Classifications

• • 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
  • C09D127/00—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 at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—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 at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/12—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 at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/14—Esterification
• • 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
  • C08F16/00—Homopolymers and 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F16/12—Homopolymers and 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
  • C08F16/32—Monomers containing two or more unsaturated aliphatic radicals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F214/18—Monomers containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/04—Polymers provided for in subclasses C08C or C08F
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers

Definitions

• the present invention relates to a novel curable fluorine-containing polymer, a curable resin composition prepared from same and a cured article and cured film obtained by curing the curable fluorine-containing polymer and also relates to an antireflection film obtained from the cured film and an antireflection-treated article provided with the antireflection film.
• an antireflection film made of a material having a low refractive index has been formed on a substrate of the displaying device.
• an antireflection film there is known, for example, a method of forming a thin film of a fluorine-containing compound by a deposition method.
• a deposition method it is difficult to form a coating film on a substrate for a large display and yet a cost is high since a vacuum equipment is required.
• An object of the present invention is to provide a curable fluorine-containing polymer which can make its hardness high by photo-curing while maintaining a low refractive index.
• Another object of the present invention is to provide an antireflection film possessing improved scratch resistance and abrasion resistance while maintaining a reflection reducing effect and also to provide an antireflection-treated article having such an antireflection film thereon.
• the present inventors have made intensive studies to achieve those objects and have found novel curable fluorine-containing polymers having an ethylenic carbon-carbon double bond in its side chain and have found that when those polymers are used, a cured article having a high hardness can be obtained while maintaining a low refractive index.
• a cured film of a specific fluorine-containing polymer having a carbon-carbon unsaturated bond at an end of its side chain is useful as an antireflection film having both of low reflection and high hardness.
• the first of the present invention relates to a curable fluorine-containing polymer having an ethylenic carbon-carbon double bond in its side chain.
• the curable fluorine-containing polymer of the present invention has a number average molecular weight of from 500 to 1,000,000 and is represented by the formula (1): ⁇ M ⁇ A ⁇ (1)
• the structural unit M is a structural unit derived from fluorine-containing ethylenic monomer and 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 is an organic group in which 1 to 3 of Y 1 (Y 1 is a monovalent organic group having 2 to 10 carbon atoms and an ethylenic carbon-carbon double bond at its end) are bonded to 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;
• a is 0 or an integer of from 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 monomer copolymerizable with the fluorine-containing ethylenic monomer represented by the formula (M),
• the structural unit M and the structural unit A are contained in amounts of from 0.1 to 100% by mole and from 0 to 99.9% by mole, respectively.
• the second of the present invention relates to a process for preparing a curable fluorine-containing polymer having a number average molecular weight of from 500 to 1,000,000 which is characterized by esterifying:
• the structural unit N is a structural unit having hydroxyl and derived from 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 ;
• Rf 1 is an organic group in which 1 to 3 of Y 5 (Y 5 is hydroxyl or a monovalent organic group having 1 to 10 carbon atoms and hydroxyl) are bonded to 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;
• a is 0 or an integer of from 1 to 3;
• b and c are the same or different and each is 0 or 1,
• the structural unit (B) is a structural unit derived from monomer copolymerizable with the fluorine-containing ethylenic monomer having hydroxyl which is represented by the above-mentioned formula (N), and the structural unit N and the structural unit B are contained in amounts of from 0.1 to 100% by mole and from 0 to 99.9% by mole, respectively, with an unsaturated carboxylic acid or its derivative having 3 to 10 carbon atoms (a total number of carbon atoms including carbon atoms of Y 3 is from 3 to 10) and represented by the formula:
• R 1 is a divalent organic group which has 1 to 7 carbon atoms and may be substituted with fluorine atom;
• 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;
• f is 0 or 1.
• the obtained curable fluorine-containing polymer is represented by the formula (1a):
• the structural unit M4 is a structural unit derived from a fluorine-containing ethylenic monomer and represented by the formula (M4):
• 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 2 is an organic group in which 1 to 3 of Y 6 having 3 to 10 carbon atoms and represented by the formula:
• R 1 , X 6 , X 7 , X 8 and f are as defined above;
• R 2 is a divalent organic group which has 1 to 7 carbon atoms and may be substituted with fluorine atom;
• g is 0 or 1
• a is 0 or an integer of from 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 monomer copolymerizable with the fluorine-containing ethylenic monomer represented by the formula (M4), and
• the structural unit M4 and the structural unit A are contained in amounts of from 0.1 to 100% by mole and from 0 to 99.9% by mole, respectively.
• the third of the present invention relates to a fluorine-containing resin composition for coating which comprises:
• the fourth of the present invention relates to an antireflection film.
• the antireflection film is
• an antireflection film which is a cured film of a fluorine-containing prepolymer, in which the fluorine-containing prepolymer has:
• a thickness of the cured film is from 0.03 to 0.5 ⁇ m
• an antireflection film which is a cured film obtained by photo-curing a coating film formed by coating a composition for coating which comprises:
• a thickness of the cured film is from 0.03 to 0.5 ⁇ m; or an antireflection film which is a cured film obtained by photo-curing a coating film formed by coating a composition for coating which comprises:
• a thickness of the cured film is from 0.03 to 0.5 ⁇ m.
• the fifth of the present invention relates to an antireflection-treated article obtained by applying the above-mentioned antireflection film on a substrate.
• the sixth of the present invention relates to a novel fluorine-containing unsaturated compound.
• the novel compound is a fluorine-containing unsaturated compound represented by the formula (4-1):
• 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′ is an organic group in which 1 to of 3 Y 3 (Y 3 is a monovalent organic group having 2 to 10 carbon atoms and an ethylenic carbon-carbon double bond at its end) are bonded to 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;
• a is 0 or an integer of from 1 to 3;
• c is 0 or 1,
• Y 3 is an organic group represented by the formula:
• Y 4 is an alkenyl group or fluorine-containing alkenyl group having 2 to 5 carbon atoms and an ethylenic carbon-carbon double bond at its end and d is 0 or 1.
• the curable fluorine-containing polymer of the first invention is, as mentioned above, the curable fluorine-containing polymer which has a number average molecular weight of from 500 to 1,000,000 and is 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 is an organic group in which 1 to 3 of Y 1 (Y 1 is a monovalent organic group having 2 to 10 carbon atoms and an ethylenic carbon-carbon double bond at its end) are bonded to 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;
• a is 0 or an integer of from 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 monomer copolymerizable with the fluorine-containing ethylenic monomer represented by the formula (M), and
• the structural unit M and the structural unit A are contained in amounts of from 0.1 to 100% by mole and from 0 to 99.9% by mole, respectively.
• the structural unit M is a structural unit derived from a fluorine-containing ethylenic monomer represented by the formula (3):
• the curable fluorine-containing polymer is a homopolymer of the above-mentioned fluorine-containing ethylenic monomer having, in its side chain, an ethylenic carbon-carbon double bond curable by a reaction or a copolymer having the fluorine-containing ethylenic monomer as an essential component.
• At least one of Y 1 is bonded to an end of Rf.
• the structural unit M is preferably a structural unit M1 represented by:
• 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 is an organic group in which 1 to 3 of Y 1 (Y 1 is a monovalent organic group having 2 to 10 carbon atoms and an ethylenic carbon-carbon double bond at its end) are bonded to 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;
• a is 0 or an integer of from 1 to 3;
• c is 0 or 1.
• the structural unit M1 is a structural unit derived from a fluorine-containing ethylenic monomer represented by:
• Rf′ is an organic group in which 1 to 3 of Y 3 (Y 3 is a monovalent organic group having 2 to 10 carbon atoms and an ethylenic carbon-carbon double bond at its end) are bonded to 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,
• Y 3 is an organic group represented by the formula:
• Y 4 is an alkenyl group or fluorine-containing alkenyl group having 2 to 5 carbon atoms and an ethylenic carbon-carbon double bond at its end, d is 0 or 1,
• the polymer containing the above-mentioned structural unit M1 is particularly low in refractive index, and is preferred particularly since a refractive index can be decreased even in the cases of a M1 homopolymer and a polymer containing the M1 in an increased amount.
• M1 More preferable example of M1 is a structural unit M2 represented by:
• Rf is an organic group in which 1 to 3 of Y 1 (Y 1 is a monovalent organic group having 2 to 10 carbon atoms and an ethylenic carbon-carbon double bond at its end) are bonded to 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.
• the structural unit M2 is a structural unit derived from a fluorine-containing ethylenic monomer represented by the formula (4-2):
• Rf is as defined in the formula (3).
• a fluorine-containing unsaturated compound represented by the formula (4-3) a fluorine-containing unsaturated compound represented by the formula (4-3):
• Rf′ is as defined in the formula (4-1), is a novel compound which has not been disclosed in any publications.
• the above-mentioned M2 is a structural unit of a fluorine-containing allyl ether having an ethylenic carbon-carbon double bond at its end and is preferred since not only a refractive index can be decreased but also polymerizability thereof, particularly homo-polymerizability and copolymerizability with the fluorine-containing ethylenic monomer are good.
• Another example of preferable M1 is a structural unit M3 represented by:
• Rf is an organic group in which 1 to 3 of Y 1 (Y 1 is a monovalent organic group having 2 to 10 carbon atoms and an ethylenic carbon-carbon double bond at its end) are bonded to 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.
• the structural unit M3 is a structural unit derived from a fluorine-containing ethylenic monomer represented by the formula (4-4):
• Rf is as defined in the formula (3).
• Rf′ is as defined in the formula (4-1) is a novel compound which has not been disclosed in any publications.
• the above-mentioned M3 is a structural unit of a fluorine-containing vinyl ether having an ethylenic carbon-carbon double bond at its end and is preferred since a refractive index can be decreased and copolymerizability with the fluorine-containing ethylenic monomer is good.
• Y 1 contained in the structural units M, M1, M2 and M3 is an organic group having 2 to 10 carbon atoms and an ethylenic carbon-carbon double bond at its end.
• the carbon-carbon double bond in Y 1 has an ability of causing polycondensation reaction, ring formation reaction and addition reaction, and thereby a cured (crosslinked) article can be obtained.
• a cured (crosslinked) article can be obtained by contact of the carbon-carbon double bond with radical or cation, there arise a polymerization reaction and condensation reaction between molecules of the curable fluorine-containing polymer of the present invention or between the curable fluorine-containing polymer and the curing (crosslinking) agent added as case demands, and thus a cured (crosslinked) article can be obtained.
• Y 1 is:
• Y 2 is an alkenyl group or fluorine-containing alkenyl group having 2 to 5 carbon atoms and an ethylenic carbon-carbon double bond at its end, d and e are the same or different and each is 0 or 1, and preferable Y 2 is:
• X 6 is H, F, CH 3 or CF 3 ;
• X 7 and X 8 are H or F since curing reactivity thereof by contact with radical or cation is high.
• Examples of the preferable Y 4 in the novel fluorine-containing unsaturated compounds of the present invention represented by (4-1), (4-3) and (4-5) are the same as the above-mentioned Y 2 .
• Examples of the preferable Y 2 and Y 4 are:
• Examples of more preferable Y 1 and Y 3 are:
• X 6 is H, F, CH 3 or CF 3
• X 7 and X 8 are H or F, which are preferred since a curing reactivity by contact with radical is particularly higher and a cured article can be obtained easily by photo-curing, etc.
• Particularly those which have a structure of —O(C ⁇ O)CF ⁇ CH 2 are preferred since a refractive index can be reduced and a curing (crosslinking) reactivity is particularly high, which enables a cured article to be obtained effectively.
• Rf contained in the structural units M, M1, M2 and M3 of the curable fluorine-containing polymer of the formula (1) of the present invention Rf′ contained in the novel fluorine-containing unsaturated compounds represented by the formulae (4-1), (4-3) and (4-5), Rf 1 contained in the structural unit N of the fluorine-containing polymer of the formula (2) having hydroxyl and further Rf 4 and Rf 6 contained in the structural units (A1) and (A2) of the curable fluorine-containing polymer of the formula (1-1), examples of preferable organic groups excluding the functional groups Y 1 , Y 3 , Y 5 , Z 1 and Z 2 are fluorine-containing alkylene groups having 1 to 40 carbon atoms and fluorine-containing alkylene groups having 2 to 100 carbon atoms and ether bond particularly in case where the number of functional groups Y 1 , Y 3 or Y 5 is one.
• fluorine atom is bonded to carbon atom contained therein.
• those organic groups are fluorine-containing alkylene groups or fluorine-containing alkylene groups having ether bond, in which fluorine atom and hydrogen atom or chlorine atom are bonded to carbon atom.
• Preferred are those having more fluorine atoms (a higher fluorine content).
• the fluorine content is not less than 50%, preferably not less than 70% on the basis of a molecular weight of the organic groups provided that oxygen atoms in the organic groups and the functional groups are eliminated from calculation. More preferred are perfluoro alkylene groups or perfluoro alkylene groups having ether bond.
• Those organic groups are preferred since a refractive index of the curable fluorine-containing polymer can be reduced, particularly since a low refractive index can be maintained even when a curing degree (density of crosslinking) is made high to increase hardness of the cured article.
• Too large number of carbon atoms is not preferable because in case of the fluorine-containing alkylene groups, there is a case where solubility in a solvent is lowered and transparency is lowered and in case of the fluorine-containing alkylene groups having ether bond, there is a case where hardness and mechanical properties of the polymer itself and the cured article obtained therefrom are lowered.
• the number of carbon atoms of the fluorine-containing alkylene groups is preferably from 1 to 20, more preferably from 1 to 10, and the number of carbon atoms of the fluorine-containing alkylene groups having ether bond is preferably from 2 to 30, more preferably from 2 to 20
• X 9 and X 9′ are F or CF 3 ; X 10 and X 10′ are H or F; o+p+q is from 1 to 30; r is 0 or 1; s and t are 0 or 1).
• n is 0 or an integer of from 1 to 30
• Rf 1 and Rf 2 are perfluoroalkyl groups having 1 to 5 carbon atoms; n is 0 or an integer of from 1 to 30)
• novel fluorine-containing unsaturated compound of the formula (4-3) are those exemplified above as the monomer giving the structural unit M2, in which Y 1 is replaced with Y 3 .
• Rf 1 and Rf 2 are perfluoroalkyl groups having 1 to 5 carbon atoms; n is 0 or an integer of from 1 to 30)
• Rf 1 and Rf 2 are perfluoroalkyl groups having 1 to 5 carbon atoms
• novel fluorine-containing unsaturated compound of the formula (4-5) are those exemplified above as the monomer giving the structural unit M3, in which Y 1 is replaced with Y 3 .
• Rf 1 and Rf 2 are perfluoroalkyl groups having 1 to 5 carbon atoms
• Examples of a preferable monomer constituting the structural unit M of the curable fluorine-containing polymer of the present invention other than M2 and M3 are, for instance,
• the structural unit A is an optional component and is not limited particularly as far as it is a monomer copolymerizable with the structural unit M, M1, M2 or M3.
• the structural unit A may be selected optionally depending on intended applications and required characteristics of the curable fluorine-containing polymer and the cured article obtained therefrom.
• Examples of the structural unit A are, for instance,
• X 11 , X 12 and X 13 are H or F;
• X 14 is H, F or CF 3 ;
• h is 0, 1 or 2;
• i is 0 or 1;
• Rf 4 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;
• Z 1 is selected from —OH, —CH 2 OH, —COOH, carboxylic acid derivative, —SO 3 H, sulfonic acid derivative, epoxy group and cyano group.
• Particularly preferred is the structural unit 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).
• Rf is the same as Rf of the formula (M).
• These structural units are preferred from the point that a refractive index of the curable fluorine-containing polymer or the cured article obtained therefrom can be kept low and the refractive index can be further reduced. Also those structural units are preferred since mechanical properties, glass transition temperature, etc. of the polymer can be adjusted by selecting monomers, particularly since the glass transition temperature can be increased by copolymerizing with the structural unit M.
• Preferred structural units of the fluorine-containing ethylenic monomers are those represented by the formula (A2):
• X 15 , X 16 and X 18 are H or F;
• X 17 is H, F or CF 3 ;
• h1, i1 and j are 0 or 1;
• Z 2 is H, F or Cl;
• Rf 5 is a fluorine-containing alkylene group having 1 to 20 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond.
• Preferred examples thereof are 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: from 1 to 10)
• CH 2 ⁇ CHOCH 2 ⁇ CF 2 ⁇ n Z 2 (Z 2 is as defined in the formula (A2), n: from 1 to 10).
• Preferred fluorine-containing aliphatic ring structural units 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, C 1 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;
• the structural units derived from ethylenic monomers not having fluorine may be introduced to the polymer in a range where the introduction does not have an adverse effect on a refractive index (in a range where the refractive index does not increase).
• non-fluorine-containing ethylenic monomer examples include as follows.
• Acrylic acid methacrylic acid, acrylic acid esters, methacrylic acid esters, maleic anhydride, maleic acid, maleic acid esters and the like.
• a structural unit of an alicyclic monomer may be introduced as a component copolymerizable with the structural unit M, more preferably as the third component in addition to the structural unit M and the structural unit of the above-mentioned fluorine-containing ethylenic monomer or non-fluorine-containing ethylenic monomer (the above-mentioned ⁇ circle over (3) ⁇ and ⁇ circle over (4) ⁇ ), which is preferable since a high glass transition temperature can be obtained and hardness can be increased.
• Examples of the alicyclic monomer are norbornene derivatives represented by:
• m is from 0 to 3;
• A, B, C and D are H, F, Cl, COOH, CH 2 OH, a perfluoroalkyl having 1 to 5 carbon atoms or the like, alicyclic monomers such as:
• various combinations and proportions of the structural units M (M1, M2 and M3) and A can be selected from the above-mentioned examples depending on intended applications, physical properties (particularly glass transition temperature, hardness, etc.), functions (transparency and refractive index) and the like.
• the curable fluorine-containing polymer of the present invention contains the structural unit M (M1, M2 or M3) as an essential component and is characterized in that the structural unit M itself has functions of maintaining a low refractive index and imparting transparency to the polymer and functions of imparting hardness, abrasion resistance, scratch resistance and solvent resistance to the cured article by curing. Therefore even if the curable fluorine-containing polymer of the present invention contains a larger amount of the structural unit M or in the extreme case, even if the polymer consists of the structural unit M (100% by mole), the low refractive index can be maintained. Further the curable fluorine-containing polymer of the present invention is preferred since the cured article having a high curing (crosslinking) density and the coating film having a high hardness and excellent abrasion resistance and scratch resistance can be obtained.
• the polymer which provides the cured article having a higher hardness (high glass transition temperature) and a low refractive index can be obtained.
• the proportion of the structural unit M may be not less than 0.1% by mole based on the whole monomers constituting the curable fluorine-containing polymer. It is preferable that the proportion is not less than 2.0% by mole, more preferably not less than 5% by mole, further preferably not less than 10% by mole in order to obtain the cured article having a high hardness, excellent abrasion resistance and scratch resistance and good chemical resistance and solvent resistance by curing (crosslinking).
• the structural unit M is contained in an amount of not less than 10% by mole, preferably not less than 20% by mole, more preferably not less than 50% by mole.
• the curable fluorine-containing polymer of the present invention is preferable particularly for the antireflection film application since a reflection reducing effect is not lowered even if the proportion of the structural unit M is increased (or even if the number of cure sites is increased).
• Preferred fluorine-containing polymers for a coating composition aiming at a low refractive index and a high hardness are curable fluorine-containing polymers represented by the formula (1-1).
• the structural unit M in the formula (1-1) is the above-mentioned structural unit having an ethylenic carbon-carbon double bond in its side chain, and the same structural units as the above-mentioned preferable examples of the formulae (M1), (M2) and (M3) can be used as the structural unit M.
• the structural unit A1 is derived from a fluorine-containing ethylenic monomer having functional group in its side chain and is represented by the formula (A1):
• the above-mentioned examples of the structural unit A1 derived from the fluorine-containing ethylenic monomer having functional group can be preferably used similarly.
• the structural unit A2 is derived from a fluorine-containing ethylenic monomer not having functional group and is represented by the formula (A2):
• X 15 , X 16 and X 18 are H or F; X 17 is H, F or CF 3 ; h1, i1 and j are 0 or 1; Z 2 is H, F or Cl; Rf 5 is a fluorine-containing alkylene group having 1 to 20 carbon atoms or a fluorine-containing alkylene group having 2 to 100 carbon atoms and ether bond.
• the above-mentioned examples of the structural unit A2 derived from the fluorine-containing ethylenic monomer not having functional group can be preferably used similarly. Among them, preferred is a structural unit derived from at least one monomer selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride and hexafluoropropylene.
• the proportions of the structural units M, A1 and A2 are from 0 to 90% by mole, from 0 to 99.9% by mole and from 0 to 99.9% by mole, respectively and A1+A2 is from 10 to 99.9% by mole. It is particularly preferable that the proportions of the structural units M, A1 and A2 are from 10 to 80% by mole, from 1 to 60% by mole and from 20 to 85% by mole, respectively and A1+A2 is from 20 to 90% by mole. When the proportion of the structural unit M is too low, hardness of the cured coating film tends to be lowered and strength thereof tends to become insufficient.
• the fluorine-containing polymer comprising those structural units M, A1 and A2
• hardness, mechanical strength and solvent resistance can be imparted to the cured coating film by a cure site of the structural unit M.
• the functional group of the structural unit A1 can impart adhesion to a substrate, solubility in a solvent and good coatability (wettability and leveling property) to the substrate.
• the structural unit A2 can impart, to the fluorine-containing polymer, a mechanical strength, solubility in a solvent and good coatability to a substrate.
• any of the structural units M, A1 and A2 have many fluorine atoms, the above-mentioned functions can be imparted while maintaining a low refractive index, and therefore the curable fluorine-containing polymer is preferred as a coating agent for an antireflection purpose.
• the molecular weight of the curable fluorine-containing polymer of the present invention can be selected, for example, in a range of from 500 to 1,000,000 in number average molecular weight.
• Preferred molecular weight is from 1,000 to 500,000, particularly from 2,000 to 200,000.
• the refractive index of the curable fluorine-containing polymer itself is not more than 1.45, more preferably not more than 1.40, particularly preferably not more than 1.38.
• the refractive index changes depending on kinds of a substrate and undercoating, but since the curing (crosslinking) can be done while maintaining a low refractive index, the polymer can be a preferable base polymer for an antireflection film.
• the curable fluorine-containing polymer is 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 the above-mentioned general-purpose solvents.
• the polymer When the polymer is soluble in general-purpose solvents, it is preferable because film forming property and homogeneity are excellent in coating application, particularly in case of forming a thin antireflection film of about 0.1 ⁇ m thick on various transparent films and displaying substrates.
• the polymer is also advantageous from the viewpoint of productivity in forming an antireflection film.
• the method ⁇ circle over (2) ⁇ is a preferable method since it is easy to obtain the curable fluorine-containing polymer of the present invention without curing reaction and also from the point that a carbon-carbon double bond having a high curing reactivity can be introduced to its side chain.
• the methods ⁇ circle over (2) ⁇ there is preferably employed, for example, a method of obtaining the curable fluorine-containing polymer of the present invention by synthesizing the fluorine-containing polymer comprising the structural unit N of fluorine-containing monomer having hydroxyl or an organic group Y 3 having hydroxyl and as case demands, the structural unit B of monomer copolymerizable with N, and then reacting the polymer with an unsaturated carboxylic acid or its derivative to introduce a carbon-carbon double bond to an end of a side chain of the polymer.
• the second of the present invention relates to the process for preparing the curable fluorine-containing polymer, which is characterized by esterification reaction, with an unsaturated carboxylic acid or its derivative, of the fluorine-containing polymer having hydroxyl and represented by the formula (2):
• the structural unit N is a structural unit having hydroxyl and 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 ;
• Rf 1 is an organic group in which 1 to 3 of Y 5 (Y 5 is hydroxyl or a monovalent organic group having 1 to 10 carbon atoms and hydroxyl) are bonded to a fluorine-containing allyl group having 1 to 40 carbon atoms or a fluorine-containing allyl group having 2 to 100 carbon atoms and ether bond;
• a is 0 or an integer of from 1 to 3;
• b and c are the same or different and each is 0 or 1,
• the structural unit B is a structural unit derived from monomer copolymerizable with the fluorine-containing ethylenic monomer having hydroxyl and represented by the above-mentioned formula (N), and the structural unit N and the structural unit B are contained in amounts of from 0.1 to 100% by mole and from 0 to 99.9% by mole, respectively.
• examples of the preferable structural unit N of the fluorine-containing polymer having hydroxyl which is a precursor represented by the formula (2) are structures which correspond to the above-exemplified respective structural units M of the curable fluorine-containing polymer and have the Y 5 having OH group instead of the Y 1 having a carbon-carbon double bond. Those structural units can be used preferably.
• the structural unit B there can be preferably used the same structural units as the above-mentioned structural unit A.
• R is H, CH 3 , F, CF 3 or Cl, or anhydrides thereof, acid halides represented by:
• R is as defined above, X is Cl or F, maleic acid, maleic anhydride, maleic acid monoalkylester and the like.
• unsaturated carboxylic acid halides are preferred since the reaction can be carried out at room temperature and gelling of a prepared polymer can be prevented.
• the method of reacting the fluorine-containing polymer having hydroxyl with ⁇ , ⁇ -unsaturated carboxylic acid halide is not limited particularly and is usually carried out by dissolving the fluorine-containing polymer having hydroxyl in a solvent and mixing the ⁇ , ⁇ -unsaturated carboxylic acid halide thereto at a temperature of from about ⁇ 20° C. to about 40° C. with stirring.
• HCl and HF are produced and therefore it is desirable to add a proper base for capturing them.
• the base are tertiary amines such as pyridine, N,N-dimethylaniline, tetramethylurea and triethylamine, magnesium metal and the like.
• an inhibitor may be present to prevent a polymerization reaction of the carbon-carbon double bonds in the starting ⁇ , ⁇ -unsaturated carboxylic acid and the obtained curable fluorine-containing polymer during the reaction.
• Examples of the inhibitor are hydroquinone, t-butyl hydroquinone, hydroquinone monomethylether and the like.
• the fluorine-containing polymer having hydroxyl before the reaction with the unsaturated carboxylic acid or its derivative can be obtained by (co)polymerizing through known method the respective component units such as the ethylenic monomer (N) having hydroxyl and the monomer (B) when used as a copolymerizable component.
• radical polymerization method, anion polymerization method, cation polymerization method and the like can be employed for the polymerization.
• the radical polymerization method is preferably used from the viewpoint that each monomer exemplified to obtain the polymer having hydroxyl of the present invention has good radial polymerizability, control of composition and molecular weight is easy and production in an industrial scale is easy.
• means for initiation is not limited particularly as far 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 molecular weight is controlled by the contents of the monomers to be used for the polymerization, the content of the polymerization initiator, the content of a chain transfer agent, temperature, etc.
• the components of the copolymer can be controlled by the starting monomer components.
• the third of the present invention relates to the composition comprising a curable fluorine-containing polymer.
• One of the compositions of the present invention is the curable fluorine-containing resin composition comprising:
• the curable fluorine-containing polymer (a) for the composition of the present invention is the above-mentioned curable fluorine-containing polymer having a carbon-carbon double bond in its side chain, and preferred examples thereof are the same as those exemplified above.
• the active energy curing initiator (b) which initiates curing with active energy functions as a catalyst which generates radical or cation only by irradiation of, for example, an electromagnetic wave having a wavelength of not more than 350 nm, namely ultraviolet light, electron beam, X-ray, ⁇ -ray and the like and initiates curing (crosslinking reaction) of the carbon-carbon double bond of the curable fluorine-containing polymer.
• an electromagnetic wave having a wavelength of not more than 350 nm, namely ultraviolet light, electron beam, X-ray, ⁇ -ray and the like and initiates curing (crosslinking reaction) of the carbon-carbon double bond of the curable fluorine-containing polymer.
• curing initiators which generate radical or cation by irradiation of ultraviolet light particularly those generating radical are used.
• This curable fluorine-containing resin composition can initiate a curing reaction easily with the above-mentioned active energy, does not require heating at high temperatures and can be subjected to the curing reaction at low temperatures. Therefore the composition is preferred from the point that it can be used on substrates, for example, transparent resin substrates which have low heat resistance and easily undergo deformation, degrading and coloring due to heat.
• the curing initiator (b) which initiates curing with active energy is optionally selected depending on kind of the carbon-carbon double bond (radical-reactivity or cation-reactivity) in the side chain of the curable fluorine-containing polymer (a), kind (wavelength range, etc.) of the active energy, intensity of irradiation, etc.
• the initiator which functions to initiate curing of the curable fluorine-containing polymer (a) having a radical-reactive carbon-carbon double bond with active energy in an ultraviolet region are, for instance, those mentioned below.
• Benzophenone benzoyl benzoate, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propylbenzophenone, acrylated benzophenone, Michler's ketone and the like.
• the present inventors have found that compatibility between the polymer and the initiator can be improved by introducing fluorine atom or an organic group having fluorine atom to the active energy curing initiator.
• initiators having a fluorine-containing alkyl group, a fluorine-containing alkylene group, a fluorine-containing alkyl group having ether bond or a fluorine-containing alkylene group having ether bond are examples.
• an initiator in which a fluorine-containing carboxylic acid (polycarboxylic acid) or the like having the above-mentioned fluorine-containing organic group is introduced into an initiator having OH group by ester bonding Experimental Example 18
• an initiator in which a fluorine-containing carboxylic acid (polycarboxylic acid) or the like is introduced into an initiator having amino group by amide bonding.
• an auxiliary for photo-initiation such as amines, sulfones or sulfines may be added.
• initiator which initiates curing of the curable fluorine-containing polymer.
• (a) having a cation-reactive carbon-carbon double bond are those mentioned below.
• Iodonium salt sulfonium salt, phosphonium salt, diazonium salt, ammonium salt, pyridinium salt and the like.
• compatibility thereof with the fluorine-containing polymer can be improved by introducing fluorine atom or a fluorine-containing organic group to the initiators like the above-mentioned case.
• Another embodiment of the curable fluorine-containing resin composition of the present invention is one using a solvent, which is preferable from the point that the composition dissolved and dispersed in the solvent can be coated on various substrates to form a coating film and the coating film can be effectively cured by irradiation with active energy or the like to obtain a cured coating film.
• the fluorine-containing resin composition for coating of the present invention is the composition comprising:
• curable fluorine-containing polymer (a) and active energy curing initiator (b) as in the above-mentioned curable fluorine-containing resin composition.
• the solvent (c) is not limited particularly as far as the curable fluorine-containing polymer (a), active energy curing initiator (b) and additives such as a curing agent, leveling agent and light-stabilizer to be added as case demands are uniformly dissolved and dispersed therein. Particularly preferred is the solvent which uniformly dissolves the curable fluorine-containing polymer (a).
• This embodiment using the solvent is preferable from the point that a coating film having a high transparency and uniformity can be obtained in high productivity particularly in the antireflection film application, etc. where a thin coating film (about 0.1 ⁇ m thick) is required.
• Examples of the solvent (c) are, for instance, cellosolve 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
• 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:
• Those fluorine-containing solvents may be used solely, in a mixture of two or more 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 of a coating film.
• the present inventors have found that at dissolving the curable fluorine-containing polymer, when the fluorine-containing alcohol solvent is mixed to the above-mentioned general-purpose solvent, a leveling property of the polymer coating film after the coating on a substrate and drying can be improved.
• the fluorine-containing alcohol to be added may be one which has a boiling point of not less than 50° C., preferably not less than 80° C. and dissolves the curable fluorine-containing polymer.
• the fluorine-containing alcohol may be used solely as a solvent, it is effective to mix the fluorine-containing alcohol in addition to the above-mentioned general purpose solvent such as ketone solvent, acetic acid ester solvent, non-fluorine-containing alcohol solvent, aromatic solvent or the like.
• an adding amount thereof is not less than 1% by weight, preferably not less than 5% by weight, more preferably not less than 10% by weight, particularly from 10% by weight to 30% by weight based on the whole solvents.
• a curing agent may be added to the curable fluorine-containing resin composition comprising the curable fluorine-containing polymer (a) and the active energy curing initiator (b) and also to the fluorine-containing resin composition for coating further containing the solvent (c).
• Preferred curing agents are those which have at least one carbon-carbon unsaturated bond and can be polymerized with radical or an acid.
• examples thereof are concretely radically polymerizable monomers such as an acrylic monomer and cationically polymerizable monomers such as a vinyl ether monomer.
• Those monomers may be monofunctional monomers having one carbon-carbon double bond or polyfunctional monomers having two or more carbon-carbon double bonds.
• Those so-called curing agents having a carbon-carbon unsaturated bond react by radical or cation generated by reaction of the active energy curing initiator (b) in the composition of the present invention with the active energy such as light and can be crosslinked with the carbon-carbon double bond in the side chain of the curable fluorine-containing polymer (a) in the composition of the present invention by copolymerization.
• Examples of the monofunctional acrylic monomer are acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, ⁇ -fluoroacrylic acid, ⁇ -fluoroacrylic acid esters, maleic acid, maleic anhydride, maleic acid esters and (meth)acrylic acid esters having epoxy, hydroxyl, carboxyl or the like.
• acrylate monomers having a fluoroalkyl group to maintain a low refractive index of the cured article preferred are compounds represented by the formula:
• X is H, CH 3 or F; Rf is a fluorine-containing alkyl group having 2 to 40 carbon atoms or a fluorine-containing alkyl group having 2 to 100 carbon atoms and ether bond.
• polyfunctional acrylic monomer there are generally known compounds obtained by replacing hydroxyl groups of polyhydric alcohols such as diol, triol and tetraol with acrylate groups, methacrylate groups or ⁇ -fluoroacrylate groups.
• Examples thereof are compounds obtained by replacing two or more hydroxyl groups of polyhydric alcohols such as 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, tripropylene glycol, neopentyl glycol, trimethylol propane, pentaerythritol and dipentaerythritol with any of acrylate groups, methacrylate groups or ⁇ -fluoroacrylate groups.
• polyhydric alcohols such as 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, tripropylene glycol, neopentyl glycol, trimethylol propane, pentaerythritol and dipentaerythritol with any of acrylate groups, methacrylate groups or ⁇ -fluoroacrylate groups.
• polyfunctional acrylic monomers obtained by replacing two or more hydroxyl groups of polyhydric alcohols having a fluorine-containing alkyl group, a fluorine-containing alkyl group having ether bond, a fluorine-containing alkylene group or a fluorine-containing alkylene group having ether bond with acrylate groups, methacrylate groups or a-fluoroacrylate groups.
• Those monomers are preferred particularly from the point that a low refractive index of the cured article can be maintained.
• Preferable examples thereof are compounds having structures obtained by replacing two or more hydroxyl groups of fluorine-containing polyhydric alcohols represented by the formulae:
• Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms
• Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms or a fluorine-containing alkyl group having 1 to 40 carbon atoms and ether bond, R 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 1 to 40 carbon atoms and ether bond, R is H or an alkyl group having 1 to 3 carbon atoms) with acrylate groups, methacrylate groups or ⁇ -fluoroacrylate groups.
• an adding amount of the active energy curing initiator (b) is optionally selected depending on the content of the carbon-carbon double bonds in the curable fluorine-containing polymer (a), an amount of the curing agent and further kinds of the initiator and active energy and an amount of irradiation energy (intensity and time) and also depending on whether or not the above-mentioned curing agent is used.
• the amount of the initiator is from 0.01 to 30 parts by weight, preferably from 0.05 to 20 parts by weight, most preferably from 0.1 to 10 parts by weight based on 100 parts by weight of the curable fluorine-containing polymer (a).
• the amount of the initiator is from 0.05 to 50% by mole, preferably from 0.1 to 20% by mole, most preferably from 0.5 to 10% by mole based on the content (the number of moles) of the carbon-carbon double bonds contained in the curable fluorine-containing polymer (a).
• the amount of the initiator is from 0.05 to 50% by mole, preferably from 0.1 to 20% by mole, most preferably from 0.5 to 10% by mole based on the total number of moles including the content (number of moles) of the carbon-carbon double bonds contained in the curable fluorine-containing polymer (a) and the number of moles of the carbon-carbon unsaturated bonds of the curing agent.
• the amount of the curing agent is optionally selected depending on intended hardness and refractive index, kind of the curing agent, the content of curable groups of the curable fluorine-containing polymer, etc.
• the amount is desirably from 1 to 80% by weight, preferably from 5 to 70% by weight, more preferably from 10 to 50% by weight based on the curable fluorine-containing polymer. If the amount of the curing agent is too large, there is a tendency that the refractive index is increased, which is not preferable.
• the content of the solvent (c) in the fluorine-containing resin composition for coating of the present invention is optionally selected depending on kinds of solids to be dissolved, the amount of the curing agent, kind of a substrate, intended coating thickness, etc. and also depending on whether or not the curing agent is used. It is preferable to decide the amount of the solvent so that a concentration of the whole solids in the composition becomes from 0.5 to 70% by weight, preferably from 1 to 50% by weight.
• composition of the present invention may be added various additives as case demands in addition to the above-mentioned compounds.
• additives are, for instance, a leveling agent, viscosity control agent, light-stabilizer, moisture absorbing agent, pigment, dye, reinforcing agent and the like.
• composition of the present invention can be added fine particles of inorganic compounds to increase hardness of the cured article.
• the fine particles of inorganic compound are not limited particularly. Preferred are compounds having a refractive index of not more than 1.5. Desirable fine particles are magnesium fluoride (refractive index: 1.38), silicon oxide (refractive index: 1.46), aluminum fluoride (refractive index: from 1.33 to 1.39), calcium fluoride (refractive index: 1.44), lithium fluoride (refractive index: from 1.36 to 1.37), sodium fluoride (refractive index: from 1.32 to 1.34), thorium fluoride (refractive index: from 1.45 to 1.50) and the like. It is desirable that a particle size of the fine particles is sufficiently small as compared with wavelengths of visible light in order to ensure transparency of the low refractive index material. The particle size is preferably not more than 100 nm, particularly preferably not more than 50 nm.
• the fine particles of inorganic compound When the fine particles of inorganic compound are used, it is desirable to use them in the form of organic sol previously dispersed in an organic dispersion in order not to lower dispersion stability in the composition and adhesion in the low refractive index material. Further in order to enhance dispersion stability of the fine particles of inorganic compound in the composition and adhesion in the low refractive index material, surfaces of the fine particles of inorganic compound can be previously modified with various coupling agents.
• the coupling agent are, for instance, organosilicon compounds; metal alkoxides such as aluminum, titanium, zirconium, antimony and a mixture thereof; salts of organic acids; coordination compounds bonded with a coordinative compound; and the like.
• the curable fluorine-containing polymer (a) or additives may be in either form of dispersion or solution in the solvent (c).
• the form of uniform solution is preferred.
• a roll coating method gravure coating method, micro-gravure coating method, flow coating method, bar coating method, spray coating method, dye coating method, spin coating method, dip coating method and the like.
• the coating method can be selected in consideration of kind and shape of a substrate, productivity, controllability of a coating thickness, etc.
• the curable resin composition of the present invention comprising the curable fluorine-containing polymer (a) and the active energy curing initiator (b) and the coating film obtained by coating the fluorine-containing resin composition for coating of the present invention on a substrate by the above-mentioned coating method and then drying can be photo-cured by irradiation of active energy rays such as ultraviolet light, electron beam or radioactive ray.
• active energy rays such as ultraviolet light, electron beam or radioactive ray.
• the carbon-carbon double bonds in the curable fluorine-containing polymer (a) of the present invention are polymerized between the molecules, and the carbon-carbon double bonds in the polymer decrease or disappear.
• hardness of the resin becomes high, a mechanical strength is increased, abrasion resistance and scratch resistance are increased and further the composition not only becomes insoluble in a solvent in which the composition is soluble before the curing but also becomes insoluble in many other kinds of solvents.
• the fourth of the present invention relates to the antireflection film.
• the antireflection film is the cured coating film of the fluorine-containing prepolymer which has a coating thickness of from 0.03 to 0.5 ⁇ m and is characterized in that the prepolymer has:
• This invention was completed based on the findings of the present inventors that when the fluorine-containing prepolymer which has a carbon-carbon unsaturated bond capable of curing (crosslinking) and is low in a refractive index is coated on a transparent substrate in a specific coating thickness and is cured, an antireflection film having a reflection reducing effect and in addition, a high hardness, abrasion resistance and scratch resistance can be obtained.
• coatability smoothness and uniformity of a coating thickness
• a low molecular weight monomer component is hard to remain in the coating film after the curing, and therefore the coating film is free from feeling of tackiness on its surface and has excellent characteristics.
• the curing can be carried out with heat and light (in a system containing an initiator).
• the antireflection film is provided on a transparent resin substrate, applying high temperatures on the substrate is not preferable because thermal deterioration and thermal deformation of the substrate are apt to occur. Therefore the curing with light is preferred, and it is preferable that the fluorine-containing prepolymer has a carbon-carbon unsaturated bond capable of photo-curing (for example, photo-polymerizing).
• coating the coating composition on a substrate forming a coating film (not-cured) by drying and then irradiating the coating film with active energy ray such as ultraviolet light, electron beam, radioactive ray or the like.
• active energy ray such as ultraviolet light, electron beam, radioactive ray or the like.
• the light irradiation may be carried out in either of air stream and inert gas stream such as nitrogen gas. Particularly the light irradiation in an inert gas stream is preferred from the viewpoint of good curing reactivity, and a coating film having a higher hardness can be obtained.
• any of fluorine-containing prepolymers can be used as far as they have a reactive carbon-carbon unsaturated bond in the side chain thereof. From the viewpoint of good reactivity, an ethylenic carbon-carbon double bond is preferred.
• Particularly preferred is a combination use of the fluorine-containing prepolymer (d1) having a radically polymerizable ethylenic carbon-carbon double bond and the initiator (e) generating radical by irradiation of active energy ray from the point that the polymerization reaction occurs rapidly, a degree of polymerization is high and the curing can be easily carried out.
• the fluorine-containing prepolymer (d2) having an acid-polymerizable carbon-carbon double bond can be used in combination with an initiator generating an acid by irradiation of active energy ray, which is preferable from the point that the curing reaction is less affected by air (oxygen), etc. at the time of light irradiation.
• the fluorine-containing prepolymer to be used for the antireflection film of the present invention is preferably the same as the above-mentioned curable fluorine-containing polymers, and among the above-mentioned examples of the curable polymer, those which have a high transparency, are non-crystalline and have a refractive index of not more than 1.40, preferably not more than 1.38 are selected. Further among them, it is preferable to optionally select the polymers depending on intended hardness, kind of a substrate, coating method, coating conditions, coating thickness, uniformity of a coating film, adhesion to the substrate, etc.
• the active energy curing initiator (e) to be used for the antireflection film of the present invention the same initiators as exemplified in the above-mentioned curable fluorine-containing resin composition can be used.
• kind and an amount of the initiator can be optionally selected in the above-mentioned range in consideration of kind (reactivity, content) of the carbon-carbon unsaturated bond in the fluorine-containing prepolymer, curing conditions, a pot life of the coating, etc.
• the solvent (f) there can be used those exemplified in the above-mentioned curable resin composition for coating.
• Kind and an amount of the solvent (f) are optionally selected from the above-mentioned examples depending on intended coatability, film forming property, uniformity of a coating thickness, productivity in coating, etc.
• the solvents those which cause dissolving and swelling of the transparent substrate are not preferred.
• Particularly preferred are those selected from ketone solvents, acetic acid ester solvents, alcohol solvents and aromatic hydrocarbon solvents.
• the same curing agent (g) as mentioned above may be used together with the curable fluorine-containing prepolymer (d).
• the use of the curing agent can make hardness of the cured coating film higher.
• the cured article has a refractive index of not more than 1.49, more preferably not more than 1.45, further preferably not more than 1.40. Most preferred is a refractive index of not more than 1.38. A lower refractive index is more advantageous from the viewpoint of a reflection reducing effect.
• a preferable coating thickness of the antireflection film to be used on various substrates varies with the refractive indices of the film and substrate and is selected in the range of from 0.03 to 0.5 ⁇ m, preferably from 0.07 to 0.2 ⁇ m, more preferably from 0.08 to 0.12 ⁇ m.
• the coating thickness is too small, there is a tendency that reduction of reflectance due to light interference in visible light becomes insufficient.
• the coating thickness is too large, since the reflectance comes to depend only on a reflection nearly at an interface between air and film, there is a tendency that reduction of reflectance due to light interference in visible light becomes insufficient.
• a proper coating thickness is set so that a wavelength exhibiting a minimum reflectance of an antireflection-treated article provided with the antireflection film is usually from 420 to 720 nm, preferably from 520 to 620 nm.
• the fifth of the present invention relates to the antireflection-treated article obtained by applying the antireflection film on a substrate.
• Kind of the article, namely kind of the substrate which is provided with the antireflection film is not limited particularly. Examples thereof are, for instance, inorganic materials such as glass, stone, concrete and tile; synthetic resins, namely vinyl chloride resin, polyethylene terephthalate, cellulose resins 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 and polyimide resin; metals such as iron, aluminum and copper; wood, paper, printed matter, printing paper, picture, etc.
• synthetic resins namely vinyl chloride resin, polyethylene terephthalate, cellulose resins such as triacetyl cellulose, polycarbonate resin, polyolefin resin, acrylic resin, phenol resin, xylene resin, urea resin, melamine resin, diallyl phthalate resin, furan
• the antireflection film can be preferably provided particularly on the transparent resin substrates such as an acrylic resin, polycarbonate, cellulose rein, polyethylene terephthalate and polyolefin resin, and a reflection reducing effect can be exhibited effectively.
• Optical parts such as prism, lens sheet, polarizing plate, optical filter, lenticular lens, Fresnel lens, screen of rear projection display, optical fiber and optical coupler;
• Transparent protection plates represented by glass for show window, glass for display case, cover for advertisement and cover for photo-stand;
• Optical recording media such as magnetic optical disk, read only type optical disks such as CD, LD and DVD, phase transition type optical disk such as PD and hologram recorder;
• Photolithography-related members for production of semiconductors such as photoresist, photomask, pellicle and reticule;
• the antireflection film of the present invention may be formed into a cured coating film having a thickness of about 0.1 ⁇ m by applying a solution of the fluorine-containing prepolymer (d) directly on a substrate and then irradiating the coating film with light, or the antireflection film may be formed, as a top coat, on one or plural undercoat layers formed on the substrate.
• the effects of the undercoat are roughly classified into three, namely an increase of scratch resistance of the top coat, protection of the substrate and an increase of a reflection reducing effect by providing the layers having a refractive index higher than that of the substrate.
• a self-repairing undercoat mentioned in JP7-168005A may be used.
• a coating generally called a hard coat may be used.
• the hard coat are cured articles from curable acrylic resin, epoxy resin and silicon alkoxide compounds, cured articles from metal alkoxide compounds and the like. A heat curing method can be applied on all of them.
• a photo-curing method (ultraviolet light) is preferred from the viewpoint of productivity.
• an additive imparting electric conductivity examples include polymers having ionic group such as —COO—, —NH 2 , —NH 3 + , —NR 11 R 12 R 13 , in which R 11 R 12 and R 13 are, for example, methyl, ethyl, n-propyl, n-butyl or the like, or —SO 3 —, silicone compounds, inorganic electrolytes (for example, NaF, CaF 2 , etc.) and the like.
• polymers having ionic group such as —COO—, —NH 2 , —NH 3 + , —NR 11 R 12 R 13 , in which R 11 R 12 and R 13 are, for example, methyl, ethyl, n-propyl, n-butyl or the like, or —SO 3 —
• silicone compounds for example, NaF, CaF 2 , etc.
• an anti-static agent to the undercoat layer of the antireflection film and/or top coat layer.
• the additive are the above-mentioned additives imparting electric conductivity and in addition, fine particles of metal oxides, fluoroalkoxysilane, surfactants (anionic, cationic, amphorytic and nonionic surfactants) and the like.
• Examples of the preferable anti-static agent to be added to the undercoat layer are fine particles of metal oxides, concretely antimony-doped tin oxide (ATO) and indium-containing tin oxide (ITO) since the anti-static effect is high, is maintained for a long period of time and is hardly affected by humid and since the refractive index of the substrate can be adjusted because transparency and refractive index of the anti-static agent are high, thereby enabling the reflection reducing effect to be enhanced. From the viewpoint of transparency, ATO is preferred, and from the viewpoint of anti-static effect or electric conductivity, ITO is preferred. Even in case where no anti-static effect is required, a reflection reducing effect can be increased with those additives since the refractive index can be adjusted easily.
• ATO concretely antimony-doped tin oxide
• ITO indium-containing tin oxide
• the thickness of the undercoat layer is preferably sub-micron or so.
• the thickness of the undercoat layer is preferably from 0.05 to 0.3 ⁇ m though it depends on the refractive index of the cured fluorine-containing prepolymer.
• An optimum refractive index is preferably from 1.55 to 1.95 though it also depends on the refractive index of the fluorine-containing polymer.
• alkoxysilane anti-static agents are preferred from the point that the refractive index is hardly increased and those agents do not have an adverse effect on the reflection reducing effect.
• Fluoroalkoxysilane is further preferred since its action to increase the refractive index is further smaller and in addition, an effect of improving surface characteristics can be expected.
• the hard coat layer can be formed by the method of coating a solution of alkoxysilane or polysilazane and then heating and curing. Also a cured film obtained from an ultraviolet curable acrylic coating or a cured film obtained by melamine-crosslinking can be used.
• the antireflection film of the present invention may be provided on an undercoat layer formed by applying a coating agent containing fine particles as a flattening agent, namely on a substrate film (for example, TAC film and the like) subjected to anti-glaring (AG) treatment.
• a coating agent containing fine particles as a flattening agent namely on a substrate film (for example, TAC film and the like) subjected to anti-glaring (AG) treatment.
• AG anti-glaring
• the antireflection film of the present invention has a high fluorine content and a low surface contact angle and also possesses water repelling property, non-tackiness and stain-proofing property and therefore can be used as both of the antireflection layer and stain-proofing layer.
• a fluorine-containing polyether compound can be added.
• the adding amount of the compound need be decided in consideration of lowering of mechanical properties and white turbidity due to phase separation from the fluorine-containing polymer.
• carboxyl group, blocked carboxyl group, hydroxyl group, epoxy group, alkoxysilane group, (meth)acryloyl group or ⁇ -fluoroacryloyl group is introduced to an end of the compound, the compound is easily fixed in the coating film (Experimental Examples 33, 34 and 35). Also there is the same effect when the same polyether compound as above is coated on a surface of a previously formed antireflection film (a coating film before or after curing).
• a solution uniform solution
• known coating methods can be employed. For example, a roll coating method, micro gravure coating method, gravure coating method, flow coating method, bar coating method, spray coating method, die coating method, spin coating method and dip coating method can be employed.
• the optimum coating method is selected from them in consideration of a balance of productivity, controllability of a coating thickness, yield, etc.
• the antireflection film formed into a film or sheet may be adhered to a substrate.
• a silane compound may be added to enhance adhesion of the antireflection film to the substrate.
• An amount of the silane compound added to the coating film may be several % by weight.
• treating of a substrate surface with a silane compound has an effect on improvement of adhesion.
• the silane compound in any of the above cases, the silane compound hardly increases the refractive index of the cured film and therefore an influence thereof on the reflection reducing effect is very small.
• the polymer was a fluorine-containing polymer consisting of the structural unit of the above-mentioned fluorine-containing allyl ether and having hydroxyl at an end of its side chain.
• the number average molecular weight of the polymer was 9,000 according to the GPC analysis using tetrahydrofuran (THF) as a solvent and the weight average molecular weight thereof was 22,000.
• a 200 ml four-necked flask equipped with a reflux condenser, thermometer, stirrer and dropping funnel was charged with 80 ml of diethyl ether, 5.0 g of the fluorine-containing allyl ether homopolymer having hydroxyl which was obtained in Preparation Example 1 and 1.0 g of pyridine, followed by cooling to 5° C. or lower with ice.
• the obtained polymer was a copolymer comprising a fluorine-containing allyl ether having
• the ether solution was coated on a NaCl plate and formed into a cast film at room temperature. According to IR analysis of the cast film, an absorption of a carbon-carbon double bond was observed at 1,661 cm ⁇ 1 , and an absorption of C ⁇ O group was observed at 1,770 cm ⁇ 1 .
• a curable fluorine-containing polymer (ether solution) was synthesized in the same manner as in Experimental Example 1 except that 0.65 g of ⁇ -fluoroacrylic acid fluoride CH 2 ⁇ CFCOF and 1.0 g of pyridine were used.
• the polymer was a copolymer comprising a fluorine-containing allyl ether having
• a curable fluorine-containing polymer (ether solution) was synthesized in the same manner as in Experimental Example 1 except that 0.35 g of ⁇ -fluoroacrylic acid fluoride CH 2 ⁇ CFCOF and 0.3 g of pyridine were used.
• the polymer was a copolymer comprising a fluorine-containing allyl ether having
• the above-mentioned coating composition was coated on a non-treated acryl plate at room temperature at 1,000 to 2,000 rpm with a spin coater, followed by drying at 50° C. for five minutes. The number of revolutions of the spin coater was adjusted so that a coating thickness after the drying became from 90 to 110 nm.
• the coating film after the drying was irradiated with ultraviolet light at an intensity of 3,000 mJ/cm 2 U using a high pressure mercury lamp.
• the coating composition prepared in (1) above was coated on an aluminum foil with an applicator so that a coating thickness became about 100 ⁇ m, followed by drying at 50° C. for ten minutes. After the light irradiation was carried out in the same manner as in (2) above, the aluminum foil was melted with diluted hydrochloric acid to obtain a sample film. A refractive index of the obtained cured film was measured in the same manner as in (3) above.
• the acryl plate having the antireflection film which was obtained in (2) above was set on a UV-VIS spectrophotometer equipped with a 5° regular reflection unit, and a reflectance was measured with light having a wavelength of 550 nm.
• Tackiness of the film is evaluated by touching with a finger according to JIS K4500.
• a cotton cloth (BEMCOT (Registered trademark) M-3 available from Asahi Chemical Co., Ltd.) is fitted to a rubbing tester, and the antireflection film 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.
• x There is a portion where a film is peeled and a substrate is seen.
• Respective coating compositions were prepared using the curable fluorine-containing polymer obtained in Experimental Example 1 by the same procedures as in Experimental Example 4 so that the concentrations of the polymer and the amounts of active energy curing initiator became those shown in Table 2.
• the coating compositions prepared in (1) above were coated on a PET film with an applicator so that a coating thickness after drying became about 100 ⁇ m, followed by drying at 50° C. for five minutes. Then the obtained coating films were peeled from the PET film to obtain cast films.
• a curable fluorine-containing polymer (ether solution) was synthesized in the same manner as in Experimental Example 1 except that 2.0 g of ⁇ -fluoroacrylic acid fluoride (CH 2 ⁇ CFCOF) and 2.0 g of pyridine were used.
• the polymer was a copolymer comprising a fluorine-containing allyl ether having
• Respective coating compositions were prepared using the curable fluorine-containing polymer obtained in Experimental Example 13 by the same procedures as in Experimental Example 4 so that the concentrations of the polymer and kinds and amounts of active energy curing initiator became those shown in Table 3.
• a fluorine-containing resin composition for coating was prepared by adding, as a curing agent,
• the obtained polymer was a fluorine-containing polymer consisting of the structural unit of the above-mentioned fluorine-containing allyl ether and having hydroxyl at an end of its side chain.
• the number average molecular weight of the polymer was 30,000 according to the GPC analysis using tetrahydrofuran (THF) as a solvent and the weight average molecular weight thereof was 59,000.
• the components of the copolymer were VdF and the fluorine-containing allyl ether having OH group in a ratio of 38:62% by mole according to 1 H-NMR and 19 F-NMR analyses.
• the number average molecular weight of the copolymer was 12,000 according to the GPC analysis using THF as a solvent and the weight average molecular weight thereof was 18,000.
• a 200 ml four-necked flask equipped with a reflux condenser, thermometer, stirrer and dropping funnel was charged with 2.0 g of 2-hydroxy-2-methyl propiophenone, 1.0 g of pyridine and 20 g of a mixture (HCFC-225) of CF 3 CF 2 CHCl/CClF 2 CF 2 CHClF and was cooled to 5° C. or lower with ice.
• a 200 ml four-necked flask equipped with a reflux condenser, thermometer, stirrer and dropping funnel was charged with 40 ml of methyl ethyl ketone (MEK), 5.0 g of the fluorine-containing allyl ether homopolymer having hydroxyl which was obtained in Preparation Example 2 and 2.0 g of pyridine, and was cooled to 5° C. or lower with ice.
• MEK methyl ethyl ketone
• the MEK solution was put in the dropping funnel and washed with water, 2% hydrochloric acid solution, 5% NaCl solution and water, followed by separation of an organic layer and drying with anhydrous magnesium sulfate. A concentration of the polymer after filtrating was 10.7% by weight.
• the obtained polymer was a copolymer comprising a fluorine-containing allyl ether having
• a curable fluorine-containing polymer (MEK solution) was synthesized in the same manner as in Experimental Example 19 except that 5.0 g of the copolymer of the fluorine-containing allyl ether having OH group and VdF which was obtained in Preparation Example 3, 1.1 g of pyridine and 1.0 g of ⁇ -fluoroacrylic acid fluoride were used. A concentration of the polymer was 9.9% by weight.
• the polymer was a copolymer comprising a fluorine-containing allyl ether having
• MEK was added to the curable fluorine-containing polymer (MEK solution) obtained in Experimental Example 19 to adjust the concentration of the polymer to 8% by weight.
• the coating composition containing the fluorine-containing active energy curing initiator was evaluated in the same manner as in (2) to (6) of Experimental Example 4 (in (2), irradiation of light was carried out at 1,500 mJ/cm 2 ), and a ratio of curing reaction when irradiated with light of 1,500 mJ/cm 2 was measured in the same manner as in Experimental Example 10. The results are shown in Table 4.
• MEK was added to the curable fluorine-containing polymer (MEK solution) obtained in Experimental Example 20 to adjust the concentration of the polymer to 8% by weight.
• the polymer was a fluorine-containing polymer consisting of the structural unit of the above-mentioned fluorine-containing allyl ether and having hydroxyl at an end of its side chain.
• the number average molecular weight of the polymer was 72,000 according to the GPC analysis using tetrahydrofuran (THF) as a solvent and the weight average molecular weight thereof was 118,000.
• a 200 ml four-necked flask equipped with a reflux condenser, thermometer, stirrer and dropping funnel was charged with 50 ml of methyl ethyl ketone (MEK), 5.0 g of the fluorine-containing allyl ether homopolymer having hydroxyl which was obtained in Preparation Example 4 and 2.5 g of pyridine, and was cooled to 5° C. or lower with ice.
• MEK methyl ethyl ketone
• the MEK solution was put in the dropping funnel and washed with water, 2% hydrochloric acid solution, 5% NaCl solution and water, followed by drying with anhydrous magnesium sulfate and separating the solution by filtrating to obtain the MEK solution.
• a concentration of the polymer was 13% by weight.
• the polymer was a copolymer comprising a fluorine-containing allyl ether having —OCOCF ⁇ CH 2 group and a fluorine-containing allyl ether having OH group in a ratio of 70:30% by mole.
• the solution was coated on a NaCl plate and formed into a cast film at room temperature. According to IR analysis of the cast film, an absorption of a carbon-carbon double bond and an absorption of C ⁇ O group were observed at 1,661 cm ⁇ 1 and 1,770 cm ⁇ 1 , respectively.
• MEK was added to the solution of fluorine-containing polymer having ⁇ -fluoroacryloyl group which was obtained in Experimental Example 23 to dilute the solution and adjust a concentration of the polymer to 5.0% by weight.
• the above-mentioned coating composition was coated on a non-treated acryl plate at room temperature at 1,000 to 2,000 rpm with a spin coater, followed by drying at 50° C. for five minutes. The number of revolutions of the spin coater was adjusted so that a coating thickness after the drying became from 90 to 110 nm.
• the coating film after the drying was irradiated with ultraviolet light at room temperature at an intensity of 1,500 mJ/cm 2 U using a high pressure mercury lamp.
• the acryl plate having the antireflection film which was obtained in (2) above was set on a visible ultraviolet spectroscope equipped with a 5° regular reflection unit, and a reflectance was measured with light having a wavelength of 550 nm. The results are shown in Table 5.
• a cotton cloth (BEMCOT (Registered trademark) M-3 available from Asahi Chemical Co., Ltd.) is fitted to a rubbing tester, and the antireflection film is rubbed by 100 rubbing cycles at a load of 100 gf/cm 2 to observe conditions of the film.
• BEMCOT Registered trademark
• M-3 available from Asahi Chemical Co., Ltd.
• Antireflection films were produced in the same manner as in (2) of Experimental Example 24 using the respective coating compositions, and physical properties of the antireflection films were evaluated in the same manner as in (4) Measurement of refractive index of cured film, (5) Measurement of reflectance of one side of film and (6) Evaluation of physical properties of antireflection film. The results are shown in Table 5.
• a fluorine-containing resin composition for coating was prepared in the same manner as in Experimental Example 17 except that
• a 200 ml four-necked flask equipped with a reflux condenser, thermometer, stirrer and dropping funnel was charged with 50 ml of MEK, 5.0 g of the copolymer comprising a fluorine-containing allyl ether having OH group and VdF and obtained in Preparation Example 3 and 2.2 g of pyridine, and was cooled to 5° C. or lower with ice.
• the MEK solution was put in the dropping funnel and washed with water, 2% hydrochloric acid solution, 5% NaCl solution and water, followed by drying with anhydrous magnesium sulfate and separating the MEK solution by filtrating.
• a concentration of the polymer was 13.0% by weight.
• the polymer was a copolymer comprising a fluorine-containing allyl ether having —OCOCF ⁇ CH 2 group and VdF in a ratio of 62:38% by mole.
• the solution was coated on a NaCl plate and formed into a cast film at room temperature. According to IR analysis of the cast film, an absorption of a carbon-carbon double bond and an absorption of C ⁇ O group were observed at 1,661 cm ⁇ 1 and 1,770 cm ⁇ 1 , respectively.
• the ether solution was put in the dropping funnel and washed with water, 2% hydrochloric acid solution, 5% NaCl solution and water, followed by drying with anhydrous magnesium sulfate and separating the solution by filtrating. After distilling off the solvent from the filtrate with an evaporator, the solution was dried for six hours in an evacuated state while heating to 70° C. and thus a transparent colorless liquid having a high viscosity was obtained.
• the coating composition obtained above was coated on a non-treated acryl plate at room temperature at 2,000 to 5,000 rpm with a spin coater, followed by drying at 50° C. for five minutes. In that case, the number of revolutions of the spin coater was adjusted so that a coating thickness after the drying became from 90 to 110 nm.
• the coating film after the drying was irradiated with ultraviolet light at room temperature at an intensity of irradiation of 1,500 mJ/cm 2 U using a high pressure mercury lamp.
• the polymer was a fluorine-containing polymer consisting of the structural unit of the above-mentioned fluorine-containing allyl ether and having hydroxyl at an end of its side chain.
• the number average molecular weight of the polymer was 24,000 according to the GPC analysis using tetrahydrofuran (THF) as a solvent and the weight average molecular weight thereof was 79,000.
• the polymer was a copolymer comprising a fluorine-containing allyl ether having —OCOCF ⁇ CH 2 group and a fluorine-containing allyl ether having OH group in a ratio of 54:46% by mole.
• the product was a copolymer comprising the above-mentioned fluorine-containing allyl ether having hydroxyl and fluorine-containing allyl ether having a methyl ester structure at an end thereof in a ratio of 42:58% by mole.
• the number average molecular weight of the polymer was 72,000 according to the GPC analysis using tetrahydrofuran (THF) as a solvent and the weight average molecular weight thereof was 117,000.
• the polymer 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 a methyl ester structure at an end thereof in a ratio of 38:4:58% by mole.
• ⁇ Coating film is dried in a state of uniform coating thickness and there is no interference pattern after the drying.
• ⁇ Coating film is dried in a state of uniform coating thickness but there is a small interference pattern after the drying.
• MEK was added to the solutions of fluorine-containing polymer having ⁇ -fluoroacryloyl group which were obtained in Experimental Example 23 (Experimental Example 46) and Experimental Example 30 (Experimental Example 47) to dilute the solutions and adjust the polymer concentration to 5.0% by weight.
• a 100 ml stainless steel autoclave equipped with a valve, pressure gauge and thermometer was charged with 10.0 g of perfluoro(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol), 50 g of CH 3 CCl 2 F (HCFC-141b) and 0.1 g of a methanol solution of 50% by weight of dinormalpropyl peroxy carbonate (NPP), and the inside of a system was sufficiently replaced with nitrogen gas while cooling with a dry ice/methanol solution. Then 8.0 g of tetrafluoroethylene (TFE) was introduced through the valve. After completion of the reaction carried out for 14 hours while shaking at 40° C., un-reacted monomer was released to terminate the reaction.
• TFE tetrafluoroethylene
• a precipitated solid was removed and dissolved in acetone, followed by re-precipitation with a solvent mixture of hexane and HCFC-225 (20/80) to separate a copolymer.
• the copolymer was vacuum-dried until a constant weight was reached. Thus 9.3 g of the copolymer was obtained.
• components of the copolymer were TFE and the fluorine-containing allyl ether having OH group in a ratio of 48:52% by mole.
• the number average molecular weight of the polymer was 24,000 according to the GPC analysis using THF as a solvent and the weight average molecular weight thereof was 36,100.
• a 100 ml stainless steel autoclave equipped with a valve, pressure gauge and thermometer was charged with 10.0 g of perfluoro(1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxanonenol), 50 g of CH 3 CCl 2 F (HCFC-141b) and 0.1 g of a methanol solution of 50% by weight of dinormalpropyl peroxy carbonate (NPP), and the inside of a system was sufficiently replaced with nitrogen gas while cooling with a dry ice/methanol solution. Then 5.8 g of chlorotrifluoroethylene (CTFE) was introduced through the valve. After completion of the reaction carried out for 20 hours while shaking at 40° C., un-reacted monomer was released to terminate the reaction.
• CFE chlorotrifluoroethylene
• a precipitated solid was removed and dissolved in acetone, followed by re-precipitation with a solvent mixture of hexane and HCFC-141b (50/50) to separate a copolymer.
• the copolymer was vacuum-dried until a constant weight was reached. Thus 5.7 g of the copolymer was obtained.
• components of the copolymer were CTFE and the fluorine-containing allyl ether having OH group in a ratio of 35:65% by mole.
• the number average molecular weight of the polymer was 10,500 according to the GPC analysis using THF as a solvent and the weight average molecular weight thereof was 7,200.
• the polymer was a copolymer comprising a fluorine-containing allyl ether having —OCOCF ⁇ CH 2 group and TFE in a ratio of 52:48% by mole.
• the polymer was a copolymer comprising a fluorine-containing allyl ether having —OCOCF ⁇ CH 2 group, a fluorine-containing allyl ether having OH group and CTFE in a ratio of 50:15:35% by mole.
• the ether solution was poured in an excessive amount of water and an organic substance was extracted with ether, followed by washing of the ether layer with water, 2% hydrochloric acid solution, 5% NaCl solution and then water, drying the ether layer with anhydrous magnesium sulfate and distilling off the ether to obtain 23 g of an organic substance.
• the obtained polymer was a fluorine-containing polymer consisting of the structural unit of the above-mentioned fluorine-containing allyl ether and having two OH groups at each side chain.
• the polymer was a polymer consisting of a structural unit derived from the fluorine-containing allyl ether represented by the formula:
• the polymer was coated on a NaCl plate and formed into a cast film at room temperature. According to IR analysis, an absorption of a carbon-carbon double bond was observed at 1,660 cm ⁇ 1 and an absorption of C ⁇ O group was observed at 1,770 cm ⁇ 1 . However an absorption of OH group could not be observed.
• a curable fluorine-containing polymer which can realize a high hardness by photo-curing while maintaining a low refractive index.
• an antireflection film possessing improved scratch resistance and abrasion resistance while maintaining a reflection reducing effect, and an antireflection-treated article provided with such an antireflection film can be provided.

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