctionnel est un composé ayant au moins 2 groupes représentés par la formule générale (1). -S-CX2CHF-Z-O-Rf (1) [Dans la formule, les X peuvent être identiques ou différents et représentent chacun H ou F ; Z représente -CF2- ou une simple liaison ; Rf représente un groupe alkyle contenant du fluor avec 1-40 atomes de carbone, qui a au moins un groupe représenté par la formule suivante : -O-C(=O)-Xa-Rb ou un groupe alkyle contenant du fluor avec 2-100 atomes de carbone, qui a une liaison éther et au moins un groupe représenté par la formule suivante : -O-C(=O)-Xa-Rb ; Xa représente -NH- ou une simple liaison ; et Rb représente un groupe organique ayant au moins une double liaison terminale.]
PCT/JP2009/056131 2008-03-31 2009-03-26 Composé contenant du fluor polyfonctionnel et son procédé de fabrication Ceased WO2009123013A1 (fr)

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KR20130112746A (ko) * 2012-04-03 2013-10-14 아라까와 가가꾸 고교 가부시끼가이샤 다관능 티오(메타)아크릴레이트 수지, 이것을 함유하는 활성 에너지선 경화형 하드코팅 수지조성물과 이것을 경화해서 얻어진 경화막, 경화막이 적층된 플라스틱 필름, 플라스틱 필름을 사용한 플라스틱 사출 성형품 및 가공제품
US10717694B2 (en) 2016-05-09 2020-07-21 3M Innovative Properties Company Hydrofluoroolefins and methods of using same
JP2022138156A (ja) * 2021-03-09 2022-09-22 ダイキン工業株式会社 ハロエーテル及びその製造方法並びにビニルエーテル及びその製造方法

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Publication number Priority date Publication date Assignee Title
KR20130112746A (ko) * 2012-04-03 2013-10-14 아라까와 가가꾸 고교 가부시끼가이샤 다관능 티오(메타)아크릴레이트 수지, 이것을 함유하는 활성 에너지선 경화형 하드코팅 수지조성물과 이것을 경화해서 얻어진 경화막, 경화막이 적층된 플라스틱 필름, 플라스틱 필름을 사용한 플라스틱 사출 성형품 및 가공제품
JP2013231167A (ja) * 2012-04-03 2013-11-14 Arakawa Chem Ind Co Ltd 多官能チオ（メタ）アクリレート樹脂、これを含有する活性エネルギー線硬化型ハードコート樹脂組成物とこれを硬化して得られた硬化膜、硬化膜が積層されたプラスチックフィルム、プラスチックフィルムを用いたプラスチック射出成型品及び加工製品。
KR101972385B1 (ko) 2012-04-03 2019-04-25 아라까와 가가꾸 고교 가부시끼가이샤 다관능 티오(메타)아크릴레이트 수지, 이것을 함유하는 활성 에너지선 경화형 하드코팅 수지조성물과 이것을 경화해서 얻어진 경화막, 경화막이 적층된 플라스틱 필름, 플라스틱 필름을 사용한 플라스틱 사출 성형품 및 가공제품
US10717694B2 (en) 2016-05-09 2020-07-21 3M Innovative Properties Company Hydrofluoroolefins and methods of using same
JP2022138156A (ja) * 2021-03-09 2022-09-22 ダイキン工業株式会社 ハロエーテル及びその製造方法並びにビニルエーテル及びその製造方法
JP7693588B2 (ja) 2021-03-09 2025-06-17 ダイキン工業株式会社 ハロエーテル及びその製造方法並びにビニルエーテル及びその製造方法

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