USRE44096E1 - Fluorine-containing compound having hydrolyzable metal alkoxide moiety, curable fluorine-containing polymer prepared from the same compound, and curable fluorine-containing resin composition comprising the same polymer - Google Patents

Fluorine-containing compound having hydrolyzable metal alkoxide moiety, curable fluorine-containing polymer prepared from the same compound, and curable fluorine-containing resin composition comprising the same polymer Download PDF

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USRE44096E1
USRE44096E1 US13/227,410 US200513227410A USRE44096E US RE44096 E1 USRE44096 E1 US RE44096E1 US 200513227410 A US200513227410 A US 200513227410A US RE44096 E USRE44096 E US RE44096E
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fluorine
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carbon atoms
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Kazuyuki Sato
Tsuyoshi Itagaki
Yasuo Itami
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Daikin Industries Ltd
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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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • 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
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon

Definitions

  • the present invention relates to a novel fluorine-containing compound and polymer having a hydrolyzable metal alkoxide moiety, and a curable fluorine-containing resin composition prepared using the polymer.
  • An object of the present invention is to provide a material which is useful for a laminated article having a practical low reflection, keeps an anti-glaring property, is free from “fading into white color” attributable to surface scattering and is excellent in adhesion.
  • the present invention relates to a curable fluorine-containing polymer (hereinafter referred to as “the first polymer”) having a hydrolyzable metal alkoxide moiety which has a number average molecular weight of from 500 to 1,000,000 and is represented by the formula (2): M N A (2) wherein the structural unit M is a structural unit which is derived from a fluorine-containing ethylenic monomer having a hydrolyzable metal alkoxide moiety and is represented by the formula (M):
  • X 1 and X 2 are the same or different, and each is H or F
  • X 3 is H, F, CH 3 or CF 3
  • X 4 and X 5 are the same or different, and each is H, F or CF 3
  • Rf 1 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and ether bond, which is an organic group in which 1 to 3 hydrogen atoms are replaced by Y 1 where Y 1 is a functional group containing, at its end, at least one hydrolyzable metal alkoxide moiety and having 1 to 50 carbon atoms; a is 0 or an integer of 1 to 3; b and c are the same or different, and each is 0 or 1,
  • the structural unit N is a structural unit derived from a fluorine-containing ethylenic monomer and represented by the formula (N):
  • Rf 2 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and ether bond, which is an organic group in which 1 to 3 hydrogen atoms are replaced by Y 2 where Y 2 is a monovalent organic group having 2 to 10 carbon atoms and containing, at its end, an ethylenic carbon-carbon double bond; a is 0 or an integer of 1 to 3; b and c are the same or different, and each is 0 or 1, the structural unit A is a structural unit derived from a monomer being copolymerizable with the fluorine-containing ethylenic monomers providing the structural units represented by the formulae (M) and (N
  • the present invention relates to a curable fluorine-containing polymer (hereinafter referred to as “the second polymer”) having a hydrolyzable metal alkoxide moiety which has a number average molecular weight of from 500 to 1,000,000 and is represented by the formula (2-1): M N A1 A2 (2-1) wherein the structural unit M is a structural unit which is derived from a fluorine-containing ethylenic monomer having a hydrolyzable metal alkoxide moiety and is represented by the above-described formula (M), the structural unit N is a structural unit which is derived from a fluorine-containing ethylenic monomer and is represented by the above-described formula (N), the structural unit A1 is a structural unit represented by the formula (A1):
  • X 11 , X 12 and X 13 are the same or different, and each is H or F;
  • X 14 is H, F or CF 3 ;
  • h is 0 or an integer of 1 or 2;
  • i is 0 or 1;
  • Rf 4 is a fluorine-containing divalent alkylene group having 1 to 40 carbon atoms or a fluorine-containing divalent alkylene group having 2 to 100 carbon atoms and ether bond;
  • Z 1 is a group selected from the group consisting of —OH, —CH 2 OH, —COOH, a carboxylic acid derivative, —SO 3 H, a sulfonic acid derivative, an epoxy group and a cyano group
  • the structural unit A2 is a structural unit represented by the formula (A2):
  • X 15 , X 16 and X 18 are the same or different, and each is H or F;
  • X 17 is H, F or CF 3 ;
  • h1, i1 and j are the same or different, and each is 0 or 1;
  • Z 2 is H, F, Cl or a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms;
  • Rf 5 is a fluorine-containing divalent alkylene group having 1 to 20 carbon atoms or a fluorine-containing divalent alkylene group having 2 to 100 carbon atoms and ether bond, the structural units M, N, A1 and A2 are contained in amounts of from 0.1 to 90% by mole, from 0 to 99.9% by mole, from 0 to 99.9% by mole and from 0 to 99.9% by mole, respectively, and N+A1+A2 is contained in an amount of from 10 to 99.9% by mole.
  • any of the curable fluorine-containing polymers it is preferable that at least one of Y 1 is bonded to the end of Rf 1 , and further in the second polymer, it is preferable that at least one of Y 2 is bonded to the end of Rf 2 .
  • the structural unit M is preferably a structural unit M1 derived from a fluorine-containing ethylenic monomer and represented by the formula (M1):
  • X 1 , X 2 , X 3 , X 4 , X 5 , Rf 1 , a and c are as defined above.
  • structural unit M is preferably a structural unit M2 derived from a fluorine-containing ethylenic monomer and represented by the formula (M2):
  • Rf 1 is as defined above, or a structural unit M3 derived from a fluorine-containing ethylenic monomer and represented by the formula (M3):
  • Rf 1 is as defined above.
  • Rf 1 is one represented by the formula: —D—Ry wherein —D— is a fluoroether unit represented by the formula (D): O—R n or R—O n (D) in which n is an integer of 1 to 20; R is at least one selected from fluorine-containing divalent alkylene groups having 1 to 5 carbon atoms where at least one of hydrogen atoms is replaced by fluorine atom, and R may be the same or different when n is not less than two; Ry is a hydrocarbon group having 1 to 39 carbon atoms where a part or the whole of hydrogen atoms may be replaced by fluorine atoms, or a hydrocarbon group having 1 to 99 carbon atoms and ether bond where a part or the whole of hydrogen atoms may be replaced by fluorine atoms, which is an organic group in which 1 to 3 hydrogen atoms are replaced by Y 1 (Y 1 is as defined above), and more specifically
  • the structural unit (A1) is a structural unit represented by the formula (A1-1):
  • Rf 4 and Z 1 are as defined in the formula (A1), or a structural unit represented by the formula (A1-2):
  • Rf 4 and Z 1 are as defined in the formula (A1), or the structural unit (A2) is a structural unit derived from at least one monomer selected from the group consisting of tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene and hexafluoropropylene.
  • the present invention also relates to a curable fluorine-containing resin composition
  • a curable fluorine-containing resin composition comprising:
  • the present invention relates to a curable fluorine-containing resin composition for coating comprising:
  • the fluorine-containing compound which has a hydrolyzable metal alkoxide moiety provides the structural unit M of the first and second polymers and is represented by the formula (1):
  • Rf 1 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and ether bond, which is an organic group in which 1 to 3 hydrogen atoms are replaced by Y 1 where Y 1 is a functional group containing, at its end, at least one hydrolyzable metal alkoxide moiety and having 1 to 50 carbon atoms; a is 0 or an integer of 1 to 3; b and c are the same or different, and each is 0 or 1, is a novel compound.
  • FIG. 1 An IR chart of a fluorine-containing allyl ether monomer having a silicon alkoxide and synthesized in Example 1.
  • FIG. 2 An IR chart of a curable fluorine-containing polymer which has a silicon alkoxide and ⁇ -fluoroacryloyl group and is synthesized in Example 3.
  • the first polymer of the present invention is the curable fluorine-containing polymer having a hydrolyzable metal alkoxide moiety which has a number average molecular weight of from 500 to 1,000,000 and is represented by the formula (2): M N A (2) wherein the structural unit M is a structural unit having a hydrolyzable metal alkoxide moiety, the structural unit N is a structural unit having an ethylenic carbon-carbon double bond and the structural unit A is an optional structural unit, and the structural units M, N and A are contained in amounts of from 0.1 to 100% by mole, from 0 to 99.9% by mole and from 0 to 99.9% by mole, respectively.
  • the structural unit M is the structural unit which is derived from a fluorine-containing ethylenic monomer having a hydrolyzable metal alkoxide moiety and is represented by the formula (M):
  • Rf 1 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and ether bond, which is an organic group in which 1 to 3 hydrogen atoms are replaced by Y 1 where Y 1 is a functional group containing, at its end, at least one hydrolyzable metal alkoxide moiety and having 1 to 50 carbon atoms; a is 0 or an integer of 1 to 3; b and c are the same or different, and each is 0 or 1.
  • the structural unit M is particularly preferably the structural unit M1 derived from a fluorine-containing ethylenic monomer and represented by the formula (M1):
  • X 1 , X 2 , X 3 , X 4 , X 5 , Rf 1 , a and c are as defined above.
  • the fluorine-containing polymer having this structural unit M1 is preferable because particularly a refractive index is low, adhesion to various substrates such as a light scattering layer is good and durability can be enhanced.
  • the structural unit M1 is the structural unit M2 derived from a fluorine-containing ethylenic monomer and represented by the formula (M2):
  • Rf 1 is as defined above.
  • This structural unit M2 is preferable because a refractive index is low, adhesion to various substrates such as a light scattering layer is good, durability can be enhanced, and in addition, copolymerizability with other fluorine-containing ethylenic monomers is good.
  • structural unit M1 is the structural unit M3 derived from a fluorine-containing ethylenic monomer and represented by the formula (M3):
  • Rf 1 is as defined above.
  • This structural unit M3 is preferable because a refractive index is low, adhesion to various substrates such as a light scattering layer is good, durability can be enhanced, and in addition, copolymerizability with other fluorine-containing ethylenic monomers is good.
  • Rf 1 contained in the structural units M, M1, M2 and M3 is, as described above, an organic group having 1 to 3 functional groups Y 1 which contains, at its end, at least one hydrolyzable metal alkoxide moiety and has 1 to 50 carbon atoms, and an upper limit of the number of carbon atoms is preferably 30, more preferably 20, particularly preferably 10.
  • the hydrolyzable metal alkoxide moiety in the Y 1 functions to cause a hydrolysis and polycondensation reaction, thereby exhibiting an effect of enhancing good adhesion durability with a substrate having hydroxyl group.
  • Rf 1 is one represented by the formula (Rf1): —D—Ry (Rf1) wherein —D— is a fluoroether unit represented by the formula (D): O—R n or R—O n (D) in which n is an integer of 1 to 20; R is at least one selected from fluorine-containing divalent alkylene groups having 1 to 5 carbon atoms where at least one of hydrogen atoms is replaced by fluorine atom, and R may be the same or different when n is not less than two; Ry is a hydrocarbon group having 1 to 39 carbon atoms where a part or the whole of hydrogen atoms may be replaced by fluorine atoms or a hydrocarbon group having 1 to 99 carbon atoms and ether bond where a part or the whole of hydrogen atoms may be replaced by fluorine atoms, which is an organic group in which 1 to 3 hydrogen atoms are replaced by Y 1 (Y 1 is as defined above).
  • R— is a fluorine-containing divalent alkylene group having 1 to 5 carbon atoms and has at least one fluorine atom, thereby being capable of contributing to further lowering of a viscosity of the compound, enhancement of heat resistance, lowering of a refractive index and enhancement of solubility in general purpose solvents as compared with conventional compounds having an alkylene ether unit or an alkoxyl group having no fluorine atom.
  • Examples of —(O—R)— or —(R—O)— in —D— are —(OCF 2 CF 2 CF 2 )—, —(CF 2 CF 2 CF 20 )— —(CF 2 CF 2 CF 2 O)—, —(OCFQ 1 CF 2 )—, —(OCF 2 CFQ 1 )—, —(OCFQ 2 )—, —(CFQ 2 O)—, —(OCH 2 CF 2 CF 2 )—, (OCF 2 CF 2 CH 2 )—, —(OCH 2 CH 2 CF 2 )—, —(OCF 2 CH 2 CH 2 )—, —(OCF 2 CF 2 CF 2 )—, —(CF 2 CF 2 CF 20 )— —(CF 2 CF 2 CF 2 O)—, —(OCFQ 2 CH 2 )—, —(CH 2 CFQ 2 O)—, —(CH 2
  • —D— is a repeating unit comprising one kind or two or more kinds selected from —(OCFQ 1 CF 2 )—, —(OCF 2 CF 2 CF 2 )—, —(OCH 2 CF 2 CF 2 )—, —(OCFQ 2 )—, —(OCQ 3 2 )—, —(CFQ 1 CF 2 O)—, —(CF 2 CF 2 CF 2 O)—, —(CH 2 CF 2 CF 20 )— —(CH 2 CF 2 CF 2 O)—, —(CFQ 2 O)— and —(CQ 3 2 O)—, particularly preferably a repeating unit comprising one kind or two or more kinds selected from —(OCFQ 1 CF 2 )—, —(OCF 2 CF 2 CF 2 )—, —(OCH 2 CF 2 CF 2 )—, —(CFQ 1 CF 2 O)—, —(—(CFQ 1
  • —O—O— structural unit (specifically —R—O—O—R—, —O—O—R—, —R—O—O— or the like) is not contained in the above described fluorine-containing ether unit —D— and the above described Rf 1 .
  • Ry is preferably a group represented by the formula (Ry): —O—Ry 1 (Ry) wherein Ry 1 is an organic-inorganic complex radical represented by the formula (Ry1): —(R 11 ) p R 12 —(Y 1a ) m (Ry1) where p is 0 or 1; m is an integer of 1 to 3; R 11 is —CONH—; R 12 is a di-, tri- or tetra-valent hydrocarbon group having 1 to 39 carbon atoms where a part or the whole of hydrogen atoms may be replaced by fluorine atoms or a di-, tri- or tetra-valent hydrocarbon group having 1 to 99 carbon atoms and ether bond where a part or the whole of hydrogen atoms may be replaced by fluorine atoms; Y 1a is a functional group represented by the formula: —[M 1 O(R 29 ) a (R 30 ) b (R 31 ) c (
  • each of X 30 and X 33 is F or CF 3 ; each of X 31 and X 32 is H or F; o+p+q is 1 to 30; r is 0 or 1; sand tare s and t are 0 or 1), and the like.
  • Examples of the metals M 1 and M 2 in Y 1a are Cu as the IB group; Ca, Sr and Ba as the IIA group; Zn as the IIB group; B, Al and Ga as the IIIA group; Y as the IIIB group; Si and Ge as the IVA group; Pb as the IVB group; P and Sb as the VA group; V and Ta as the VB group; W as the VIB group; and La and Nd as the lanthanide.
  • metals of the IVA group are preferable as Y 1a , and especially —Si(OCH 3 ) 3 , —Si(OC 2 H 5 ) 3 , —SiCH 3 (OC 2 H 5 ) 2 and the like are preferable from the viewpoint of good adhesion to a substrate having hydroxyl group and durability after hydrolysis and polycondensation, and also —[SiO(OCH 3 ) 2 ] n —Si(OCH 3 ) 3 , —[SiO(OC 2 H 5 ) 2 ] n —Si(OC 2 H 5 ) 3 and the like, where n is an integer of 1 to 11, are preferable from the viewpoint of enhancement of surface hardness in addition to good adhesion to a substrate having hydroxyl group and durability thereof after hydrolysis and polycondensation.
  • —Si(OCH 3 ) 3 , —Si(OC 2 H 5 ) 3 , —SiCH 3 (OC 2 H 5 ) 2 and the like are particularly preferable as Y 1a .
  • examples of Y 1a are:
  • Ca of the IIA group —Ca(OR 39 ), and a suitable example is —Ca(OCH 3 );
  • Zn of the IIB group —Zn(OR 39 ), and a suitable example is —Zn(OC 2 H 5 );
  • B of the IIIA group —B(OR 39 ) 2 , and a suitable example is —B(OCH 3 ) 2 ;
  • Y of the IIIB group —Y(OR 39 ) 2 , and a suitable example is —Y(OC 4 H 9 ) 2 ;
  • Pb of the IVB group —Pb(OR 39 ) 3
  • a suitable example is —Pb(OC 4 H 9 ) 3 ;
  • Ta of the VB group —Ta(OR 39 ) 4
  • a suitable example is —Ta(OC 3 H 7 ) 4 ;
  • W of the VIB group —W(OR 39 ) 5 , and a suitable example is —W(OC 2 H 5 ) 5 ;
  • La of the lanthanide —La(OR 39 ) 2
  • a suitable example is —La(OC 3 H 7 ) 2 ;
  • R 39 is a hydrocarbon group having 1 to 10 carbon atoms in which a part or the whole of hydrogen atoms may be replaced by fluorine atoms.
  • the structural unit M is preferably the structural unit M1, and the structural unit M1 is preferably the structural unit M2 or the structural unit M3.
  • the structural unit M is preferably the structural unit represented by the formula (2-2):
  • X 1 , X 2 , X 3 , X 4 , X 5 , D, Ry, a, b and c are as defined above, from the viewpoint of decreasing a refractive index and a viscosity and also from the viewpoint of excellent adhesion durability to a substrate having hydroxyl group and heat resistance.
  • the structural unit of the formula (2-2) is a structural unit represented by the formula (2-3):
  • X 1 , X 2 , X 3 , X 4 , X 5 , D, Ry, a and c are as defined above.
  • the structural unit N is an optional structural unit which is derived from a fluorine-containing ethylenic monomer and is represented by the formula (N):
  • X 1 and X 2 are the same or different, and each is H or F;
  • X 3 is H, F, CH 3 or CF 3 ;
  • X 4 and X 5 are the same or different, and each is H, F or CF 3 ;
  • the structural unit N is a structural unit N1 derived from a fluorine-containing ethylenic monomer and represented by the formula (N1):
  • X 1 , X 2 , X 3 , X 4 , X 5 , Rf 2 , a and c are as defined above.
  • the fluorine-containing polymer having this structural unit N1 is preferable because a curing reactivity by contact with a radical or a cation can be enhanced.
  • the structural unit N1 is a structural unit N2 derived from a fluorine-containing ethylenic monomer and represented by the formula (N2):
  • Rf 2 is as defined above.
  • This structural unit N2 is a structural unit of a fluorine-containing allyl ether having an ethylenic carbon-carbon double bond at its end, and is preferable because not only near infrared transparency can be enhanced but also a refractive index can be decreased, and also polymerizability is good and copolymerizability with other fluorine-containing ethylenic monomers is satisfactory.
  • An another preferable example of the structural unit N1 is a structural unit N3 derived from a fluorine-containing ethylenic monomer and represented by the formula (N3):
  • Rf 2 is as defined above.
  • This structural unit N3 is a structural unit of a fluorine-containing vinyl ether having an ethylenic carbon-carbon double bond at its end, and is preferable because not only near infrared transparency can be enhanced but also a refractive index can be decreased, and also copolymerizability with other fluorine-containing ethylenic monomers is satisfactory.
  • the Y 2 contained in the structural units N, N1, N2 and N3 is, as described supra, a monovalent organic group having 2 to 10 carbon atoms and containing an ethylenic carbon-carbon double bond at its end.
  • This carbon-carbon double bond contained in the Y 2 has an ability of causing a polycondensation reaction, and can provide a cured (crosslinked) article.
  • a polymerization reaction or a condensation reaction is caused between the fluorine-containing polymer molecules or between the fluorine-containing polymer and the curing (crosslinking) agent to be added as case demands, for example, by a contact with a radical or a cation, and thereby a cured (crosslinked) article can be provided.
  • the first preferable Y 2 is: O d C ⁇ O e Y 2a wherein Y 2a is an alkenyl group or fluorine-containing alkenyl group having 2 to 5 carbon atoms and containing an ethylenic carbon-carbon double bond at its end; d and e are the same or different and each is 0 or 1.
  • Y 2a is: —CX 6 ⁇ CX 7 X 8 wherein X 6 is H, F, CH 3 or CF 3 ; X 7 and X 8 are the same or different and each is H or F, and this group is preferable because a curing reactivity by a contact with a radical or a cation is high.
  • Y 2a Preferable examples of Y 2a are:
  • Y 2 is: —O(C ⁇ O)CX 6 ⁇ CX 7 X 8 wherein X 6 is H, F, CH 3 or CF 3 ; X 7 and X 8 are the same or different and each is H or F, and this group is preferable because a curing reactivity by a contact with a radical is high and a cured article can be obtained easily by photo-curing.
  • those having a structure of —O(C ⁇ O)CF ⁇ CH 2 are preferable because near infrared transparency can be enhanced, a curing (crosslinking) reactivity is especially high and a cured article can be obtained efficiently.
  • the above described organic group Y 2 having a carbon-carbon double bond in its side chain may be introduced into the end of the polymer trunk chain.
  • —Rf 2 — (a group obtained by removing Y 2 from the mentioned —Rf 2 ) contained in the structural units N, N1, N2 and N3 is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond.
  • a fluorine atom is to be bonded to the carbon atom contained therein, and is generally a fluorine-containing alkylene group or a fluorine-containing alkylene group having ether bond, in which a fluorine atom and hydrogen atom or a chlorine atom are bonded to the carbon atom.
  • the Rf 2 containing more fluorine atoms (a high fluorine content), and more preferable is a perfluoroalkylene group or a perfluoroalkylene group having ether bond.
  • the fluorine content of the fluorine-containing polymer is not less than 25% by mass, preferably not less than 40% by mass. This fluorine content is preferable because not only a near infrared transparency of the fluorine-containing polymer can be enhanced but also a refractive index thereof can be decreased, and even if a curing degree (crosslinking density) is increased particularly for the purpose of enhancing heat resistance and elastic modulus of a cured article, a near infrared transparency can be maintained high or a refractive index can be maintained low.
  • the number of carbon atoms of fluorine-containing alkylene groups is preferably 1 to 20, more preferably 1 to 10, and the number of carbon atoms of fluorine-containing alkylene groups having ether bond is preferably 2 to 30, more preferably 2 to 20.
  • each of X 34 and X 37 is F or CF 3 ; each of X 35 and X 36 is H or F; o+p+q is 1 to 30; r is 0 or 1; sand tare s and t are 0 or 1), and the like.
  • the structural unit N constituting the fluorine-containing polymer used in the present invention is preferably the structural unit N1, and further the structural unit N1 is preferably the structural unit N2 or the structural unit N3. Then examples of the structural unit N2 and the structural unit N3 are explained below.
  • Preferable examples of the monomers constituting the structural unit N2 are:
  • Rf 7 and Rf 8 are perfluoroalkyl groups having 1 to 5 carbon atoms; n is 0 or an integer of 1 to 30; X is H, CH 3 , F or CF 3 .
  • Preferable examples of the monomers constituting the structural unit N3 are:
  • Rf 9 and Rf 10 are perfluoroalkyl groups having 1 to 5 carbon atoms; m is 0 or an integer of 1 to 30; n is an integer of 1 to 3; X is H, CH 3 , F or CF 3 .
  • monomers constituting the structural unit N of the fluorine-containing polymer other than the structural unit N2 and N3 are, for instance,
  • the structural unit A is a structural unit derived from a monomer copolymerizable with the fluorine-containing ethylenic monomers providing the structural units represented by the formulae (M) and (N).
  • the structural unit A is an optional component and is not limited as long as it is a monomer copolymerizable with the structural units M and N.
  • the structural unit A may be optionally selected depending on intended applications of the fluorine-containing polymer and the cured article obtained therefrom and required characteristics.
  • Examples of the structural unit A are, for instance, the following structural units.
  • These structural units (A1) are preferable because adhesion of the fluorine-containing polymer and the cured article thereof to a substrate and solubility in a solvent, particularly in general purpose solvents can be imparted and also because functions such as crosslinkability can be imparted.
  • Preferred structural units A1 of the fluorine-containing ethylenic monomer having functional group are structural units represented by the formula (A1):
  • X 11 , X 12 and X 13 are the same or different and each is H or F;
  • X 14 is H, F or CF 3 ;
  • h is 0 or an integer of 1 or 2;
  • i is 0 or 1;
  • Rf 4 is a fluorine-containing divalent alkylene group having 1 to 40 carbon atoms or a fluorine-containing divalent alkylene group having 2 to 100 carbon atoms and ether bond;
  • Z 1 is a functional group selected from the group consisting of —OH, CH 2 OH, —COOH, a carboxylic acid derivative, —SO 3 H, a sulfonic acid derivative, an epoxy group and a cyano group, and particularly preferred are structural units which are derived from: CH 2 ⁇ CFCF 2 ORf 4 —Z 1 wherein Rf 4 and Z 1 are as defined above, and are represented by the formula (A1-1):
  • Rf 4 and Z 1 are as defined in the formula (A1).
  • Rf 4 and Z 1 are as defined in the formula (A1).
  • fluorine-containing ethylenic monomer having functional group examples include:
  • These structural units A2 are preferable from the point that a refractive index of the fluorine-containing polymer and the cured article obtained therefrom can be maintained low and because a refractive index can be further decreased. Also these structural units are preferable from the point that by selecting the monomer, mechanical characteristics and glass transition temperature of the polymer can be adjusted, and particularly the glass transition temperature can be increased by copolymerization with the structural units M and N.
  • Examples of the preferred structural units (A2) of the fluorine-containing ethylenic monomer are those represented by the formula (A2):
  • X 15 , X 16 and X 18 are the same or different and each is H or F;
  • X 17 is H, F or CF 3 ;
  • h1, i1 and j are the same or different and each is 0 or 1;
  • Z 2 is H, F, Cl or a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms;
  • Rf 5 is a fluorine-containing divalent alkylene group having 1 to 20 carbon atoms or a fluorine-containing divalent alkylene group having 2 to 100 carbon atoms and ether bond.
  • Examples thereof are preferably structural units derived from monomers such as:
  • CH 2 ⁇ CF CF 2 n Z 2 (Z 2 is as defined in the formula (A2), n is from 1 to 10) and CH 2 ⁇ CHOCH 2 CF 2 n Z 2 (Z 2 is as defined in the formula (A2), n is from 1 to 10).
  • these structural units are structural units derived from at least one monomer selected from the group consisting of tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene and hexafluoropropylene because a refractive index of the curable fluorine-containing polymer and the cured article obtained therefrom can be maintained low.
  • Examples of the preferred fluorine-containing aliphatic ring structural unit A3 are those represented by the formula (A3):
  • X 19 , X 20 , X 23 , X 24 , X 25 and X 26 are the same or different and each is H or F;
  • X 21 and X 22 are the same or different and each is H, F, Cl or CF 3 ;
  • Rf 6 is a fluorine-containing alkylene group having 1 to 10 carbon atoms or a fluorine-containing alkylene group having 2 to 10 carbon atoms and ether bond;
  • Rf 6 , X 21 and X 22 are as defined above.
  • fluorine-containing aliphatic ring structural units are, for instance,
  • those structural units A4 can enhance solubility in general-purpose solvents and can improve compatibility with additives, for example, a photocatalyst and a curing agent to be added as case demands.
  • non-fluorine-containing ethylenic monomer examples include as follows.
  • CH 2 ⁇ CHOR CH 2 ⁇ CHOCOR (R: hydrocarbon group having 1 to 20 carbon atoms) and the like.
  • Acrylic acid methacrylic acid, acrylic esters, methacrylic acid esters, maleic anhydride, maleic acid, maleic acid esters and the like.
  • Monomers obtained by replacing a part or the whole of hydrogen atoms of those non-fluorine-containing ethylenic monomers with heavy hydrogen atoms are more preferred from the viewpoint of transparency.
  • the structural unit A5 of an alicyclic monomer may be introduced as a component copolymerizable with the structural units M and N, more preferably as the third component in addition to the structural units M and N and the structural unit of the above-mentioned fluorine-containing ethylenic monomer or non-fluorine-containing ethylenic monomer (the above-mentioned A3 or A4), thereby making a glass transition temperature and a hardness high.
  • Examples of the alicyclic monomer A5 are norbornene derivatives represented by:
  • m is 0 or an integer of from 1 to 3;
  • A, B, C and D are the same or different and each is H, F, Cl, COOH, CH 2 OH, a perfluoroalkyl group having 1 to 5 carbon atoms or the like, alicyclic monomers such as:
  • the first fluorine-containing polymer may be a homopolymer of the structural unit M or may be a copolymer of the structural unit M with the structural unit N and further the structural unit A.
  • the homopolymer is advantageous from the point that a refractive index can be maintained low, functions of imparting a near infrared transparency and adhesion durability to a substrate having hydroxyl group can be imparted, and further a high hardness of a coating film can be obtained.
  • the content of the structural unit M may be not less than 0.1% by mole based on the whole structural units constituting the fluorine-containing polymer, and it is preferable that the content is not less than 2.0% by mole, preferably not less than 5% by mole, more preferably not less than 10% by mole in order to obtain a cured article having a high hardness by curing (crosslinking) and excellent abrasion resistance, scratch resistance, chemical resistance and solvent resistance.
  • the content of the structural unit M is not less than 10% by mole, preferably not less than 20% by mole, further preferably not less than 30% by mole, particularly preferably not less than 40% by mole.
  • An upper limit thereof is less than 100% by mole.
  • a molecular weight, for example, a number average molecular weight of the fluorine-containing polymer can be selected within a range from 500 to 1,000,000, preferably from 1,000 to 500,000, particularly from 2,000 to 200,000.
  • the number average molecular weight is most preferably selected within a range from 5,000 to 100,000.
  • the second polymer of the present invention is a curable fluorine-containing polymer having a hydrolyzable metal alkoxide moiety which has a number average molecular weight of from 500 to 1,000,000 and is represented by the formula (2-1): M N A1 A2 (2-1) wherein the structural unit M and the structural unit N are the same as in the first polymer and the structural unit A1 and the structural unit A2 are as defined above, the structural units M, N, A1 and A2 are contained in amounts of from 0.1 to 90% by mole, from 0 to 99.9% by mole, from 0 to 99.9% by mole and from 0 to 99.9% by mole, respectively, and N+A1+A2 is contained in an amount of from 10 to 99.9% by mole.
  • the content of the structural unit M in the second fluorine-containing polymer is not less than 0.1% by mole based on the whole structural units constituting the fluorine-containing polymer.
  • the content is not less than 2.0% by mole, preferably not less than 5% by mole, more preferably not less than 10% by mole.
  • the content is not less than 10% by mole, preferably not less than 20% by mole, more preferably not less than 50% by mole.
  • An upper limit of the content is less than 100% by mole.
  • the contents of the structural units N, A1 and A2 are each not more than 99.9% by mole.
  • the total percent by mole of N+A1+A2 is from 10 to 99.9% by mole.
  • a more preferable total percent by mole of N+A1+A2 is not less than 20% by mole, further preferably not less than 30% by mole, and not more than 60% by mole, further preferably not more than 50% by mole.
  • a molar ratio (N/(N+A1+A2)) of the structural unit N to the sum of the structural units N, A1 and A2 in the second fluorine-containing polymer is preferably 1/100 to 100/100, more preferably 30/100 to 100/100, further preferably 50/100 to 100/100, particularly preferably 70/100 to 100/100.
  • a molar ratio (A1/(N+A1+A2)) of the structural unit A1 to the sum of the structural units N, A1 and A2 in the second fluorine-containing polymer is preferably 1/100 to 50/100, more preferably 1/100 to 40/100, further preferably 1/100 to 30/100.
  • a molecular weight, for example, a number average molecular weight of the second fluorine-containing polymer can be selected within a range from 500 to 1,000,000, preferably from 1,000 to 500,000, particularly preferably from 2,000 to 200,000.
  • the number average molecular weight is most preferably selected within a range from 5,000 to 100,000.
  • the second polymer comprises, as essential structural units, the structural unit N and/or the structural unit A which are optional structural units of the first polymer, and is specifically so defined.
  • various combinations of the structural unit M, the structural unit N and the structural unit A can be selected from the above described examples, depending on intended applications, physical properties (particularly glass transition temperature, hardness, etc.), functions (transparency) and the like.
  • the fluorine-containing polymer is preferably soluble in general purpose solvents, for example, in at least one of ketone solvents, acetic acid ester solvents, alcohol solvents and aromatic solvents or in solvent mixtures containing at least one of general purpose solvents.
  • the fluorine-containing polymer being soluble in general purpose solvents is preferable because film forming property and homogeneity are excellent particularly in forming a thin film having a thickness of not more than 0.3 ⁇ m 3 ⁇ m, for example, of the order of 0.1 ⁇ m in a process for forming a coating film, and also is advantageous from the viewpoint of productivity.
  • the method of (3) is preferable because the curable fluorine-containing polymer of the present invention having a hydrolyzable metal alkoxide moiety is obtained without a curing reaction of the carbon-carbon double bond at an end of a side chain of the fluorine-containing polymer.
  • radical polymerization method anionic polymerization method, cationic polymerization method and the like can be employed.
  • the radical polymerization method is particularly preferable because in the case of the monomers exemplified for obtaining the polymer having a hydrolyzable metal alkoxide moiety, it is easy to control quality of the polymer such as a composition and a molecular weight and produce the polymer on an industrial scale.
  • the fluorine-containing ethylenic monomer providing the structural unit M namely the fluorine-containing compound having a hydrolyzable metal alkoxide moiety and represented by the formula (1):
  • X 1 and X 2 are the same or different, and each is H or F;
  • X 3 is H, F, CH 3 or CF 3 ;
  • X 4 and X 5 are the same or different, and each is H, F or CF 3 ;
  • Rf 1 is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and ether bond, which is an organic group in which 1 to 3 hydrogen atoms are replaced by Y 1 where Y 1 is a functional group containing, at its end, at least one hydrolyzable metal alkoxide moiety and having 1 to 50 carbon atoms;
  • a is 0 or an integer of 1 to 3;
  • b and c are the same or different, and each is 0 or 1, is a novel compound.
  • a means of initiating the polymerization of such a novel fluorine-containing compound is not limited particularly as long as the polymerization proceeds radically.
  • the polymerization is initiated, for example, with an organic or inorganic radical polymerization initiator, heat, light, ionizing radiation or the like.
  • the polymerization can be carried out by solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization or the like.
  • the present invention also relates to the curable fluorine-containing resin composition
  • the curable fluorine-containing resin composition comprising:
  • thermally curable or two-component cold curing agents in addition to active energy curing initiators can be used, and active energy curing initiators are preferable because the composition is applicable to, for example, transparent resin substrates since a curing reaction can be carried out at relatively low temperatures.
  • the active energy curing initiator is a compound which generates a radical or a cation (acid) only by irradiation of active energy rays such as electromagnetic wave having a wavelength of not more than 350 nm, namely ultraviolet ray, electron beam, X-ray or ⁇ -ray, and functions as a catalyst for initiating the curing (crosslinking reaction) of the crosslinkable group (for example, carbon-carbon double bond) of the fluorine-containing prepolymer.
  • active energy rays such as electromagnetic wave having a wavelength of not more than 350 nm, namely ultraviolet ray, electron beam, X-ray or ⁇ -ray
  • the curing (crosslinking reaction) of the crosslinkable group for example, carbon-carbon double bond
  • initiators generating a radical or a cation (acid) by means of ultraviolet ray particularly those generating a radical are used.
  • the curable fluorine-containing resin composition of the present invention since a curing reaction can be initiated easily with the above described active energy rays, heating at high temperature is not necessary, and a curing reaction can be carried out at relatively low temperature. Therefore, the composition is preferable since it is applicable to substrates, for example, even transparent resin substrates which have low heat resistance and are easily subject to deformation, decomposition and coloration with heat.
  • composition of the present invention is suitable particularly as a starting material for a laminated article which has anti-glaring property and low reflection and is used for suppressing lowering of visibility of an image in image displaying apparatuses such as a liquid crystal display (LCD), a flat panel display (FPD), an organic electroluminescent device (EL) and a plasma display (PDP).
  • LCD liquid crystal display
  • FPD flat panel display
  • EL organic electroluminescent device
  • PDP plasma display
  • the curing agent (b) in the composition of the present invention is optionally selected depending on kind of the crosslinkable group (for example, a hydrolyzable metal alkoxide moiety or a carbon-carbon double bond) in the fluorine-containing polymer (a) (whether the group is radically reactive or cationically (acid) reactive), kind of active energy rays (wavelength range) to be used, intensity of irradiation, and the like.
  • kind of the crosslinkable group for example, a hydrolyzable metal alkoxide moiety or a carbon-carbon double bond
  • the fluorine-containing polymer (a) whether the group is radically reactive or cationically (acid) reactive
  • kind of active energy rays wavelength range
  • the initiator photo-radical generator
  • active energy rays in an ultraviolet region are, for instance, as follows.
  • Acetophenone chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, ⁇ -aminoacetophenone and the like.
  • Benzoin benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethylketal and the like.
  • Benzophenone benzoylbenzoic acid, methyl o-benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propylbenzophenone, acrylated benzophenone, Michler's ketone and the like.
  • photo initiators such as amines, sulfones and sulfines may be added as case demands.
  • cationically (acid) reactive initiators photoacid generators
  • Iodonium salt sulfonium salt, phosphonium salt, diazonium salt, ammonium salt, pyridinium salt and the like.
  • curable fluorine-containing resin composition of the present invention may be blended various additives, as case demands, in addition to the above described compounds.
  • additives are, for instance, a silane coupling agent, a plasticizer, a discoloration inhibitor, an antioxidant, an inorganic filler, a leveling agent, a viscosity regulating agent, a light stabilizer, a water absorbent, a pigment, a dye, a reinforcing agent and the like.
  • composition of the present invention can be blended fine particles or ultrafine particles of inorganic compounds for the purposes of increasing a hardness of a cured article and regulating a refractive index.
  • the fine particles of inorganic compound are not limited particularly, and preferred are compounds having a refractive index of not more than 1.5. Specifically desirable are fine particles of magnesium fluoride (refractive index: 1.38), silicon oxide (refractive index: 1.46), aluminum fluoride (refractive index: 1.33 to 1.39), calcium fluoride (refractive index: 1.44), 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) and the like. It is desirable that a particle size of the fine particles is small enough as compared with a wavelength of visible light in order to secure transparency of the material having a low refractive index. Specifically the particle size is not more than 100 nm, particularly preferably not more than 50 nm.
  • the fine particles of inorganic compound are used in the form of organic sol in which the fine particles have been previously dispersed in an organic dispersant in order not to lower dispersion stability in the composition, adhesion in the low refractive index material and the like.
  • Further surfaces of the fine particles of inorganic compound can be decorated previously with various coupling agents or the like in order to enhance dispersion stability, adhesion in the low refractive index material and the like of the fine particles of inorganic compound in the composition.
  • the coupling agents are, for instance, organosilicon compounds; metal alkoxides such as aluminum, titanium, zirconium, antimony and a mixture thereof; salts of organic acid; coordination compounds having ligand; and the like.
  • the curable fluorine-containing polymer (a) or the additives may be in the form of dispersion or solution in the solvent (c). Being in the form of uniform solution is preferred to form a uniform thin coating film and also to enable the film to be formed at relatively low temperature.
  • the present invention also relates to the curable fluorine-containing resin composition for coating obtained by blending a solvent to the above-mentioned curable fluorine-containing resin composition
  • the solvent to be used is not limited particularly as long as the fluorine-containing polymer (a), the curing agent, and additives to be added as case demands such as a leveling agent and a light stabilizer are uniformly dissolved or dispersed in it. Particularly preferred is a solvent dissolving the fluorine-containing polymer (a) uniformly.
  • solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate and ethyl cellosolve acetate
  • ester solvents such as diethyl oxalate, ethyl pyruvate, ethyl-2-hydroxybutyrate, ethyl acetoacetate, butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 2-hydroxyisobutyrate and ethyl 2-hydroxyisobutyrate; propylene glycol solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol solvents such as propylene glyco
  • a fluorine-containing solvent may be used as case demands.
  • fluorine-containing solvent examples include CH 3 CCl 2 F (HCFC-141b), a mixture of CF 3 CF 2 CHCl 2 and CClF 2 CF 2 CHClF (HCFC-225), perfluorohexane, perfluoro(2-butyltetrahydrofuran), methoxy-nonafluorobutane, 1,3-bistrifluoromethylbenzene, and in addition, fluorine-containing alcohols such as:
  • fluorine-containing solvents may be used solely, in a mixture thereof or in a mixture of one or more of the fluorine-containing solvents and non-fluorine-containing solvents.
  • ketone solvents acetic acid ester solvents, alcohol solvents and aromatic solvents are preferred from the viewpoint of coatability and productivity in coating.
  • the solid content of the coating composition is good enough as far as coatability is good, a low molecular weight monomer component etc. hardly remain in the coating film after the curing and the surface of the coating film is free from tackiness.
  • the solid content may be selected within a range of the order of 0.5 to 10% by mass.
  • the curable fluorine-containing resin composition of the present invention is formed into a cured article or a cured film by curing, for example, by photocuring, and can be applied to various substrates and can be used to various applications.
  • kind of a product namely kind of a substrate which is provided with a low reflection by means of the cured article or the cured film is not limited particularly.
  • the substrate are, for instance, inorganic materials such as glass, stone, concrete and tile; metals such as iron, aluminum and copper; wood, paper, printed matter, printing paper, picture and the like.
  • resins such as a vinyl chloride resin, polyethylene terephthalate, cellulose resin such as triacetyl cellulose, polycarbonate resin, polyolefin resin, acrylic resin, phenol resin, xylene resin, urea resin, melamine resin, diallyl phthalate resin, furan resin, amino resin, alkyd resin, urethane resin, vinyl ester resin, polyimide resin and polyamide resin.
  • an anti-glaring substrate for liquid crystal display has a surface coated with fine inorganic particles, and is used preferably and as a result, can effectively exhibit anti-glaring property and a low reflection effect.
  • composition of the present invention is effectively applied on the following articles.
  • Optical parts such as prism, lens sheet, polarizing plate, optical filter, lenticular lens, Fresnel lens, screen of rear projection display, lens for reduction projection type exposure meter, optical fiber and optical coupler; transparent protection plates represented by glass for show window, glass for show case, a cover for advertisement and a cover for photo-stand; protection plates for CRT, liquid crystal display, plasma display and rear projection display; optical recording media represented by optical magnetic disk, read-only type optical disks such as CD•LD•DVD, phase transition type optical disk such as PD and hologram recording; photolithography-related members for production of semiconductors such as photoresist, photomask, pellicle and reticule; protection covers for light emitters such as halogen lamp, fluorescent lamp and incandescent lamp; and sheet or film for adhering to the above-mentioned articles.
  • transparent protection plates represented by glass for show window, glass for show case, a cover for advertisement and a cover for photo-stand
  • composition of the present invention is also effectively applied as a sealing agent on the following articles.
  • Photo-semiconductor i.e. light emission devices such as LED; photodetectors such as photo transistor, photo diode and CCD; and semiconductor devices (photo-semiconductor device) such as EPROM.
  • composition of the present invention is also effective as an adhesive when applied to articles in the form mentioned below.
  • Measuring is carried out at room temperature with a Fourier-transform infrared spectrophotometer 1760X available from Perkin Elmer Co., Ltd.
  • the fluorine content (% by mass) is obtained by burning 10 mg of a sample by an oxygen flask combustion method, absorbing cracked gas in 20 ml of de-ionized water and then measuring a fluorine ion concentration in the fluorine ion-containing solution through fluoride-ion selective electrode method (using a fluorine ion meter model 901 available from Orion).
  • FIG. 1 An IR chart is shown in FIG. 1 .
  • this polymer was a copolymer comprising a fluorine-containing allyl ether having OH group and a fluorine-containing allyl ether having —Si(OR) 3 group in a percent by mole ratio of 50:50.
  • a number average molecular weight of the polymer was 9,000, and a weight average molecular weight thereof was 22,000.
  • the ether solution after the reaction was poured into the dropping funnel, and after repeating washing with water, 2% hydrochloric acid solution, 5% NaCl solution and then water, was dried with anhydrous magnesium sulfate, and then the ether solution was separated by filtration.
  • this ether solution was a copolymer comprising a fluorine-containing allyl ether having OCOCF ⁇ CH 2 group, a fluorine-containing allyl ether having OH group, and a fluorine-containing allyl ether having —Si(OR) 3 group in a percent by mole ratio of 40:10:50.
  • the obtained copolymer was coated on a silicon wafer, and formed into a cast film at room temperature. According to IR analysis of the cast film, an absorption of carbon-carbon double bond was observed at 1,661 cm ⁇ 1 , an absorption of C ⁇ O group, at 1,770 cm ⁇ 1 , and an absorption of Si(OCH 3 ) 3 group, at 1,100 cm ⁇ 1 . An IR chart is shown in FIG. 2 .
  • ether solution having silicon alkoxide and ⁇ -fluoroacryloyl group and obtained in Example 3 was added methyl isobutyl ketone (MIBK), and then ether was distilled off with an evaporator to adjust the polymer concentration to 3.75% by weight.
  • MIBK methyl isobutyl ketone
  • a fluorine-containing resin composition for coating containing no silicon alkoxide was prepared in the same manner as in Example 4 except that the fluorine-containing allyl ether having —Si(OR) 3 group was not contained in the fluorine-containing resin composition prepared by means of Examples 2 to 4.
  • the above-mentioned coating composition was applied to an un-coated PET film subjected to anti-glaring treatment with an applicator, and dried at 25° C. for five minutes.
  • the dried coating film was irradiated with ultraviolet light at an intensity of 3,000 mJ/cm 2 U at room temperature using a high pressure mercury lamp.
  • the 3.75% MIBK solution of the curable fluorine-containing polymer (the polymer solution before adding the curing catalyst in the above-mentioned (1) of Examples 4 and 5) was coated on a PET film with an applicator so that a coating thickness after the drying became about 100 ⁇ m. After drying at 50° C. for 10 minutes, an obtained cast film was peeled from the PET film, and a refractive index thereof was measured using an Abbe's refractometer at 25° C. with light having a wavelength of 550 nm. The results are shown in Table 1.
  • the coating compositions prepared in the above-mentioned (1) of Examples 4 and 5 were coated on an aluminum foil with an applicator so that a coating thickness became about 100 ⁇ m, followed by drying at 50° C. for 10 minutes. After the dried coating film was subjected to irradiation of light in the same manner as in (2) above, the aluminum foil was molten with diluted hydrochloric acid to make a sample film. A refractive index of the obtained cured film was measured in the same manner as in (3) above. The results are shown in Table 1.
  • Tackiness was evaluated by touching with fingers according to JIS K4500.
  • condition (dissolved or peeled) of the coating film surface is evaluated.
  • a cotton cloth (BEMCOT (Registered trademark) M-3 available from Asahi Chemical Co., Ltd.) is fitted to a rubbing tester, and the laminated article is rubbed by 100 rubbing cycles at a load of 100 gf/cm 2 . Then the condition of the film is observed.
  • BEMCOT Registered trademark
  • M-3 available from Asahi Chemical Co., Ltd.
  • a PET film provided with the laminated article was set on a thin film reflectance meter F-20 (available from Filmetrics Co.), and a reflectance was measured with light having a wavelength of 550 nm.
  • Example 4 Example 5 Com. Ex. 1 Substrate film Anti-glare PET Anti-glare PET Anti-glare PET Curable fluorine- Example 3 Un-coated containing polymer Content of 40 50 —O(C ⁇ O)CF ⁇ CH 2 group (% by mole) Solvent MIBK MIBK Concentration of 3.75 3.75 polymer (% by weight) Active energy curing Curing Curing initiator initiator 1 initiator 1 Ratio to polymer 3 3 (% by weight) Amount of ultraviolet 4200 4200 light (mJ/cm) Refractive index Before curing 1.380 1.367 After curing 1.387 1.375 Dry to touch ⁇ ⁇ Un-coated Solvent resistance ⁇ X Abrasion resistance ⁇ X Reflectance on 4.82 4.70 8.00 one side of film (%) Curing initiator 1: 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one
  • the present invention can provide a material which is free from fading into white due to surface scattering while maintaining anti-glaring property and is useful as a laminated article having excellent adhesion and practical low reflection.

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US7585926B2 (en) 2009-09-08
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