Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • 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
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
• • 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
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/52—Amides or imides
  • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F20/56—Acrylamide; Methacrylamide
• • 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
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • 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
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/65—Additives macromolecular

Definitions

• the present invention relates to a modifier, a composition, a hard coat film, an article provided with the hard coat film, and an image display device.
• Display devices using a cathode ray tube (CRT), plasma display (PDP), electroluminescence display (ELD), fluorescent display (VFD), field emission display (FED), and image display device such as liquid crystal display (LCD) In order to prevent the display surface from being damaged, it is preferable to provide an optical film (hard coat film) having a hard coat layer on the substrate.
• CTR cathode ray tube
• PDP plasma display
• ELD electroluminescence display
• VFD fluorescent display
• FED field emission display
• LCD liquid crystal display
• An agent may be added to the coating composition.
• the leveling agent By using the leveling agent, the surface tension of the coating film is reduced, and the wettability (homogeneous coating property) of the coating composition to the substrate during coating and the surface state of the coating film surface are improved.
• the leveling agent is unevenly distributed on the surface of the coating film, so that the water and oil repellency of the coating film surface is high.
• Patent Document 1 discloses a polymer obtained by polymerizing a fluorinated alkyl group-containing ethylenically unsaturated monomer as an essential component, and a specific amount of a fluorinated alkyl group-containing ethylenically unsaturated monomer.
• a fluorine-based surfactant comprising a monomer and a polymer obtained by polymerizing an ethylenically unsaturated monomer containing a hydrophilic structural unit as an essential component.
• An object of the present invention is to provide a modifier suitable for the formation of a coating film having a good surface shape and excellent recoatability, a composition containing the modifier, a hard coat film containing the modifier, an object of the present invention is to provide an article and an image display device including the hard coat film.
• a modifier comprising a polymer having a weight average molecular weight of 1,000 to 50,000, obtained by polymerizing a monomer having two or more groups having a radical polymerizable double bond and containing at least one nitrogen atom.
• the polymer has at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms.
• the polymer has a fluorine atom.
• ⁇ 4> The modifier according to any one of ⁇ 1> to ⁇ 3>, wherein the polymer has a structure represented by the following general formula (s).
• R 1s represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
• R 2s has an alkyl group having 1 to 20 carbon atoms having at least one fluorine atom or at least one fluorine atom.
• An alkenyl group having 2 to 20 carbon atoms is represented. * Represents a bond.
• ⁇ 5> The modifier according to any one of ⁇ 1> to ⁇ 4>, wherein the group having a radical polymerizable double bond is a group represented by any one of the following general formulas (Z1) to (Z6).
• R m1 in the general formula (Z3) and R m2 in the general formula (Z4) each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
• the monomer has three or more groups having the radical polymerizable double bond.
• NI general formulas
• L 11 , L 12 and L 13 each independently represent a divalent or trivalent linking group
• R 11 , R 12 and R 13 each independently represent a hydrogen atom or a methyl group
• n11 to n13 each independently represents 1 or 2.
• n11 represents 2
• two R 11 may be the same or different.
• n12 represents 2
• two R 12 may be the same or different.
• n13 represents 2
• two R 13 may be the same or different.
• R 21 and R 22 each independently represent a hydrogen atom or a methyl group.
• L 21 represents a divalent to hexavalent linking group.
• n21 represents an integer of 1 to 5. If n21 represents an integer of 2 or more, it may be different even multiple R 22 are each identical.
• L 31 and L 32 each independently represent a divalent to tetravalent linking group
• L 33 represents a divalent linking group
• R 31 and R 32 each independently represent a hydrogen atom or methyl
• n31 and n32 each independently represents an integer of 1 to 3.
• n31 represents an integer of 2 or more
• the plurality of R 31 may be the same or different.
• n32 represents an integer of 2 or more
• the plurality of R 32 may be the same or different.
• composition as described in ⁇ 9> containing at least 1 sort (s) chosen from polyorgano silsesquioxane and the compound (a2) which has a 2 or more (meth) acryloyl group in 1 molecule.
• the hard coat layer includes at least one selected from polyorganosilsesquioxane and a cured product of the compound (a2) having two or more (meth) acryloyl groups in one molecule,
• the functional layer includes a mixed layer, Having the base material, the hard coat layer, and the mixed layer in this order, ⁇ 11>, wherein the mixed layer includes a cured product (b1) of a compound having an epoxy group and a cured product of a compound (b2) having two or more (meth) acryloyl groups in one molecule.
• the functional layer includes a scratch-resistant layer, The substrate, the hard coat layer, the mixed layer, and the scratch-resistant layer in this order, The hard-coated film according to ⁇ 12>, wherein the scratch-resistant layer includes a cured product of the compound (c1) having two or more (meth) acryloyl groups in one molecule.
• An image display device comprising the hard coat film according to any one of ⁇ 11> to ⁇ 13> as a surface protective film.
• a modifier suitable for forming a coating film having a good surface shape and excellent recoatability, a composition containing the modifier, a hard coat film containing the modifier, An article and an image display apparatus provided with the hard coat film can be provided.
• the modifier of the present invention is a polymer having a weight average molecular weight of 1,000 to 50,000, which is obtained by polymerizing a monomer having two or more groups having a radical polymerizable double bond and containing at least one nitrogen atom. It is a modifier composed of coalescence.
• a monomer having two or more groups having a radical polymerizable double bond and containing at least one nitrogen atom is also referred to as “monomer (K1)”.
• a polymer obtained by polymerizing the monomer (K1) and having a weight average molecular weight of 1,000 to 50,000 is also referred to as “polymer (L1)”.
• the modifier of the present invention is suitable for forming a coating film having a good surface shape and excellent recoatability.
• the monomer (K1) has two or more groups having a radical polymerizable double bond
• the polymer (L1) obtained by polymerizing the monomer (K1) has a branched structure.
• the monomer (K1) has a nitrogen atom
• the polymer (L1) obtained by polymerizing the monomer (K1) also has a nitrogen atom.
• the matrix resin forming component (curable component) in the composition containing the modifier (polymer (L1)) of the present invention and the like.
• the modifying agent is applied to the surface of the coating film because the compatibility between the modifier and the solvent in the upper layer forming composition is good.
• the monomer (K1) has two or more groups having a radical polymerizable double bond.
• the modifier of the present invention has a branched structure and is included in the composition containing the modifier. Compatibility with curable components and the like is improved.
• the group having a radical polymerizable double bond that the monomer (K1) has is not particularly limited. Moreover, the group which has 2 or more radically polymerizable double bonds which a monomer (K1) has may be the same, or may differ.
• the number of groups having a radical polymerizable double bond in the monomer (K1) is preferably 3 or more, more preferably 3 or more and 9 or less, and more preferably 3 or more and 6 or less. Is more preferable.
• the branched structure of the modifier becomes a highly branched structure, and there is little entanglement between the molecular chains of the modifier, and compatibility with curable components And the solubility in various organic solvents is improved, and the uniform coatability of the composition and the surface state of the resulting coating film are improved. Further, by controlling the number of radically polymerizable double bonds to 9 or less, it becomes easy to control the molecular weight during radical polymerization.
• the group having a radical polymerizable double bond is preferably any of groups represented by the following general formulas (Z1) to (Z6).
• R m1 in the general formula (Z3) and R m2 in the general formula (Z4) each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
• R m1 in the general formula (Z3) and R m2 in the general formula (Z4) are preferably a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. More preferably, it is a hydrogen atom, a methyl group, or an ethyl group.
• the group having a radical polymerizable double bond is preferably a group represented by the general formula (Z1), (Z2), (Z3) or (Z4), and represented by the general formula (Z1) or (Z2). It is more preferred that
• the group represented by the general formula (Z3) or (Z4) is a group having a radical polymerizable double bond and a group having a nitrogen atom.
• the monomer (K1) has at least one nitrogen atom.
• the polymer (L1) also has a nitrogen atom, and the modifier of the present invention and the curable component contained in the composition containing the modifier, etc. Compatibility is improved. As will be described later, the compatibility with the polyorganosilsesquioxane is improved particularly when the modifier has a nitrogen atom.
• the nitrogen atom is preferably contained in the polymer (L1) as at least one structure selected from an isocyanuric ring, a urethane bond, an amide bond, and a urea bond, and the polymer (as an isocyanuric ring, a urethane bond, or an amide bond) More preferably, it is contained in L1), and it is still more preferred that it is contained in the polymer (L1) as an isocyanuric ring.
• the polymer (L1) preferably has at least one selected from an isocyanuric ring, a urethane bond, an amide bond, and a urea bond, more preferably has an isocyanuric ring, a urethane bond, or an amide bond. More preferably, it has a ring.
• the number of nitrogen atoms contained in the monomer (K1) is preferably 2 or more, and more preferably 3 or more, from the viewpoint of improving compatibility with the curable component and the like.
• the monomer (K1) is preferably a compound represented by any one of the following general formulas (NI) to (NIII).
• L 11 , L 12 and L 13 each independently represent a divalent or trivalent linking group
• R 11 , R 12 and R 13 each independently represent a hydrogen atom or a methyl group
• n11 to n13 each independently represents 1 or 2.
• n11 represents 2
• two R 11 may be the same or different.
• n12 represents 2
• two R 12 may be the same or different.
• n13 represents 2
• two R 13 may be the same or different.
• R 21 and R 22 each independently represent a hydrogen atom or a methyl group.
• L 21 represents a divalent to hexavalent linking group.
• n21 represents an integer of 1 to 5. If n21 represents an integer of 2 or more, it may be different even multiple R 22 are each identical.
• L 31 and L 32 each independently represent a divalent to tetravalent linking group
• L 33 represents a divalent linking group
• R 31 and R 32 each independently represent a hydrogen atom or methyl
• n31 and n32 each independently represents an integer of 1 to 3.
• n31 represents an integer of 2 or more
• the plurality of R 31 may be the same or different.
• n32 represents an integer of 2 or more
• the plurality of R 32 may be the same or different.
• L 11 , L 12 and L 13 each independently represent a divalent or trivalent linking group.
• the divalent linking group represented by L 11 , L 12 and L 13 include an alkylene group, a cycloalkylene group, an arylene group, —O—, —CO—, —COO—, —NH—, —NHCO— and —NHCOO. -, -S-, or a divalent linking group obtained by combining these groups.
• the alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, such as an ethylene group, n-propylene group, i-propylene group, n-butylene group, n- Examples include a hexylene group.
• the alkylene group may be linear or branched.
• the cycloalkylene group is preferably a cycloalkylene group having 6 to 20 carbon atoms, more preferably a cycloalkylene group having 6 to 10 carbon atoms, and examples thereof include a cyclohexylene group and a cycloheptylene group.
• the arylene group is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms, and examples thereof include a phenylene group and a naphthylene group.
• the alkylene group, cycloalkylene group or arylene group may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, an amino group, a cyano group, a nitro group, a halogen atom, an alkyl group, and a cycloalkyl group. Group, aryl group, alkoxy group, acyl group and the like.
• the divalent linking group represented by L 11 , L 12 and L 13 is an alkylene group or an alkylene group and —O—, —CO—, —COO—, —NH—, —NHCO—, —NHCOO—, —
• a divalent linking group in combination with at least one group selected from S— is preferable, and an alkylene group is more preferable.
• Examples of the trivalent linking group L 11, L 12 and L 13 represent, from a divalent linking group represented by L 11, L 12 and L 13 of the above, formed by dividing one arbitrary hydrogen atom linking group Is mentioned.
• R 11 , R 12 and R 13 each independently represent a hydrogen atom or a methyl group, and preferably represents a hydrogen atom.
• n11 to n13 each independently represents 1 or 2. n11 to n13 preferably represent 1.
• the compound represented by the general formula (NI) can be synthesized according to the method described in JP-A No. 2004-141732.
• R 21 and R 22 each independently represent a hydrogen atom or a methyl group, and preferably represents a hydrogen atom.
• L 21 represents a divalent to hexavalent linking group, and the divalent linking group is the same as the divalent linking group represented by the aforementioned L 11 , L 12 and L 13 .
• L 21 represents a trivalent to hexavalent linking group, a linking group formed by removing one to four arbitrary hydrogen atoms from the divalent linking groups represented by the aforementioned L 11 , L 12 and L 13 , respectively.
• Groups. n21 represents an integer of 1 to 5, and preferably represents an integer of 1 to 3.
• the compound represented by the general formula (NII) can be synthesized according to the method described in JP2012-206992.
• R 31 and R 32 each independently represent a hydrogen atom or a methyl group, and preferably represent a hydrogen atom.
• L 31 and L 32 each independently represent a divalent to tetravalent linking group, and the divalent linking group is the same as the divalent linking group represented by the aforementioned L 11 , L 12 and L 13 .
• L 31 and L 32 represent a trivalent or tetravalent linking group, one or two arbitrary hydrogen atoms are selected from the divalent linking group represented by the aforementioned L 11 , L 12 and L 13 , respectively.
• L 33 represents a divalent linking group, and is the same as the divalent linking group represented by the aforementioned L 11 , L 12 and L 13 .
• n31 and n32 each independently represents an integer of 1 to 3, and preferably represents 1 or 2.
• the compound represented by the general formula (NIII) can be synthesized according to the method described in JP-A-2016-65199.
• the monomer (K1) is more preferably a compound represented by the above general formula (NI).
• the monomer (K1) a commercially available product may be used.
• the monomer (K1) containing a nitrogen atom as a urethane bond UA-306H, UA-306I, UA-306T, UA-510H, and UF manufactured by Kyoeisha Chemical Co., Ltd.
• UV-1400B UV-1700B, UV-6300B, UV-6550B, UV-7550B, UV -7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-76 0B, UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3210EA, UV-3310EA, UV-3310B, UV-3310B 3500BA, UV-3520TL, UV-3700B, UV-6100B, UV-6640B, UV-2000B, UV-2010B, UV-2250EA.
• purple light UV-2750B manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
• UL-503LN manufactured by Kyoeisha Chemical Co., Ltd.
• Unidic 17-806 manufactured by Dainippon Ink and Chemicals, Inc., 17-813, V-4030, V-4000BA, and Daicel.
• Examples include EB-1290K manufactured by UCB, Hicorp AU-2010 and AU-2020 manufactured by Tokushi.
• the modifier (polymer (L1)) of the present invention preferably has at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms.
• a fluorine atom, a silicon atom, or a linear or branched alkyl group having 3 or more carbon atoms in the modifier, the surface tension of the coating film when the composition containing the modifier is applied is further reduced. , Homogeneous coatability becomes better.
• the transferability of the modifier to the coating film surface is further improved, and the surface state of the coating film surface is improved.
• the linear or branched alkyl group having 3 or more carbon atoms is preferably a linear or branched alkyl group having 3 to 30 carbon atoms, and more preferably a linear or branched alkyl group having 4 to 20 carbon atoms.
• the modifier of the present invention more preferably has a fluorine atom.
• fluorine is added to the monomer (K1).
• a raw material monomer other than the monomer (K1) (referred to as monomer (K2)) is introduced with at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms.
• the modifier contains at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms. It may be introduced.
• the modifier of the present invention is at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms by copolymerizing the monomer (K1) and the monomer (K2). It is preferable from the viewpoint of improving the surface condition of the coating film surface.
• the monomer (K2) has at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms.
• the fluorine atom is preferably contained in the monomer (K2) as an alkyl group having 1 to 20 carbon atoms having at least one fluorine atom or an alkenyl group having 2 to 20 carbon atoms having at least one fluorine atom.
• the silicon atom is preferably contained in the monomer (K2) as a siloxane bond, and more preferably contained in the monomer (K2) as a polysiloxane structure.
• the monomer (K2) is preferably a compound having a (meth) acryloyl group, and more preferably any compound represented by the following general formulas (s1) to (s3).
• R 1s represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
• R 2s has an alkyl group having 1 to 20 carbon atoms having at least one fluorine atom or at least one fluorine atom.
• An alkenyl group having 2 to 20 carbon atoms is represented.
• R 1s preferably represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, a methyl group, an ethyl group, or n- More preferably, it represents a propyl group, and particularly preferably represents a hydrogen atom or a methyl group.
• the alkyl group or alkenyl group represented by R 2s preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.
• the number of fluorine atoms contained in the alkyl group or alkenyl group represented by R 2s is preferably 1 to 20, and more preferably 3 to 17.
• R 2s is at least one fluorine atom from the viewpoint of reducing the surface energy of the composition containing the modifier of the present invention, improving the homogenous coatability, and improving the surface shape.
• the compound represented by the general formula (s1) is more preferably a compound represented by the following general formula (s11).
• R 1s represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
• ma and na each independently represents an integer of 0 or more
• X 1 represents a hydrogen atom or a fluorine atom.
• R 1s in the general formula (s11), the general formula (s1) in the same meaning as R 1s of, and preferred examples are also the same.
• ma and na each independently represents an integer of 0 or more.
• ma is preferably an integer of 1 to 10, and more preferably an integer of 1 to 5.
• na is preferably an integer of 4 to 12, and more preferably an integer of 4 to 10.
• X 1 represents a hydrogen atom or a fluorine atom, and is preferably a fluorine atom.
• Examples of the monomer represented by the general formula (s1) include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, and 2- (par Fluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (Perfluoro-3-methylbutyl) ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (me
• R 1s represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
• R 3s , R 4s , R 6s and R 7s each independently represents an alkyl group having 1 to 20 carbon atoms
• R 5s represents an alkyl group having 1 to 20 carbon atoms
• mm represents an integer of 1 to 10
• nn represents an integer of 1 or more Represents.
• the plurality of R 3s and R 4s may be the same or different.
• Examples of the alkyl group having 1 to 20 carbon atoms represented by R 3s , R 4s , R 6s and R 7s include a methyl group, an ethyl group and a hexyl group.
• the alkyl group represented by R 3s , R 4s , R 6s and R 7s is preferably an alkyl group having 1 to 10 carbon atoms.
• Examples of the haloalkyl group having 1 to 20 carbon atoms represented by R 3s , R 4s , R 6s and R 7s include a trifluoromethyl group and a pentafluoroethyl group.
• the haloalkyl group represented by R 3s , R 4s , R 6s and R 7s is preferably a fluorinated alkyl group having 1 to 10 carbon atoms.
• Examples of the aryl group having 6 to 20 carbon atoms represented by R 3s , R 4s , R 6s and R 7s include a phenyl group and a naphthyl group.
• the aryl group represented by R 3s , R 4s , R 6s and R 7s is preferably an aryl group having 6 to 20 carbon atoms.
• R 3s , R 4s , R 6s and R 7s are preferably a methyl group, a trifluoromethyl group or a phenyl group, and more preferably a methyl group.
• Examples of the alkyl group having 1 to 20 carbon atoms represented by R 5s include a methyl group, an ethyl group, and a hexyl group.
• the alkyl group represented by R 5s is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.
• mm represents an integer of 1 to 10.
• mm is preferably an integer of 1 to 6.
• nn is preferably an integer of 1 to 1000, more preferably an integer of 20 to 500, and still more preferably an integer of 30 to 200.
• One-terminal (meth) acryloyl group-containing polysiloxane macromer for example, Silaplane FM-0721, 0725, 0711 (above, products) Name, manufactured by JNC Corporation), AK-5, AK-30, AK-32 (above, trade name, manufactured by Toagosei Co., Ltd.), KF-100T, X-22-169AS, KF-102, X -22-3701IE, X-22-164B, X-22-164C, X-22-5002, X-22-173B, X-22-174D, X-22-167B, X-22-161AS Name, manufactured by Shin-Etsu Chemical Co., Ltd.).
• R 1s represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
• R 8s represents a linear or branched alkyl group having 3 or more carbon atoms.
• R 1s in the general formula (s3) of the general formula (s1) in the same meaning as R 1s of, and preferred examples are also the same.
• the linear or branched alkyl group having 3 or more carbon atoms represented by R 8s is preferably a linear or branched alkyl group having 3 to 30 carbon atoms, more preferably a linear or branched alkyl group having 6 to 20 carbon atoms. preferable.
• the monomer (K2) is preferably a monomer represented by the general formula (s1). That is, the modifier (polymer (L1)) of the present invention preferably has a structure represented by the following general formula (s).
• R 1s represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
• R 2s has an alkyl group having 1 to 20 carbon atoms having at least one fluorine atom or at least one fluorine atom.
• An alkenyl group having 1 to 20 carbon atoms is represented. * Represents a bond.
• R 1s and R 2s are the same as R 1s and R 2s in the general formula (s1), and preferred examples are also the same. * Represents a bond.
• the content of the structure selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms in the modifier of the present invention is preferably 1 to 99 mol%, and preferably 10 to 90 mol. % Is more preferable.
• the modifier of the present invention may be a homopolymer of monomer (K1) or a copolymer of monomer (K1) and monomer (K2).
• the ratio of the two can be appropriately adjusted depending on the monomer type to be used.
• the content of the monomer (K2) with respect to the total monomer amount is 20 to 90.
• the mol% is preferable, and 40 to 80 mol% is more preferable.
• the solvent extractability can be kept good.
• By adjusting the amount to 40 to 80 mol% a good balance between the improvement of the surface state of the polymer and the solvent extractability can be maintained.
• the modifier of the present invention may be a modifier obtained by polymerizing raw material monomers other than the monomer (K1) and the monomer (K2).
• the modifier (polymer (L1)) of the present invention has a weight average molecular weight of 1,000 to 50,000. By setting the weight average molecular weight to 50000 or less, the composition becomes soluble in a general-purpose organic solvent. Therefore, the hard coat layer forming composition can be prepared as a solution in which the modifier is dissolved in the organic solvent. It becomes possible to coat various general-purpose substrates such as acetyl cellulose (TAC), polyethylene terephthalate (PET), polycarbonate (PC), and polymethyl methacrylate resin (PMMA) with a uniform coated surface. Moreover, the effect which improves surface-surface shape becomes large because Mw shall be 1000 or more.
• TAC acetyl cellulose
• PET polyethylene terephthalate
• PC polycarbonate
• PMMA polymethyl methacrylate resin
• the modifier is soluble in an organic solvent means that the modifier / organic solvent (25 ° C.) is mixed at 1/4 (mass ratio) and allowed to stand for 5 minutes. It shows that the later solution turbidity is 1.0 ppm (parts per million) or less.
• the molecular weight distribution (Mw / Mn) of the modifier of the present invention is preferably 1.00 to 5.00, and more preferably 1.00 to 3.00.
• the weight average molecular weight of the modifier of the present invention is preferably 1000 to 30000, more preferably 1000 to 8000, and still more preferably 1000 to 5000.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) of the modifier of the present invention are values measured by gel permeation chromatography (GPC) under the following conditions.
• radical polymerization such as solution, suspension, and emulsification is preferable from the viewpoint of molecular weight control, and solution polymerization is particularly preferable.
• organic solvents can be suitably used.
• organic solvents include dibutyl ether, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole, phenetole, dimethyl carbonate, carbonate Methyl ethyl, diethyl carbonate, acetone, methyl ethyl ketone (MEK), diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, Methyl propionate, ethyl propionate
• radical polymerization initiator a known radical polymerization initiator can be used without any limitation.
• the number average molecular weight (Mn) of the resulting modifier is represented by the following formula (1).
• Factors affecting the molecular weight of a polymer synthesized by solution radical polymerization include a monomer / initiator concentration ratio [M] / [I] and a monomer / solvent concentration ratio [M] / [S]. That is, the molecular weight of the polymer can be controlled by lowering the monomer concentration and / or adjusting the initiator concentration.
• the modifier of the present invention can be solubilized in a general-purpose organic solvent (for example, MEK) by adjusting the concentration of the compound (M) and / or the initiator concentration in the polymerization reaction.
• a general-purpose organic solvent for example, MEK
• the radical polymerization concentration (monomer concentration with respect to the solvent during radical solution polymerization) is preferably 3 to 40% by mass, and more preferably 5 to 35% by mass.
• the amount of the radical polymerization initiator is preferably 250 mol% or more in terms of the monomer (K1) ratio.
• composition of the present invention contains the above-described modifier of the present invention.
• the composition of this invention can be used suitably for formation of the members produced by lamination
• the composition of this invention can contain a sclerosing
• the composition of the present invention can be suitably used as a composition for forming a hard coat layer for forming a hard coat layer in a hard coat film.
• the composition for forming a hard coat layer containing the modifier of the present invention is excellent in wettability (homogeneous coatability) with respect to the substrate during coating, and the surface state of the hard coat layer surface is good. Moreover, it is excellent also in the recoat property at the time of apply
• hardenable component is included in a composition.
• the curable component preferably includes at least one selected from polyorganosilsesquioxane and a compound (a2) having two or more (meth) acryloyl groups in one molecule.
• polyorganosilsesquioxane examples include polyorganosilsesquioxane (a1) having an epoxy group described later.
• Examples of the compound (a2) having two or more (meth) acryloyl groups in one molecule include the same compounds as the compound (b2) having two or more (meth) acryloyl groups in one molecule described later. .
• polyorgano silsesquioxane (a1) which has an epoxy group from the high compatibility with a modifier.
• a matrix resin forming component suitably used for the hard coat layer of such an optical film, polyorganosilsesxane is exemplified.
• composition of the present invention containing polyorganosilsesquioxane is preferably used as a composition for forming a hard coat layer in a flexible hard coat film.
• the composition for forming a hard coat layer usually takes the form of a liquid.
• the composition for forming a hard coat layer may be prepared by dissolving or dispersing the modifier of the present invention, the curable component, and if necessary, various additives and a polymerization initiator in an appropriate solvent. preferable.
• the hard coat film of the present invention is A hard coat film having a base material and a functional layer, wherein the functional layer includes at least one hard coat layer,
• the hard coat layer includes at least one selected from polyorganosilsesquioxane and a cured product of the compound (a2) having two or more (meth) acryloyl groups in one molecule,
• the outermost functional layer on the side having the hard coat layer with respect to the base material is a hard coat film containing the above-described modifier of the present invention.
• the functional layer is not particularly limited.
• a hard coat layer a low refractive index layer, a high refractive index layer, a mixed layer, a scratch-resistant layer, a low reflectance layer, an antifouling layer, an inorganic oxide layer ( AR layer), a barrier layer, and a combination thereof.
• the functional layer includes a mixed layer, Having the base material, the hard coat layer, and the mixed layer in this order,
• the mixed layer is a hard coat film containing a cured product (b1) of a compound having an epoxy group and a cured product of a compound (b2) having two or more (meth) acryloyl groups in one molecule. Is preferred.
• the functional layer includes a scratch-resistant layer, The substrate, the hard coat layer, the mixed layer, and the scratch-resistant layer in this order,
• the scratch-resistant layer is preferably a hard coat film containing a cured product of the compound (c1) having two or more (meth) acryloyl groups in one molecule.
• the modifier of the present invention can exhibit an effect when added to any of the hard coat layer and other functional layers, but the recoating effect is particularly remarkable when added to the hard coat layer. Moreover, since the modifier of this invention is excellent in solvent extractability, when it adds to the composition for hard-coat layer formation and a hard-coat film is created, it can be contained also in the outermost functional layer. The presence state of the modifier in the form of a hard coat film can be confirmed by, for example, a time-of-flight mass spectrometer (TOF-Sims).
• TOF-Sims time-of-flight mass spectrometer
• the base material of the hard coat film of the present invention will be described.
• the substrate preferably has a visible light region transmittance of 70% or more, more preferably 80% or more, and still more preferably 90% or more.
• the substrate preferably includes a polymer.
• polymer As the polymer, a polymer excellent in optical transparency, mechanical strength, thermal stability and the like is preferable.
• polystyrene polymers examples include polycarbonate polymers, polyester polymers such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and styrene polymers such as polystyrene and acrylonitrile / styrene copolymer (AS resin).
• PET polyethylene terephthalate
• PEN polyethylene naphthalate
• AS resin acrylonitrile / styrene copolymer
• Polyolefins such as polyethylene and polypropylene, polyolefin polymers such as norbornene resins, ethylene / propylene copolymers, (meth) acrylic polymers such as polymethyl methacrylate, vinyl chloride polymers, amides such as nylon and aromatic polyamides Polymer, imide polymer, sulfone polymer, polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinylidene chloride polymer, vinyl alcohol polymer, vinyl butyral polymer, arylate polymer, polyoxy A methylene polymer, an epoxy polymer, a cellulose polymer represented by triacetyl cellulose, a copolymer of the above polymers, or a mixture of the above polymers. The polymer may also be mentioned.
• amide-based polymers and imide-based polymers such as aromatic polyamides have a large number of breaks and folds measured by an MIT tester according to JIS (Japanese Industrial Standards) P8115 (2001), and have a relatively high hardness. It can be preferably used.
• an aromatic polyamide as in Example 1 of Japanese Patent No. 5699454, a polyimide described in JP-T-2015-508345, JP-T-2016-521216, and WO2017 / 014287 is preferably used as a base material. Can be used.
• the substrate can also be formed as a cured layer of an acrylic, urethane, acrylurethane, epoxy, silicone or other ultraviolet curable or thermosetting resin.
• the substrate may contain a material that further softens the polymer.
• the softening material refers to a compound that improves the number of breaks and folds.
• a rubber elastic body, a brittleness improving agent, a plasticizer, a slide ring polymer, or the like can be used as the softening material.
• the softening materials described in paragraph numbers ⁇ 0051> to ⁇ 0114> in JP-A-2016-170443 can be suitably used as the softening material.
• the softening material may be mixed with the polymer alone, or may be used in combination with a plurality as appropriate, or may be used alone or in combination with a plurality of softening materials without mixing with the polymer. It is good also as a base material.
• the amount of these softening materials to be mixed is not particularly limited, and a single polymer having a sufficient number of times of bending at breaks may be used alone as a film base material, or a softening material may be mixed. As a softening material (100%), a sufficient number of times of breaking and bending may be provided.
• additives for example, an ultraviolet absorber, a matting agent, an antioxidant, a peeling accelerator, a retardation (optical anisotropy) adjusting agent, etc.
• additives for example, an ultraviolet absorber, a matting agent, an antioxidant, a peeling accelerator, a retardation (optical anisotropy) adjusting agent, etc.
• They may be solid or oily. That is, the melting point or boiling point is not particularly limited.
• the timing of adding the additive may be added at any time in the step of producing the base material, or may be performed by adding the step of adding the additive to the material preparation step.
• the amount of each material added is not particularly limited as long as the function is manifested.
• additives described in paragraph numbers ⁇ 0117> to ⁇ 0122> in JP-A No. 2016-167043 can be suitably used.
• the above additives may be used alone or in combination of two or more.
• UV absorber examples of the ultraviolet absorber include benzotriazole compounds, triazine compounds, and benzoxazine compounds.
• the benzotriazole compound is a compound having a benzotriazole ring, and specific examples thereof include various benzotriazole-based UV absorbers described in paragraph 0033 of JP2013-111835A.
• the triazine compound is a compound having a triazine ring, and specific examples thereof include various triazine-based ultraviolet absorbers described in paragraph 0033 of JP2013-111835A.
• As the benzoxazine compound for example, those described in paragraph 0031 of JP 2014-209162 A can be used.
• the content of the ultraviolet absorber in the substrate is, for example, about 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer contained in the substrate, but is not particularly limited.
• the UV absorber reference can also be made to paragraph 0032 of JP2013-111835A.
• an ultraviolet absorber having high heat resistance and low volatility is preferable.
• examples of such ultraviolet absorbers include UVSORB101 (manufactured by Fujifilm Fine Chemicals Co., Ltd.), TINUVIN 360, TINUVIN 460, TINUVIN 1577 (manufactured by BASF), LA-F70, LA-31, LA-46 (manufactured by ADEKA), and the like. Is mentioned.
• the base material preferably has a small difference in refractive index between the flexible material and various additives used for the base material and the polymer.
• the imide polymer means a polymer containing at least one or more repeating structural units represented by the formula (PI), the formula (a), the formula (a ′) and the formula (b).
• the repeating structural unit represented by a formula (PI) is a main structural unit of an imide type polymer.
• the repeating structural unit represented by the formula (PI) is preferably 40 mol% or more, more preferably 50 mol% or more, still more preferably 70 mol% or more, based on all repeating structural units of the imide-based polymer. It is still more preferably 90 mol% or more, and particularly preferably 98 mol%.
• G in the formula (PI) represents a tetravalent organic group, and A represents a divalent organic group.
• G 2 in the formula (a) represents a trivalent organic group, and A 2 represents a divalent organic group.
• G 3 in the formula (a ′) represents a tetravalent organic group, and A 3 represents a divalent organic group.
• G 4 and A 4 in the formula (b) each represent a divalent organic group.
• the organic group of the tetravalent organic group represented by G includes an acyclic aliphatic group, a cyclic aliphatic group, and an aromatic group. And a group selected from the group consisting of:
• the organic group of G is preferably a tetravalent cyclic aliphatic group or a tetravalent aromatic group from the viewpoints of transparency and flexibility of the substrate containing the imide-based polymer.
• the aromatic group include a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group having two or more aromatic rings and connected to each other directly or by a bonding group. Etc.
• the organic group of G is a cyclic aliphatic group, a cyclic aliphatic group having a fluorine-based substituent, a monocyclic aromatic group having a fluorine-based substituent, A condensed polycyclic aromatic group having a fluorine-based substituent or a non-condensed polycyclic aromatic group having a fluorine-based substituent is preferable.
• the fluorine-based substituent means a group containing a fluorine atom.
• the fluorine-based substituent is preferably a fluoro group (fluorine atom, -F) and a perfluoroalkyl group, more preferably a fluoro group and a trifluoromethyl group.
• the organic group of G is, for example, a saturated or unsaturated cycloalkyl group, a saturated or unsaturated heterocycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkylaryl group, a heteroalkylaryl.
• Examples of the bonding group include —O—, an alkylene group having 1 to 10 carbon atoms, —SO 2 —, —CO— or —CO—NR— (where R represents a methyl group, an ethyl group, a propyl group, etc. 3 represents an alkyl group or a hydrogen atom).
• the carbon number of the tetravalent organic group represented by G is usually 2 to 32, preferably 4 to 15, more preferably 5 to 10, and further preferably 6 to 8.
• the organic group of G is a cycloaliphatic group or an aromatic group, at least one of carbon atoms constituting these groups may be replaced with a heteroatom.
• Heteroatoms include O, N, or S.
• G examples include groups represented by the following formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), or formula (26). It is done. * In the formula indicates a bond.
• Z in the formula (26) represents a single bond, —O—, —CH 2 —, —C (CH 3 ) 2 —, —Ar—O—Ar—, —Ar—CH 2 —Ar—, —Ar—.
• C (CH 3 ) 2 —Ar— or —Ar—SO 2 —Ar— is represented.
• Ar represents an aryl group having 6 to 20 carbon atoms, and may be, for example, a phenylene group. At least one of the hydrogen atoms of these groups may be substituted with a fluorine-based substituent.
• the organic group of the divalent organic group represented by A includes an acyclic aliphatic group, a cyclic aliphatic group, and an aromatic group.
• the divalent organic group represented by A is preferably selected from a divalent cycloaliphatic group and a divalent aromatic group.
• the aromatic group include a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group having two or more aromatic rings and connected to each other directly or by a bonding group. Groups. From the viewpoint of transparency of the resin film and suppression of coloring, it is preferable that a fluorine-based substituent is introduced into the organic group of A.
• the organic group of A is, for example, a saturated or unsaturated cycloalkyl group, a saturated or unsaturated heterocycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkylaryl group, a heteroalkylaryl.
• the hetero atom include O, N, or S.
• Examples of the bonding group include —O—, an alkylene group having 1 to 10 carbon atoms, —SO 2 —, —CO—, or —CO—NR— (R represents methyl Group, an alkyl group having 1 to 3 carbon atoms such as an ethyl group or a propyl group, or a hydrogen atom).
• the carbon number of the divalent organic group represented by A is usually 2 to 40, preferably 5 to 32, more preferably 12 to 28, and further preferably 24 to 27.
• A include groups represented by the following formula (30), formula (31), formula (32), formula (33), or formula (34).
• * In the formula indicates a bond.
• Z 1 to Z 3 are each independently a single bond, —O—, —CH 2 —, —C (CH 3 ) 2 —, —SO 2 —, —CO— or —CO—NR— (R is Represents a C 1-3 alkyl group such as a methyl group, an ethyl group, or a propyl group, or a hydrogen atom.
• Z 1 and Z 2 , and Z 2 and Z 3 are each preferably in the meta position or the para position with respect to each ring.
• Z 1 and the single bond at the terminal, Z 2 and the single bond at the terminal, and Z 3 and the single bond at the terminal are in the meta position or the para position, respectively.
• Z 1 and Z 3 are —O— and Z 2 is —CH 2 —, —C (CH 3 ) 2 — or —SO 2 —.
• One or two or more hydrogen atoms of these groups may be substituted with a fluorine-based substituent.
• At least one of the hydrogen atoms constituting at least one of A and G is at least one selected from the group consisting of a fluorine-based substituent, a hydroxyl group, a sulfone group, and an alkyl group having 1 to 10 carbon atoms. It may be substituted with a functional group.
• the organic group of A and the organic group of G are each a cyclic aliphatic group or an aromatic group, it is preferable that at least one of A and G has a fluorine-based substituent, and both A and G are More preferably, it has a fluorine-based substituent.
• G 2 in the formula (a) is a trivalent organic group.
• This organic group can be selected from the same groups as the organic group of G in formula (PI) except that it is a trivalent group.
• Examples of G 2 include groups in which any one of the four bonds of the groups represented by formulas (20) to (26) listed as specific examples of G is replaced with a hydrogen atom. Can do.
• A2 in formula (a) can be selected from the same groups as A in formula (PI).
• G 3 in formula (a ′) can be selected from the same groups as G in formula (PI).
• a 3 in formula (a ′) can be selected from the same groups as A in formula (PI).
• G 4 in the formula (b) is a divalent organic group.
• This organic group can be selected from the same groups as the organic group of G in formula (PI) except that it is a divalent group.
• Examples of G 4 include groups in which any two of the four bonds of the groups represented by formulas (20) to (26) listed as specific examples of G are replaced with hydrogen atoms. Can do.
• a 4 in formula (b) can be selected from the same groups as A in formula (PI).
• the imide polymer contained in the substrate containing the imide polymer includes a diamine and a tetracarboxylic acid compound (including an analog of a tetracarboxylic acid compound such as an acid chloride compound and a tetracarboxylic dianhydride) or a tricarboxylic acid compound ( It may be a condensed polymer obtained by polycondensation with at least one of an acid chloride compound and a tricarboxylic acid compound analog such as a tricarboxylic acid anhydride). Further, dicarboxylic acid compounds (including analogs such as acid chloride compounds) may be polycondensed.
• the repeating structural unit represented by the formula (PI) or the formula (a ′) is usually derived from a diamine and a tetracarboxylic acid compound.
• the repeating structural unit represented by the formula (a) is usually derived from diamines and tricarboxylic acid compounds.
• the repeating structural unit represented by the formula (b) is usually derived from diamines and dicarboxylic acid compounds.
• tetracarboxylic acid compound examples include aromatic tetracarboxylic acid compounds, alicyclic tetracarboxylic acid compounds, and acyclic aliphatic tetracarboxylic acid compounds. Two or more of these may be used in combination.
• the tetracarboxylic acid compound is preferably tetracarboxylic dianhydride.
• tetracarboxylic dianhydrides include aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and acyclic aliphatic tetracarboxylic dianhydrides.
• the tetracarboxylic acid compound may be an alicyclic tetracarboxylic compound or an aromatic tetracarboxylic acid compound. preferable.
• the tetracarboxylic acid compound includes an alicyclic tetracarboxylic acid compound having a fluorine-based substituent and an aromatic tetracarboxylic acid compound having a fluorine-based substituent. And an alicyclic tetracarboxylic acid compound having a fluorine-based substituent is more preferable.
• tricarboxylic acid compounds include aromatic tricarboxylic acids, alicyclic tricarboxylic acids, acyclic aliphatic tricarboxylic acids, and related acid chloride compounds, acid anhydrides, and the like.
• the tricarboxylic acid compound is preferably selected from aromatic tricarboxylic acids, alicyclic tricarboxylic acids, acyclic aliphatic tricarboxylic acids, and related acid chloride compounds. Two or more tricarboxylic acid compounds may be used in combination.
• the tricarboxylic acid compound is an alicyclic tricarboxylic acid compound or an aromatic tricarboxylic acid compound from the viewpoints of solubility of the imide-based polymer in a solvent and transparency and flexibility when a substrate containing the imide-based polymer is formed. It is preferable. From the viewpoint of transparency of a substrate containing an imide-based polymer and suppression of coloring, the tricarboxylic acid compound is an alicyclic tricarboxylic acid compound having a fluorine-based substituent or an aromatic tricarboxylic acid compound having a fluorine-based substituent. Is more preferable.
• dicarboxylic acid compounds examples include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, acyclic aliphatic dicarboxylic acids, and related acid chloride compounds, acid anhydrides, and the like.
• the dicarboxylic acid compound is preferably selected from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, acyclic aliphatic dicarboxylic acids and related acid chloride compounds. Two or more dicarboxylic acid compounds may be used in combination.
• the dicarboxylic acid compound is an alicyclic dicarboxylic acid compound or an aromatic dicarboxylic acid compound from the viewpoints of solubility of the imide-based polymer in a solvent and transparency and flexibility when a substrate containing the imide-based polymer is formed. It is preferable. From the viewpoint of transparency of the substrate containing the imide-based polymer and suppression of coloring, the dicarboxylic acid compound is an alicyclic dicarboxylic acid compound having a fluorine-based substituent or an aromatic dicarboxylic acid compound having a fluorine-based substituent. Is more preferable.
• diamines examples include aromatic diamines, alicyclic diamines and aliphatic diamines, and these may be used in combination of two or more.
• the diamine is derived from an alicyclic diamine and an aromatic diamine having a fluorine-based substituent. It is preferable to be selected.
• an imide-based polymer If such an imide-based polymer is used, it has particularly excellent flexibility, high light transmittance (for example, 85% or more, preferably 88% or more for 550 nm light), low yellowness (YI value). 5 or less, preferably 3 or less), and a resin film having a low haze (1.5% or less, preferably 1.0% or less) is easily obtained.
• the imide polymer may be a copolymer containing a plurality of different types of repeating structural units.
• the weight average molecular weight of the polyimide polymer is usually 10,000 to 500,000.
• the weight average molecular weight of the imide polymer is preferably 50,000 to 500,000, and more preferably 70,000 to 400,000.
• the weight average molecular weight is a standard polystyrene equivalent molecular weight measured by gel permeation chromatography (GPC). If the weight average molecular weight of the imide polymer is large, high flexibility tends to be obtained, but if the weight average molecular weight of the imide polymer is too large, the viscosity of the varnish tends to be high and the workability tends to be lowered.
• the imide-based polymer may contain a halogen atom such as a fluorine atom that can be introduced by the above-described fluorine-based substituent.
• a halogen atom such as a fluorine atom that can be introduced by the above-described fluorine-based substituent.
• a halogen atom is preferably a fluorine atom.
• the content of halogen atoms in the polyimide polymer is preferably 1 to 40% by mass, more preferably 1 to 30% by mass based on the mass of the polyimide polymer.
• the base material containing an imide-based polymer may contain one or more ultraviolet absorbers.
• the ultraviolet absorber can be appropriately selected from those usually used as an ultraviolet absorber in the field of resin materials.
• the ultraviolet absorber may contain a compound that absorbs light having a wavelength of 400 nm or less.
• Examples of the ultraviolet absorber that can be appropriately combined with the imide polymer include at least one compound selected from the group consisting of benzophenone compounds, salicylate compounds, benzotriazole compounds, and triazine compounds.
• system compound refers to a derivative of a compound to which “system compound” is attached.
• a “benzophenone compound” refers to a compound having benzophenone as a host skeleton and a substituent bonded to benzophenone.
• the content of the ultraviolet absorber is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and usually 10% by mass or less with respect to the total mass of the resin film. Yes, preferably 8% by mass or less, more preferably 6% by mass or less.
• the base material containing the imide polymer may further contain an inorganic material such as inorganic particles.
• the inorganic material is preferably a silicon material containing a silicon atom.
• the tensile elastic modulus of the base material containing the imide polymer can easily be 4.0 GPa or more.
• the method for controlling the tensile modulus of the base material containing the imide polymer is not limited to the blending of the inorganic material.
• Examples of the silicon material containing a silicon atom include silica particles, quaternary alkoxysilanes such as tetraethyl orthosilicate (TEOS), and silicon compounds such as silsesquioxane derivatives.
• TEOS tetraethyl orthosilicate
• silicon compounds such as silsesquioxane derivatives.
• silica particles are preferable from the viewpoints of transparency and flexibility of a substrate containing an imide-based polymer.
• the average primary particle diameter of the silica particles is usually 100 nm or less. When the average primary particle diameter of the silica particles is 100 nm or less, the transparency tends to be improved.
• the average primary particle diameter of the silica particles in the substrate containing the imide polymer can be determined by observation with a transmission electron microscope (TEM).
• the primary particle diameter of the silica particles can be a constant direction diameter measured by a transmission electron microscope (TEM).
• the average primary particle diameter can be obtained as an average value of ten primary particle diameters measured by TEM observation.
• the particle distribution of the silica particles before forming the substrate containing the imide polymer can be determined by a commercially available laser diffraction particle size distribution meter.
• the mixing ratio of the imide polymer and the inorganic material is preferably 1: 9 to 10: 0 in mass ratio, with the total of both being 10: 3 to 7 to 10. : 0 is more preferable, 3: 7 to 8: 2 is still more preferable, and 3: 7 to 7: 3 is still more preferable.
• the ratio of the inorganic material to the total mass of the imide polymer and the inorganic material is usually 20% by mass or more, preferably 30% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less.
• the mixing ratio of the imide polymer and the inorganic material is within the above range, the transparency and mechanical strength of the substrate containing the imide polymer tend to be improved. Moreover, the tensile elasticity modulus of the base material containing an imide polymer can be easily set to 4.0 GPa or more.
• the base material containing the imide polymer may further contain components other than the imide polymer and the inorganic material as long as the transparency and flexibility are not significantly impaired.
• components other than the imide-based polymer and the inorganic material include colorants such as antioxidants, mold release agents, stabilizers, and bluing agents, flame retardants, lubricants, thickeners, and leveling agents.
• the proportion of components other than the imide-based polymer and the inorganic material is preferably more than 0% and not more than 20% by mass, more preferably more than 0% and not more than 10% by mass with respect to the mass of the resin film 10. is there.
• Si / N which is the atomic ratio of silicon atoms to nitrogen atoms, is 8 or more in at least one main surface 10a.
• This atomic ratio Si / N is determined by evaluating the composition of a substrate containing an imide-based polymer by X-ray photoelectron spectroscopy (XPS), and the abundance of silicon atoms and nitrogen atoms obtained thereby. It is a value calculated from the abundance of.
• Si / N in the main surface 10a of the base material containing the imide polymer is 8 or more, sufficient adhesion with the functional layer 20 described later is obtained.
• Si / N is more preferably 9 or more, further preferably 10 or more, preferably 50 or less, and more preferably 40 or less.
• the thickness of the substrate is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, and most preferably 50 ⁇ m or less. If the thickness of the base material is reduced, the difference in curvature between the front surface and the back surface at the time of bending is reduced, and cracks and the like are less likely to occur. On the other hand, from the viewpoint of easy handling of the substrate, the thickness of the substrate is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and most preferably 15 ⁇ m or more.
• the base material may be formed by thermally melting a thermoplastic polymer, or may be formed by solution film formation (solvent casting method) from a solution in which the polymer is uniformly dissolved.
• solvent casting method solution film formation
• the above-mentioned softening material and various additives can be added at the time of hot melting.
• the substrate is produced by a solution casting method
• the above-described softening material and various additives can be added to the polymer solution (hereinafter also referred to as a dope) in each preparation step. Further, the addition may be performed at any time in the dope preparation process, but may be performed by adding an additive to the final preparation process of the dope preparation process.
• the hard coat layer of the hard coat film of the present invention comprises a cured product of the composition of the present invention.
• the hard coat layer in the invention preferably contains at least one selected from polyorganosilsesquioxane and a cured product of the compound (a2) having two or more (meth) acryloyl groups in one molecule.
• the hard coat layer in the present invention preferably contains polyorganosilsesquioxane, and more preferably contains a cured product of polyorganosilsesquioxane (a1) having an epoxy group.
• the hard coat layer in the present invention is obtained by curing the curable composition containing the modifier of the present invention and the polyorganosilsesquioxane (a1) having an epoxy group by heating and / or irradiation with ionizing radiation. It is preferable that
• polyorganosilsesquioxane (a1) having an epoxy group The polyorganosilsesquioxane (a1) having an epoxy group (also referred to as “polyorganosilsesquioxane (a1)”) has at least a siloxane structural unit containing an epoxy group, and has the following general formula (1 It is preferable that it is polyorganosilsesquioxane represented by this.
• Rb represents a group containing an epoxy group
• Rc represents a monovalent group
• the plurality of Rb and Rc may be the same or different.
• the plurality of Rc may form a bond with each other.
• [SiO 1.5 ] in the general formula (1) represents a structural portion constituted by a siloxane bond (Si—O—Si) in the polyorganosilsesquioxane.
• Polyorganosilsesquioxane is a network-type polymer or polyhedral cluster having a siloxane structural unit derived from a hydrolyzable trifunctional silane compound, and can form a random structure, ladder structure, cage structure, etc. by a siloxane bond.
• the structural portion represented by [SiO 1.5 ] may be any of the structures described above, but preferably contains a lot of ladder structures. By forming the ladder structure, the deformation recovery property of the hard coat film can be kept good.
• the formation of the ladder structure is qualitatively determined by the presence or absence of absorption derived from Si—O—Si stretching characteristic of the ladder structure appearing in the vicinity of 1020-1050 cm ⁇ 1 when measuring FT-IR (Fourier Transform Infrared Spectroscopy). Can be confirmed.
• Rb represents a group containing an epoxy group.
• the group containing an epoxy group include known groups having an oxirane ring.
• Rb is preferably a group represented by the following formulas (1b) to (4b).
• ** represents a connecting part with Si in the general formula (1)
• R 1b , R 2b , R 3b and R 4b represent a substituted or unsubstituted alkylene group.
• the alkylene group represented by R 1b , R 2b , R 3b and R 4b is preferably a linear or branched alkylene group having 1 to 10 carbon atoms.
• a methylene group for example, a methylene group, a methylmethylene group, a dimethylmethylene group, ethylene Group, i-propylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-decylene group and the like.
• the alkylene group represented by R 1b , R 2b , R 3b and R 4b has a substituent
• examples of the substituent include a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, and a cyano group.
• R 1b , R 2b , R 3b and R 4b are preferably an unsubstituted linear alkylene group having 1 to 4 carbon atoms, an unsubstituted branched alkylene group having 3 or 4 carbon atoms, and an ethylene group N-propylene group or i-propylene group is more preferable, and ethylene group or n-propylene group is more preferable.
• the polyorganosilsesquioxane (a1) preferably has an alicyclic epoxy group (a group having a condensed ring structure of an epoxy group and an alicyclic group).
• Rb in the general formula (1) is preferably an alicyclic epoxy group, more preferably a group having an epoxycyclohexyl group, and even more preferably a group represented by the above formula (1b). .
• Rb in the general formula (1) is a group bonded to a silicon atom in a hydrolyzable trifunctional silane compound used as a raw material for polyorganosilsesquioxane (a group other than an alkoxy group and a halogen atom; Derived from Rb in the hydrolyzable silane compound represented by the formula (B).
• Rb represents a connecting portion with Si in the general formula (1).
• Rc represents a monovalent group.
• the monovalent group represented by Rc includes a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group.
• a substituted aralkyl group may be mentioned.
• Examples of the alkyl group represented by Rc include alkyl groups having 1 to 10 carbon atoms, such as methyl group, ethyl group, propyl group, n-butyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group. And a linear or branched alkyl group such as an isopentyl group.
• Examples of the cycloalkyl group represented by Rc include cycloalkyl groups having 3 to 15 carbon atoms, such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
• Examples of the alkenyl group represented by Rc include alkenyl groups having 2 to 10 carbon atoms, and examples thereof include linear or branched alkenyl groups such as vinyl group, allyl group, and isopropenyl group.
• Examples of the aryl group represented by Rc include aryl groups having 6 to 15 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.
• Examples of the aralkyl group represented by Rc include aralkyl groups having 7 to 20 carbon atoms, and examples thereof include a benzyl group and a phenethyl group.
• Examples of the substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted aryl group, and substituted aralkyl group include a hydrogen atom or main chain bone in each of the above-described alkyl group, cycloalkyl group, alkenyl group, aryl group, and aralkyl group. At least one kind selected from the group consisting of an ether group, an ester group, a carbonyl group, a halogen atom (fluorine atom, etc.), an acrylic group, a methacryl group, a mercapto group, and a hydroxy group (hydroxyl group). And a group substituted with.
• Rc is preferably a substituted or unsubstituted alkyl group, and more preferably an unsubstituted alkyl group having 1 to 10 carbon atoms.
• the plurality of Rc may form a bond with each other. It is preferable that two or three Rc form a bond with each other, and it is more preferable that two Rc form a bond with each other.
• the group (Rc 2 ) formed by bonding two Rc's to each other is preferably an alkylene group formed by bonding the substituted or unsubstituted alkyl group represented by Rc described above.
• Examples of the alkylene group represented by Rc 2 include methylene group, ethylene group, propylene group, isopropylene group, n-butylene group, isobutylene group, s-butylene group, t-butylene group, n-pentylene group, isopentylene group, s-pentylene group, t-pentylene group, n-hexylene group, isohexylene group, s-hexylene group, t-hexylene group, n-heptylene group, isoheptylene group, s-heptylene group, t-heptylene group, n-octylene group And linear or branched alkylene groups such as isooctylene group, s-octylene group and t-octylene group.
• the alkylene group represented by Rc 2 is preferably an unsubstituted alkylene group having 2 to 20 carbon atoms, more preferably an unsubstituted alkylene group having 2 to 20 carbon atoms, and still more preferably an unsubstituted alkylene group having 2 to 8 carbon atoms.
• An alkylene group particularly preferably an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, or an n-octylene group.
• the group formed by bonding three Rc to each other (Rc 3 ) is preferably a trivalent group in which any hydrogen atom in the alkylene group is reduced by one in the alkylene group represented by Rc 2 described above. .
• Rc represents a group bonded to a silicon atom in a hydrolyzable silane compound used as a raw material for polyorganosilsesquioxane (a group other than an alkoxy group and a halogen atom; (Rc 1 to Rc 3 in the hydrolyzable silane compounds represented by (C1) to (C3)).
• q is more than 0 and r is 0 or more.
• q / (q + r) is preferably 0.5 to 1.0.
• the network formed by the organic crosslinking group is sufficiently formed. Therefore, each performance of hardness and resistance to repeated bending can be kept good.
• q / (q + r) is more preferably 0.7 to 1.0, further preferably 0.9 to 1.0, and particularly preferably 0.95 to 1.0.
• r / (q + r) is preferably 0.005 to 0.20.
• r / (q + r) is more preferably 0.005 to 0.10, further preferably 0.005 to 0.05, and particularly preferably 0.005 to 0.025.
• the number average molecular weight (Mn) in terms of standard polystyrene as determined by gel permeation chromatography (GPC) of polyorganosilsesquioxane (a1) is preferably 500 to 6000, more preferably 1000 to 4500, and still more preferably. 1500 to 3000.
• the molecular weight dispersity (Mw / Mn) in terms of standard polystyrene by GPC of the polyorganosilsesquioxane (a1) is, for example, 1.0 to 4.0, preferably 1.1 to 3.7. Preferably it is 1.2 to 3.0, more preferably 1.3 to 2.5. Mn represents the number average molecular weight.
• the weight average molecular weight and molecular weight dispersity of the polyorganosilsesquioxane (a1) were measured by the following apparatus and conditions. Measuring device: Product name “LC-20AD” (manufactured by Shimadzu Corporation) Column: Shodex KF-801 ⁇ 2, KF-802, and KF-803 (manufactured by Showa Denko KK) Measurement temperature: 40 ° C Eluent: Tetrahydrofuran (THF), sample concentration 0.1-0.2% by mass Flow rate: 1 mL / min Detector: UV-VIS detector (trade name “SPD-20A”, manufactured by Shimadzu Corporation) Molecular weight: Standard polystyrene conversion
• the polyorganosilsesquioxane (a1) can be produced by a known production method, and is not particularly limited, but can be produced by a method in which one or more hydrolyzable silane compounds are hydrolyzed and condensed.
• a hydrolyzable silane compound a hydrolyzable trifunctional silane compound (compound represented by the following formula (B)) for forming a siloxane structural unit containing an epoxy group is used as the hydrolyzable silane compound. It is preferable.
• r in general formula (1) is more than 0, it is preferable to use a compound represented by the following formula (C1), (C2) or (C3) as the hydrolyzable silane compound.
• Rb in the formula (B) has the same meaning as Rb in the general formula (1), and preferred examples thereof are also the same.
• X 2 in the formula (B) represents an alkoxy group or a halogen atom.
• the alkoxy group for X 2 include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, and an isobutyloxy group.
• the halogen atom in X 2 for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• X 2 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. Note that three X 2 can be the same, respectively, may be different.
• the compound represented by the above formula (B) is a compound that forms a siloxane structural unit having Rb.
• Rc 1 in the formula (C1) has the same meaning as Rc in the general formula (1), and preferred examples thereof are also the same.
• Rc 2 in the formula (C2) has the same meaning as group (Rc 2) formed by two Rc in the general formula (1) are bonded to each other, and so are the preferable examples.
• Rc 3 in formula (C3) is synonymous with the group (Rc 3 ) formed by bonding three Rc in general formula (1) to each other, and preferred examples are also the same.
• X 3 in the above formulas (C1) to (C3) has the same meaning as X 2 in the above formula (B), and preferred examples are also the same.
• the plurality of X 3 may be the same or different.
• hydrolyzable silane compound a hydrolyzable silane compound other than the compounds represented by the above formulas (B) and (C1) to (C3) may be used in combination.
• hydrolyzable trifunctional silane compounds other than the compounds represented by the above formulas (B) and (C1) to (C3), hydrolyzable monofunctional silane compounds, hydrolyzable bifunctional silane compounds, and the like.
• Rc is derived from Rc 1 to Rc 3 in the hydrolyzable silane compounds represented by the above formulas (C1) to (C3)
• q / (q + r) in order to adjust q / (q + r) in the general formula (1), What is necessary is just to adjust the compounding ratio (molar ratio) of the compounds represented by the formulas (B) and (C1) to (C3).
• the value represented by the following (Z2) is set to 0.5 to 1.0, and these compounds are hydrolyzed. And may be produced by a condensation method.
• (Z2) compound represented by formula (B) (molar amount) / ⁇ compound represented by formula (B) (molar amount) + compound represented by formula (C1) (molar amount) + formula (C2 ) Compound represented by (molar amount) ⁇ 2 + Compound represented by formula (C3) (molar amount) ⁇ 3 ⁇
• the usage-amount and composition of the said hydrolysable silane compound can be suitably adjusted according to the structure of the desired polyorgano silsesquioxane (a1).
• the hydrolysis and condensation reaction of the hydrolyzable silane compound can be performed simultaneously or sequentially.
• the order which performs reaction is not specifically limited.
• the hydrolysis and condensation reaction of the hydrolyzable silane compound can be performed in the presence or absence of a solvent, and is preferably performed in the presence of a solvent.
• a solvent include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate and ethyl acetate.
• Esters such as isopropyl acetate and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; alcohols such as methanol, ethanol, isopropyl alcohol and butanol Etc.
• a ketone or ether is preferable.
• a solvent can be used individually by 1 type and can also be used in combination of 2 or more type.
• the amount of the solvent used is not particularly limited, and can be appropriately adjusted in the range of 0 to 2000 parts by mass with respect to 100 parts by mass of the total amount of the hydrolyzable silane compound depending on the desired reaction time. .
• the hydrolysis and condensation reaction of the hydrolyzable silane compound is preferably allowed to proceed in the presence of a catalyst and water.
• the catalyst may be an acid catalyst or an alkali catalyst.
• the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid, formic acid and trifluoroacetic acid; methanesulfonic acid, trifluoromethanesulfonic acid, p -Sulfonic acids such as toluenesulfonic acid; solid acids such as activated clay; Lewis acids such as iron chloride.
• alkali catalyst examples include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metals such as magnesium hydroxide, calcium hydroxide, and barium hydroxide. Hydroxides; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; carbonates of alkaline earth metals such as magnesium carbonate; lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate Alkali metal bicarbonates such as lithium acetate, sodium acetate, potassium acetate, cesium acetate, etc.
• alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide
• alkaline earth metals such as magnesium hydroxide, calcium hydroxide, and barium hydroxide.
• Hydroxides carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate
• a catalyst can also be used individually by 1 type and can also be used in combination of 2 or more type. Further, the catalyst can be used in a state dissolved or dispersed in water or
• the amount of the catalyst used is not particularly limited, and can be appropriately adjusted within a range of 0.002 to 0.200 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound.
• the amount of water used in the hydrolysis and condensation reaction is not particularly limited, and can be appropriately adjusted within a range of 0.5 to 20 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound.
• the method for adding water is not particularly limited, and the total amount of water to be used (total amount used) may be added all at once or sequentially. When adding sequentially, you may add continuously or intermittently.
• reaction conditions for performing the hydrolysis and condensation reaction of the hydrolyzable silane compound it is particularly possible to select reaction conditions such that the condensation rate of the polyorganosilsesquioxane (a1) is 80% or more. is important.
• the reaction temperature for the hydrolysis and condensation reaction is, for example, 40 to 100 ° C., preferably 45 to 80 ° C. By controlling the reaction temperature within the above range, the condensation rate tends to be controlled to 80% or more.
• the reaction time for the hydrolysis and condensation reaction is, for example, 0.1 to 10 hours, preferably 1.5 to 8 hours.
• the hydrolysis and condensation reaction can be performed under normal pressure, or can be performed under pressure or under reduced pressure.
• the atmosphere for performing the hydrolysis and condensation reaction may be, for example, an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or in the presence of oxygen such as air. An atmosphere is preferred.
• a polyorganosilsesquioxane (a1) is obtained by hydrolysis and condensation reaction of the hydrolyzable silane compound. After completion of the hydrolysis and condensation reaction, it is preferable to neutralize the catalyst in order to suppress the ring opening of the epoxy group.
• polyorganosilsesquioxane (a1) can be combined with, for example, separation means such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, and the like. Separation and purification may be performed by separation means or the like.
• the condensation ratio of the polyorganosilsesquioxane (a1) is preferably 80% or more from the viewpoint of the hardness of the film.
• the condensation rate is more preferably 90% or more, and further preferably 95% or more.
• the condensation rate is calculated using a 29 Si NMR (nuclear magnetic resonance) spectrum measurement on a hard coat film sample having a hard coat layer containing a cured product of polyorganosilsesquioxane (a1) and using the measurement result. It is possible.
• the epoxy group is preferably ring-opened by a polymerization reaction.
• the ring opening rate of the epoxy group of the cured product of polyorganosilsesquioxane (a1) is preferably 40% or more from the viewpoint of the hardness of the film.
• the ring opening rate is more preferably 50% or more, and further preferably 60% or more.
• the ring-opening rate is determined by FT-IR (Fourier Transformed Spectroscopy) single reflection ATR (Attenuated Total) for samples before and after fully curing and heat-treating the composition for forming a hard coat layer containing polyorganosilsesquioxane (a1). It is possible to calculate from the change in peak height derived from the epoxy group.
• Polyorganosilsesquioxane (a1) may be used alone or in combination of two or more having different structures.
• the content of the cured product of polyorganosilsesquioxane (a1) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more with respect to the total mass of the hard coat layer. preferable.
• the preferred content of the cured product of the curable component when the hard coat layer in the present invention is a cured product of a composition containing another curable component instead of the polyorganosilsesquioxane (a1) is also described above. It is the same.
• composition for forming a hard coat layer only one type of the modifier of the present invention may be used, or two or more types having different structures may be used in combination.
• the content of the polymer of the present invention in the composition for forming a hard coat layer can be adjusted as appropriate depending on the effect of improving the coating amount and the surface state of the polymer, but the content of the polymer is 0.00.
• the content is preferably from 001 mass% to 20 mass%, more preferably from 0.005 mass% to 10 mass%, and still more preferably from 0.01 mass% to 1 mass%.
• Solid content means components other than a solvent.
• the hard coat layer may contain components other than those described above.
• the hard coat layer may contain a dispersant, an antifouling agent, an antistatic agent, an ultraviolet absorber, and the like.
• a hard-coat layer may contain the hardened
• the hard coat layer does not contain a cured product of a compound having a (meth) acryloyl group, or the content of a cured product of a compound having a (meth) acryloyl group is such that the polyorganosilsesquioxane (a1) and (meta It is preferable that it is less than 10 mass% with respect to the total amount of the hardened
• the thickness of the hard coat layer is not particularly limited, but is preferably 1 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, and still more preferably 10 to 20 ⁇ m.
• the thickness of the hard coat layer is calculated by observing the cross section of the hard coat film with an optical microscope.
• the cross-section sample can be created by a microtome method using a cross-section cutting apparatus ultramicrotome, a cross-section processing method using a focused ion beam (FIB) apparatus, or the like.
• a preferred embodiment of the hard coat film of the present invention is to have a mixed layer on the surface of the hard coat layer opposite to the substrate side.
• the mixed layer preferably contains a cured product of the compound (b1) having an epoxy group and a cured product of the compound (b2) having two or more (meth) acryloyl groups in one molecule.
• the cured product of the compound (b1) having an epoxy group and the cured product of the compound (b2) having two or more (meth) acryloyl groups in one molecule are the compound (b1) having an epoxy group and 2 in one molecule. It is preferable that the curable composition containing the compound (b2) having at least one (meth) acryloyl group is cured by heating and / or irradiation with ionizing radiation.
• Compound having an epoxy group (b1) As the compound (b1) having an epoxy group (also referred to as “epoxy compound (b1)”), a compound having one or more epoxy groups (oxirane ring) in the molecule can be used, and is not particularly limited. Examples thereof include an epoxy compound containing a ring, an aromatic epoxy compound, an aliphatic epoxy compound, and a polyorganosilsesquioxane (a1) having an epoxy group used for forming the hard coat layer.
• Examples of the epoxy compound containing an alicyclic ring include known compounds having one or more alicyclic rings and one or more epoxy groups in the molecule, and are not particularly limited. (1) a compound having an alicyclic epoxy group; (2) A compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond; (3) The compound (glycidyl ether type epoxy compound) etc. which have an alicyclic ring and a glycidyl ether group in a molecule
• numerator are mentioned.
• Examples of the compound (1) having an alicyclic epoxy group include compounds represented by the following formula (i).
• Y represents a single bond or a linking group (a divalent group having one or more atoms).
• the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of a carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and Examples include a group in which a plurality of these are linked.
• Examples of the divalent hydrocarbon group include a substituted or unsubstituted linear or branched alkylene group having 1 to 18 carbon atoms, a divalent substituted or unsubstituted alicyclic hydrocarbon group, and the like.
• Examples of the alkylene group having 1 to 18 carbon atoms include methylene group, methylmethylene group, dimethylmethylene group, ethylene group, i-propylene group, and n-propylene group.
• divalent alicyclic hydrocarbon group examples include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group and cyclohexylidene group.
• alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized include, for example, vinylene group, propenylene group, 1-butenylene group And straight-chain or branched alkenylene groups having 2 to 8 carbon atoms such as 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group and the like.
• the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.
• alicyclic epoxy compound represented by the above formula (i) include 3,4,3 ′, 4′-diepoxybicyclohexane, and the following formulas (i-1) to (i-10): The compound etc. which are represented by these are mentioned.
• l and m each represents an integer of 1 to 30.
• R ′ in the following formula (i-5) is an alkylene group having 1 to 8 carbon atoms, and in particular, a straight chain having 1 to 3 carbon atoms such as methylene group, ethylene group, n-propylene group, i-propylene group, etc. A chain or branched alkylene group is preferred.
• n1 to n6 each represents an integer of 1 to 30.
• Other examples of the alicyclic epoxy compound represented by the above formula (i) include 2,2-bis (3,4-epoxycyclohexyl) propane and 1,2-bis (3,4-epoxycyclohexyl). ) Ethane, 2,3-bis (3,4-epoxycyclohexyl) oxirane, bis (3,4-epoxycyclohexylmethyl) ether and the like.
• Examples of the compound (2) in which the epoxy group is directly bonded to the alicyclic ring with a single bond include compounds represented by the following formula (ii).
• R ′′ is a group obtained by removing p hydroxyl groups (—OH) from the structural formula of p-valent alcohol (p-valent organic group), and p and n each represent a natural number.
• the divalent alcohol [R ′′ (OH) p] include polyhydric alcohols (such as alcohols having 1 to 15 carbon atoms) such as 2,2-bis (hydroxymethyl) -1-butanol.
• p is preferably 1 to 6
• n is preferably 1 to 30.
• n in each group in () (inside the outer parenthesis) may be the same or different.
• Examples of the compound (3) having an alicyclic ring and a glycidyl ether group in the molecule include glycidyl ethers of alicyclic alcohols (particularly alicyclic polyhydric alcohols). More specifically, for example, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2-bis [3,5-dimethyl-4- (2,3-epoxypropoxy) Compound obtained by hydrogenating bisphenol A type epoxy compound such as cyclohexyl] propane (hydrogenated bisphenol A type epoxy compound); bis [o, o- (2,3-epoxypropoxy) cyclohexyl] methane, bis [o , P- (2,3-epoxypropoxy) cyclohexyl] methane, bis [p, p- (2,3-epoxypropoxy) cyclohexyl] methane, bis [3,5-dimethyl-4- (2, 3-Epoxypropoxy) cycl
• aromatic epoxy compound examples include epibis type glycidyl ether type epoxy resins obtained by condensation reaction of bisphenols (for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc.) and epihalohydrin; High molecular weight epibis type glycidyl ether type epoxy resin obtained by further addition reaction of bis type glycidyl ether type epoxy resin with the above bisphenols; phenols (eg, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, etc.) and aldehydes (eg, formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicy A novolak-alkyl type glycidyl ether type epoxy resin obtained by further condensing a polyhydric alcohol obtained by condensation reaction with an aldehyde, etc.
• bisphenols for example, bisphenol A,
• Examples of the aliphatic epoxy compound include glycidyl ether of an alcohol having no s-valent cyclic structure (s is a natural number); mono- or polyvalent carboxylic acid (for example, acetic acid, propionic acid, butyric acid, stearic acid, Glycidyl esters of adipic acid, sebacic acid, maleic acid, itaconic acid, etc .; epoxidized products of oils and fats having double bonds such as epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil; polyolefins such as epoxidized polybutadiene (poly And epoxidized products of alkadienes).
• mono- or polyvalent carboxylic acid for example, acetic acid, propionic acid, butyric acid, stearic acid, Glycidyl esters of adipic acid, sebacic acid, maleic acid, itaconic acid, etc .
• Examples of the alcohol having no s-valent cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol; ethylene glycol, 1,2-propanediol, 1 Divalent alcohols such as 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol; Examples include trihydric or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. That.
• the s-valent alcohol may be polyether polyol, polyester polyol, polycarbonate polyo
• the epoxy compound (b1) is preferably a polyorganosilsesquioxane having an epoxy group, and the preferred range is the same as that of the polyorganosilsesquioxane (a1) having an epoxy group of the hard coat layer described above. .
• the epoxy compound (b1) may be used alone or in combination of two or more different structures.
• the content of the cured product of the epoxy compound (b1) is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, and more preferably 25% by mass with respect to the total mass of the mixed layer. More preferably, it is 75 mass% or less.
• Compound (b2) having two or more (meth) acryloyl groups in one molecule Compound (b2) having two or more (meth) acryloyl groups in one molecule (also referred to as “polyfunctional (meth) acrylate compound (b2)”) has three or more (meth) acryloyl groups in one molecule. It is preferable that it is a compound which has this.
• the polyfunctional (meth) acrylate compound (b2) may be a crosslinkable monomer, a crosslinkable oligomer, or a crosslinkable polymer.
• Examples of the polyfunctional (meth) acrylate compound (b2) include esters of polyhydric alcohols and (meth) acrylic acid. Specifically, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipenta Examples include erythritol tetra (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol hexa (meth) acrylate, etc., but in terms of high crosslinking, pentaerythritol triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol Pen
• the content of the cured product of the polyfunctional (meth) acrylate compound (b2) in the mixed layer is 10 mass relative to the total amount of the cured product of the epoxy compound (b1) and the cured product of the polyfunctional (meth) acrylate compound (b2). % Or more is preferable.
• the content of the cured product of the polyfunctional (meth) acrylate compound (b2) in the mixed layer is 10 with respect to the total amount of the cured product of the epoxy compound (b1) and the cured product of the polyfunctional (meth) acrylate compound (b2). % By mass to 90% by mass is preferable, and 20% by mass to 80% by mass is more preferable.
• the mixed layer may contain components other than those described above, for example, a dispersant, a leveling agent, an antifouling agent, an antistatic agent, an ultraviolet absorber, a cured product of another polymerizable compound, and the like. Also good.
• a general-purpose leveling agent can be used as the leveling agent, but it is also preferable to use the modifier of the present invention.
• Examples of cured products of other polymerizable compounds include cured products of compounds having an epoxy group and a (meth) acryloyl group in one molecule. Specific examples of the compound include Daicel Cyclomer M100, Kyoeisha Chemical Co., Ltd. trade name Light Ester G, Nippon Kasei Chemical Co., Ltd.
• 4HBAGE Showa Polymers trade name SP series, such as SP-1506, 500, SP-1507.
• SP series such as SP-1506, 500, SP-1507.
• VR series such as VR-77
• EA-1010 / ECA trade names EA-1120, EA-1025, EA-6310 / ECA manufactured by Shin-Nakamura Chemical Co., Ltd.
• the thickness of the mixed layer is preferably 0.05 ⁇ m to 10 ⁇ m. When the thickness is 0.05 ⁇ m or more, the scratch resistance of the film is improved, and when the thickness is 10 ⁇ m or less, the hardness and the repeated bending resistance are improved.
• the thickness of the mixed layer is more preferably from 0.1 ⁇ m to 5 ⁇ m, still more preferably from 0.1 ⁇ m to 3 ⁇ m.
• the total thickness of the mixed layer and the scratch-resistant layer is preferably within the above range.
• the hard coat layer and the mixed layer are preferably bonded by a covalent bond.
• the epoxy group of the polyorganosilsesquioxane (a1) in the hard coat layer and the epoxy group of the epoxy compound (b1) in the mixed layer form a bond at the interface of both layers.
• the hard coat film of the present invention may further have other layers in addition to the hard coat layer and the mixed layer.
• an aspect having an easy-adhesion layer for improving adhesion between the base material and the hard coat layer, an aspect having an antistatic layer for imparting antistatic properties, and an antifouling layer on the mixed layer The aspect which has the antifouling layer for providing property and the abrasion-resistant layer for providing abrasion resistance is mentioned preferably, You may provide these two or more.
• the hard coat film of the present invention preferably has a scratch-resistant layer on the surface of the mixed layer opposite to the hard coat layer, whereby the scratch resistance can be further improved.
• the scratch-resistant layer preferably contains a cured product of the compound (c1) having two or more (meth) acryloyl groups in one molecule (also referred to as “polyfunctional (meth) acrylate compound (c1)”).
• the polyfunctional (meth) acrylate compound (c1) is the same as the above-mentioned polyfunctional (meth) acrylate compound (b2), and the preferred range is also the same.
• Only one type of polyfunctional (meth) acrylate compound (c1) may be used, or two or more types having different structures may be used in combination.
• the content of the cured product of the polyfunctional (meth) acrylate compound (c1) is preferably 80% by mass or more, more preferably 85% by mass or more, and more preferably 90% by mass or more with respect to the total mass of the scratch-resistant layer. Further preferred.
• the scratch-resistant layer may contain components other than those described above, and may contain, for example, inorganic particles, leveling agents, antifouling agents, antistatic agents, slip agents, and the like. In particular, it is preferable to contain the following fluorine-containing compound as a slipping agent.
• the fluorine-containing compound may be a monomer, oligomer, or polymer.
• the fluorine-containing compound preferably has a substituent that contributes to bond formation or compatibility with the polyfunctional (meth) acrylate compound (c1) in the scratch-resistant layer. These substituents may be the same or different, and a plurality of substituents are preferable.
• This substituent is preferably a polymerizable group, and may be any polymerizable reactive group exhibiting any one of radical polymerizable, cationic polymerizable, anionic polymerizable, polycondensable and addition polymerizable.
• Examples of preferable substituents Includes acryloyl group, methacryloyl group, vinyl group, allyl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, and amino group. Of these, a radical polymerizable group is preferable, and an acryloyl group and a methacryloyl group are particularly preferable.
• the fluorine-containing compound may be a polymer or an oligomer with a compound containing no fluorine atom.
• the fluorine-containing compound is preferably a fluorine-based compound represented by the following general formula (F).
• R A represents a polymerizable unsaturated group.
• the polymerizable unsaturated group is preferably a group having an unsaturated bond that can cause a radical polymerization reaction by irradiation with an active energy ray such as an ultraviolet ray or an electron beam (that is, a radical polymerizable group).
• an active energy ray such as an ultraviolet ray or an electron beam
• examples include acryloyl group, (meth) acryloyloxy group, vinyl group, allyl group, (meth) acryloyl group, (meth) acryloyloxy group, and groups in which any hydrogen atom in these groups is substituted with a fluorine atom Is preferably used.
• Rf represents a (per) fluoroalkyl group or a (per) fluoropolyether group.
• the (per) fluoroalkyl group represents at least one of a fluoroalkyl group and a perfluoroalkyl group
• the (per) fluoropolyether group is at least one of a fluoropolyether group and a perfluoropolyether group.
• the (per) fluoroalkyl group is preferably a group having 1 to 20 carbon atoms, more preferably a group having 1 to 10 carbon atoms.
• the (per) fluoroalkyl group has a linear structure (for example, —CF 2 CF 3 , —CH 2 (CF 2 ) 4 H, —CH 2 (CF 2 ) 8 CF 3 , —CH 2 CH 2 (CF 2 ) 4 H) even in branched structures (eg —CH (CF 3 ) 2 , —CH 2 CF (CF 3 ) 2 , —CH (CH 3 ) CF 2 CF 3 , —CH (CH 3 ) (CF 2 ) 5 CF 2 H) even in an alicyclic structure (preferably a 5- or 6-membered ring, such as a perfluorocyclohexyl group and a perfluorocyclopentyl group and an alkyl group substituted with these groups) There may be.
• the (per) fluoropolyether group refers to a case where the (per) fluoroalkyl group has an ether bond, and may be a monovalent or divalent group.
• the fluoropolyether group include —CH 2 OCH 2 CF 2 CF 3 , —CH 2 CH 2 OCH 2 C 4 F 8 H, —CH 2 CH 2 OCH 2 CH 2 C 8 F 17 , —CH 2 CH 2 OCF 2 CF 2 OCF 2 CF 2 H, C 4-20 fluorocycloalkyl group having 4 or more fluorine atoms, and the like can be given.
• perfluoropolyether group for example, — (CF 2 O) pf — (CF 2 CF 2 O) qf —, — [CF (CF 3 ) CF 2 O] pf — [CF (CF 3 )] qf -,-(CF 2 CF 2 CF 2 O) pf -,-(CF 2 CF 2 O) pf- and the like.
• the above pf and qf each independently represents an integer of 0 to 20. However, pf + qf is an integer of 1 or more.
• the total of pf and qf is preferably 1 to 83, more preferably 1 to 43, and still more preferably 5 to 23.
• the fluorine-containing compound preferably has a perfluoropolyether group represented by — (CF 2 O) pf — (CF 2 CF 2 O) qf — from the viewpoint of excellent scratch resistance.
• the fluorine-containing compound preferably has a perfluoropolyether group and a plurality of polymerizable unsaturated groups in one molecule.
• W represents a linking group.
• W include an alkylene group, an arylene group, a heteroalkylene group, and a linking group obtained by combining these groups. These linking groups may further have an oxy group, a carbonyl group, a carbonyloxy group, a carbonylimino group, a sulfonamide group, and the like, and a functional group in which these groups are combined.
• W is preferably an ethylene group, more preferably an ethylene group bonded to a carbonylimino group.
• the fluorine atom content of the fluorine-containing compound is not particularly limited, but is preferably 20% by mass or more, more preferably 30 to 70% by mass, and further preferably 40 to 70% by mass.
• fluorine-containing compounds examples include R-2020, M-2020, R-3833, M-3833, Optool DAC (trade name) manufactured by Daikin Chemical Industries, Ltd., and MegaFac F-171 manufactured by DIC. , F-172, F-179A, RS-78, RS-90, defender MCF-300 and MCF-323 (named above), but are not limited thereto.
• the product of nf and mf (nf ⁇ mf) is preferably 2 or more, and more preferably 4 or more.
• the weight average molecular weight (Mw) of the fluorine-containing compound having a polymerizable unsaturated group can be measured using molecular exclusion chromatography, for example, gel permeation chromatography (GPC).
• Mw of the fluorine-containing compound used in the present invention is preferably 400 or more and less than 50000, more preferably 400 or more and less than 30000, and still more preferably 400 or more and less than 25000.
• the addition amount of the fluorine-containing compound is preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass, still more preferably 0.5 to 5% by mass, based on the total mass of the scratch-resistant layer. 0.5 to 2% by mass is particularly preferable.
• the film thickness of the scratch-resistant layer is preferably 0.1 ⁇ m to 4 ⁇ m, more preferably 0.1 ⁇ m to 2 ⁇ m, and particularly preferably 0.1 ⁇ m to 1 ⁇ m. Further, the total thickness of the mixed layer and the scratch-resistant layer is preferably 0.1 ⁇ m to 10 ⁇ m.
• the method for producing the hard coat film of the present invention is not particularly limited.
• the hard coat film is a hard coat film having a hard coat layer on the substrate
• a method of completely curing the hard coat layer after applying the composition for forming a hard coat layer on the substrate may be mentioned.
• the hard coat film is a hard coat film having a substrate, a hard coat layer, and a mixed layer in this order
• a hard coat layer forming composition is applied and semi-cured on the substrate
• a method (Aspect A) in which each layer is fully cured after the composition for forming a mixed layer is applied onto the semi-cured hard coat layer.
• the composition for forming a mixed layer is applied and then semi-cured, and the composition for forming the scratch-resistant layer is applied onto the semi-cured mixed layer. Thereafter, it is preferable to completely cure each layer.
• a means for forming a mixed layer in the hard coat film an uncured hard coat layer and a scratch-resistant layer are laminated on a substrate, and mixed by interfacial mixing at the interface between the two. After forming a layer, the aspect which took in the method of fully hardening each layer is mentioned.
• a laminate in which an uncured hard coat layer is formed on a substrate and an uncured scratch resistant layer is separately formed on a temporary support is prepared, and the scratch resistant layer side of the laminate is the hard scratch layer side.
• composition for forming a hard coat layer a composition containing the modifier of the present invention and a polyorganosilsesquioxane (a1) containing an epoxy group
• an epoxy compound (b1) a composition for forming a mixed layer
• an epoxy compound (b1) The above-mentioned aspect A will be described in detail with reference to specific examples of the case where the composition containing the polyfunctional (meth) acrylate compound (b2) is used.
• Aspect A is specifically a production method including the following steps (I) to (IV).
• Step (I) is a step of providing a coating film by applying a composition for forming a hard coat layer containing the above-mentioned polyorganosilsesquioxane (a1) containing an epoxy group on a substrate.
• the substrate is as described above.
• the composition for forming a hard coat layer is a composition for forming the aforementioned hard coat layer.
• the composition for forming a hard coat layer usually takes a liquid form.
• the hard coat layer forming composition is prepared by dissolving or dispersing a modifier, polyorganosilsesquioxane (a1), and various additives and a polymerization initiator in an appropriate solvent as required. It is preferable.
• the concentration of the solid content is generally about 10 to 90% by mass, preferably 20 to 80% by mass, and particularly preferably about 40 to 70% by mass.
• the polyorganosilsesquioxane (a1) contains a cationic polymerizable group (epoxy group).
• the composition for forming a hard coat layer preferably contains a cationic photopolymerization initiator in order to initiate and advance the polymerization reaction of the polyorganosilsesquioxane (a1) by light irradiation. Only one cationic photopolymerization initiator may be used, or two or more cationic photopolymerization initiators having different structures may be used in combination. Hereinafter, the cationic photopolymerization initiator will be described.
• cationic photopolymerization initiator Any cationic photopolymerization initiator may be used as long as it can generate a cation as an active species by light irradiation, and any known cationic photopolymerization initiator can be used without any limitation. Specific examples include known sulfonium salts, ammonium salts, iodonium salts (for example, diaryl iodonium salts), triaryl sulfonium salts, diazonium salts, iminium salts, and the like.
• cationic photopolymerization initiators represented by formulas (25) to (28) shown in paragraphs 0050 to 0053 of JP-A-8-143806, paragraphs of JP-A-8-283320
• the cationic photopolymerization initiator can be synthesized by a known method, and is also available as a commercial product. Examples of commercially available products include CI-1370, CI-2064, CI-2397, CI-2624, CI-2939, CI-2734, CI-2758, CI-2823, CI-2855 and CI-5102 manufactured by Nippon Soda Co., Ltd.
• a diazonium salt, an iodonium salt, a sulfonium salt, and an iminium salt are preferable from the viewpoint of the sensitivity of the photopolymerization initiator to light and the stability of the compound. In terms of weather resistance, iodonium salts are most preferred.
• iodonium salt cationic photopolymerization initiators include, for example, B2380 manufactured by Tokyo Chemical Industry Co., Ltd., BBI-102 manufactured by Midori Chemical Co., Ltd., WPI-113 manufactured by Wako Pure Chemical Industries, Ltd. Examples include WPI-124, WPI-169 manufactured by Wako Pure Chemical Industries, WPI-170 manufactured by Wako Pure Chemical Industries, and DTBPI-PFBS manufactured by Toyo Gosei Chemical.
• the content of the polymerization initiator in the hard coat layer forming composition may be appropriately adjusted within a range in which the polymerization reaction (cationic polymerization) of the polyorganosilsesquioxane (a1) proceeds well, and is particularly limited. It is not something.
• the amount is, for example, in the range of 0.1 to 200 parts by weight, preferably 1 to 20 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the polyorganosilsesquioxane (a1). .
• composition for forming a hard coat layer may further contain one or more optional components in addition to the modifier, polyorganosilsesquioxane (a1), and polymerization initiator.
• optional component include a solvent and various additives.
• the solvent that can be included as an optional component is preferably an organic solvent, and one or two or more organic solvents can be mixed and used in an arbitrary ratio.
• organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone; cellosolves such as ethyl cellosolve; toluene, xylene And the like; glycol ethers such as propylene glycol monomethyl ether; acetates such as methyl acetate, ethyl acetate, and butyl acetate; and diacetone alcohol.
• the amount of the solvent in the composition can be appropriately adjusted within a range that can ensure the coating suitability of the composition.
• the amount can be 50 to 500 parts by mass, preferably 80 to 200 parts by mass with respect to 100 parts by mass of the total amount of the modifier, polyorganosilsesquioxane (a1) and the polymerization initiator. be able to.
• the composition can optionally contain one or more known additives as required.
• additives include a dispersant, an antifouling agent, an antistatic agent, and an ultraviolet absorber.
• a dispersant for details thereof, reference can be made to, for example, paragraphs 0032 to 0034 of JP2012-229212A.
• the present invention is not limited to these, and various additives that can be generally used in the polymerizable composition can be used.
• what is necessary is just to adjust the addition amount of the additive to a composition suitably, and is not specifically limited.
• composition for forming a hard coat layer used in the present invention can be prepared by mixing the various components described above simultaneously or sequentially in an arbitrary order.
• the preparation method is not particularly limited, and a known stirrer or the like can be used for the preparation.
• a method for applying the composition for forming a hard coat layer is not particularly limited, and a known method can be used. Examples include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and die coating.
• Step (II) is a step of semi-curing the coating film (i).
• an X-ray, an electron beam, an ultraviolet-ray, visible light, infrared rays etc. are mentioned, an ultraviolet-ray is used preferably.
• the coating film is UV curable, it is to cure the curable compound by irradiation with irradiation dose of ultraviolet rays 2mJ / cm 2 ⁇ 1000mJ / cm 2 by an ultraviolet lamp preferred. More preferably 2mJ / cm 2 ⁇ 100mJ / cm 2, and further preferably from 5mJ / cm 2 ⁇ 50mJ / cm 2.
• the ultraviolet lamp type a metal halide lamp, a high-pressure mercury lamp, or the like is preferably used.
• the oxygen concentration at the time of curing is not particularly limited, but when it contains a component that easily undergoes curing inhibition (a compound having a (meth) acryloyl group), the oxygen concentration should be adjusted to 0.1 to 2.0% by volume. It is preferable because a semi-cured state in which the surface functionality remains can be formed. In addition, when it does not contain components that are susceptible to curing inhibition (compounds having a (meth) acryloyl group), the atmosphere at the time of curing is replaced with dry nitrogen, so that the epoxy group reacts with water vapor in the air. This is preferable because it can be removed.
• a drying treatment may be performed after step (I), before step (II), after step (II), before step (III), or both.
• the drying process can be performed by blowing warm air, disposing in a heating furnace, conveying in the heating furnace, or the like.
• the heating temperature may be set to a temperature at which the solvent can be removed by drying, and is not particularly limited.
• the heating temperature refers to the temperature of warm air or the atmospheric temperature in the heating furnace.
• the hard coat film of the present invention has a laminated structure with high adhesion, and can exhibit higher scratch resistance.
• the mixed layer forming composition containing the epoxy compound (b1) and the polyfunctional (meth) acrylate compound (b2) is applied onto the semi-cured coating film (i).
• the composition for forming a mixed layer is a composition for forming the aforementioned mixed layer.
• the composition for forming a mixed layer usually takes the form of a liquid.
• the mixed layer forming composition is prepared by dissolving or dispersing the epoxy compound (b1), the polyfunctional (meth) acrylate compound (b2), and various additives and a polymerization initiator in an appropriate solvent as necessary. It is preferable to be prepared.
• the concentration of the solid content is generally about 2 to 90% by mass, preferably 2 to 80% by mass, and particularly preferably about 2 to 70% by mass.
• the composition for mixed layer formation contains an epoxy compound (b1) (cationic polymerizable compound) and a polyfunctional (meth) acrylate compound (b2) (radical polymerizable compound).
• the mixed layer forming composition preferably contains a radical photopolymerization initiator and a cationic photopolymerization initiator. Only one radical photopolymerization initiator may be used, or two or more radical photopolymerization initiators having different structures may be used in combination. The same applies to the cationic photopolymerization initiator.
• each photoinitiator is demonstrated one by one.
• radical photopolymerization initiator Any radical photopolymerization initiator may be used as long as it can generate radicals as active species by light irradiation, and any known radical photopolymerization initiator can be used without any limitation. Specific examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone.
• radical photopolymerization initiator triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4- Ethyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Etc. may be used in combination.
• the above radical photopolymerization initiators and auxiliaries can be synthesized by known methods and can also be obtained as commercial products.
• the content of the radical photopolymerization initiator in the mixed layer forming composition is not particularly limited as long as the polymerization reaction (radical polymerization) of the radical polymerizable compound proceeds favorably. .
• the content of the radical photopolymerization initiator in the mixed layer forming composition is not particularly limited as long as the polymerization reaction (radical polymerization) of the radical polymerizable compound proceeds favorably.
• the range of 0.1 to 20 parts by mass preferably in the range of 0.5 to 10 parts by mass, and more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the radically polymerizable compound contained in the composition. It is.
• the cationic photoinitiator which can be included in the above-mentioned composition for hard-coat layer formation is mentioned.
• the content of the cationic photopolymerization initiator in the mixed layer forming composition is not particularly limited as long as the polymerization reaction (cationic polymerization) of the cationic polymerizable compound proceeds favorably. .
• the amount is, for example, in the range of 0.1 to 200 parts by weight, preferably 1 to 150 parts by weight, more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound.
• the composition for forming a mixed layer may further contain one or more optional components in addition to the epoxy compound (b1), the polyfunctional (meth) acrylate compound (b2), and the polymerization initiator.
• the optional component include solvents and various additives that can be used in the hard coat layer forming composition.
• composition for forming a mixed layer used in the present invention can be prepared by mixing the various components described above simultaneously or sequentially in an arbitrary order.
• the preparation method is not particularly limited, and a known stirrer or the like can be used for the preparation.
• composition for mixed layer formation it does not specifically limit as a coating method of the composition for mixed layer formation, A well-known method can be used.
• Step (IV) is a step in which the coating film (i) and the coating film (ii) are fully cured.
• the coating film is preferably cured by irradiating ionizing radiation from the coating film side.
• the ionizing radiation for hardening the coating film (i) can be used suitably in the said process (II).
• the irradiation dose of ionizing radiation for example when the coating film is ultraviolet-curable, preferably to cure the curable compound by irradiation with irradiation dose of ultraviolet rays of 10mJ / cm 2 ⁇ 6000mJ / cm 2 by an ultraviolet lamp. More preferably 50mJ / cm 2 ⁇ 6000mJ / cm 2, further preferably 100mJ / cm 2 ⁇ 6000mJ / cm 2. It is also preferable to combine heating during irradiation with ionizing radiation in order to accelerate the curing of the coating film.
• the heating temperature is preferably 40 ° C. or higher and 140 ° C. or lower, and preferably 60 ° C. or higher and 140 ° C. or lower. It is also preferable to irradiate ionizing radiation multiple times.
• the oxygen concentration at the time of curing is preferably 0 to 1.0% by volume, more preferably 0 to 0.1% by volume, and most preferably 0 to 0.05% by volume.
• the process of providing layers other than a hard-coat layer and a mixed layer, for example, an abrasion-resistant layer it is preferable to include the following steps (IV ′) to (VI) after the steps (I) to (III).
• Step (IV ′) is a step of semi-curing the coating film (ii) formed in the step (III).
• the coating film is preferably cured by irradiating ionizing radiation from the coating film side.
• the ionizing radiation and irradiation amount for semi-hardening the coating film (i) can be used suitably.
• a drying treatment may be performed after step (III), before step (IV ′), after step (IV ′), before step (V), or both.
• the (meth) acryloyl group in the polyfunctional (meth) acrylate compound (c1) contained in the composition for forming a scratch-resistant layer forms a bond in the step (VI) described later.
• the hard coat film of the present invention has a laminated structure with high adhesion, and can exhibit higher scratch resistance.
• the oxygen concentration during curing is not particularly limited, but it is preferable to adjust the oxygen concentration to 0.1 to 2.0% by volume.
• the semi-curing can be adjusted by setting the oxygen concentration in the above range.
• the scratch-resistant layer-forming composition containing the polyfunctional (meth) acrylate compound (c1) is applied onto the semi-cured coating film (ii) to form a coating film (iii). It is a process.
• the composition for forming a scratch-resistant layer is a composition for forming the aforementioned scratch-resistant layer.
• the composition for forming a scratch-resistant layer usually takes the form of a liquid.
• the composition for forming a scratch-resistant layer may be prepared by dissolving or dispersing the polyfunctional (meth) acrylate compound (c1) and, if necessary, various additives and a polymerization initiator in an appropriate solvent. preferable.
• the concentration of the solid content is generally about 2 to 90% by mass, preferably 2 to 80% by mass, and particularly preferably about 2 to 70% by mass.
• the composition for forming a scratch-resistant layer contains a polyfunctional (meth) acrylate compound (c1) (radical polymerizable compound).
• the scratch-resistant layer-forming composition preferably contains a radical photopolymerization initiator. Only one radical photopolymerization initiator may be used, or two or more radical photopolymerization initiators having different structures may be used in combination.
• a radical photoinitiator the radical photoinitiator which can be contained in the above-mentioned composition for mixed layer formation is mentioned.
• the content of the radical photopolymerization initiator in the composition for forming a scratch-resistant layer is not particularly limited as long as the polymerization reaction (radical polymerization) of the radical polymerizable compound proceeds favorably. .
• the polymerization reaction (radical polymerization) of the radical polymerizable compound proceeds favorably.
• the range of 0.1 to 20 parts by mass preferably in the range of 0.5 to 10 parts by mass, and more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the radically polymerizable compound contained in the composition. It is.
• the mixed layer forming composition may further contain one or more optional components in addition to the polyfunctional (meth) acrylate compound (c1) and the polymerization initiator.
• the optional component include the solvent and various additives that can be used in the hard coat layer forming composition in addition to the fluorine-containing compound.
• composition for forming a scratch-resistant layer used in the present invention can be prepared by mixing the various components described above simultaneously or sequentially in any order.
• the preparation method is not particularly limited, and a known stirrer or the like can be used for the preparation.
• a method for applying the composition for forming a scratch-resistant layer is not particularly limited, and a known method can be used.
• Step (VI) is a step in which the coating film (i), coating film (ii), and coating film (iii) are fully cured.
• the coating film is preferably cured by irradiating ionizing radiation from the coating film side.
• the ionizing radiation and irradiation amount for hardening a coating film (i) and a coating film (ii) can be used suitably in the said process (IV).
• a drying treatment may be performed as necessary.
• the present invention also relates to an article provided with the above-described hard coat film of the present invention and an image display device including the hard coat film of the present invention as a surface protective film.
• the hard coat film of the present invention is particularly preferably applied to a flexible display in a smartphone or the like.
• the structure and weight average molecular weight (Mw) of the modifier used in the present invention are as shown in Table 1 below.
• the composition ratio in Table 1 represents the charge ratio of each raw material monomer used for the synthesis of the modifier as a mass ratio.
• Table 1 below also describes the type and amount of polymerization initiator used in the synthesis (molar ratio relative to monomer (K1)).
• the monomer (K2) represented by the abbreviations in Table 1 is as follows.
• FM-0711 Silaplane FM-0711 (manufactured by JNC Corporation, reactive silicone)
• the structures 1 to 6 of the respective modifiers are as follows. In each of the following structures, in order from the left, the structure is derived from the monomer (K2) and the structure is derived from the monomer (K1).
• ⁇ Preparation of base material> (Manufacture of polyimide powder) Under a nitrogen stream, 832 g of N, N-dimethylacetamide (DMAc) was added to a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller and a condenser, and then the temperature of the reactor was adjusted to 25. C. To this, 64.046 g (0.2 mol) of bistrifluoromethylbenzidine (TFDB) was added and dissolved.
• DMAc N, N-dimethylacetamide
• the number average molecular weight (Mn) of the obtained compound (A) was 2310, and dispersity (Mw / Mn) was 2.1. Note that 1 mmHg is about 133.322 Pa.
• Example 1 ⁇ Preparation of composition for forming hard coat layer> (Hardcoat layer forming composition HC-1) CPI-100P, modifier (1-1) and MIBK (methyl isobutyl ketone) are added to the MIBK solution containing the above compound (A), and the concentration of each component is adjusted to the following concentration. The mixture was added to the mixing tank and stirred. The obtained composition was filtered through a polypropylene filter having a pore size of 0.4 ⁇ m to obtain a hard coat layer forming composition HC-1.
• MIBK methyl isobutyl ketone
• Compound (A) 98.6 parts by mass CPI-100P 1.3 parts by mass Modifier (1-1) 0.1 parts by mass Methyl isobutyl ketone 100.0 parts by mass
• the compound used in the composition for hard-coat layer formation is as follows.
• CPI-100P Cationic photopolymerization initiator, manufactured by San Apro Co., Ltd.
• Compound (A) 42.85 parts by mass DPHA 42.85 parts by mass CPI-100P 1.3 parts by mass Irgacure 127 5.0 parts by mass Leveling agent-1 8.0 parts by mass Methyl ethyl ketone 500.0 parts by mass
• the compound used in the composition for mixed layer formation is as follows.
• DPHA A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.
• Irgacure 127 radical photopolymerization initiator, manufactured by BASF
• composition SR-1 for scratch-resistant layer formation ⁇ Preparation of composition for forming scratch-resistant layer> (Composition SR-1 for scratch-resistant layer formation) Each component having the composition described below was charged into a mixing tank, stirred, and filtered through a polypropylene filter having a pore size of 0.4 ⁇ m to obtain a scratch-resistant layer forming composition SR-1.
• the compounds used in the composition for forming a scratch-resistant layer are as follows.
• RS-90 slip agent, manufactured by DIC Corporation
• the hard coat layer forming composition HC-1 was applied on the substrate S-1 using a die coater. After drying at 120 ° C. for 1 minute, the hard coat layer was semi-cured by irradiating ultraviolet rays with an illuminance of 18 mW / cm 2 and an irradiation amount of 10 mJ / cm 2 using an air-cooled mercury lamp at 25 ° C. (this The hard coat film having the hard coat layer in a semi-cured state at the time is referred to as “hard coat film (A)”).
• a mixed layer forming composition by adding MEK to the mixed layer forming composition M-1 and diluting the solid content concentration to 1/10, and apply it to the semi-cured hard coat layer using a die coater. did. After drying at 120 ° C. for 1 minute, using an air-cooled mercury lamp at 25 ° C. and an oxygen concentration of 1%, the mixed layer is semi-cured by irradiating ultraviolet rays with an illuminance of 18 mW / cm 2 and an irradiation amount of 10 mJ / cm 2. The mixed layer was provided on the hard coat layer. On the semi-cured mixed layer, the scratch-resistant layer forming composition SR-1 was applied using a die coater. After drying at 120 ° C.
• the hard coat layer, the mixed layer, and the scratch-resistant layer were completely cured by irradiating with an ultraviolet ray having an illuminance of 60 mW / cm 2 and an irradiation amount of 800 mJ / cm 2 using an air-cooled mercury lamp under a concentration of 100 ppm. Thereafter, the obtained film is heat-treated at 120 ° C.
• Hard coat films 2 to 10 were obtained in the same manner as in Example 1 except that the modifier species in the hard coat layer forming composition HC-1 and the film thickness of the mixed layer were changed as shown in Table 2. .
• Example 11 The types of modifiers and curable components in the hard coat layer forming composition HC-1 were changed as shown in Table 2 to obtain hard coat layer forming composition HC-11.
• the hard coat layer forming composition HC-11 was applied onto the substrate S-1 using a die coater.
• Example 1 except that the modifier in the hard coat layer forming composition HC-1 was changed to comparative modifiers 1x to 3x and the thickness of the mixed layer was changed to the thickness shown in Table 2. Thus, comparative hard coat films 1 to 3 were obtained.
• Comparative Example 4 A comparative hard coat film 4 was obtained in the same manner as in Example 1 except that the modifier in the hard coat layer forming composition HC-1 was not added.
• solvent extractability In the production of the hard coat film, the solvent extractability was evaluated using the hard coat film (A) dried and semi-cured after applying the composition for forming a hard coat layer. Two types of films were prepared: a hard coat film (B) (after MEK cleaning) in which the hard coat layer surface of the hard coat film (A) was washed away with MEK. The surface of the hard coat layer of the hard coat films (A) and (B) using a Quantara SXM type ESCA (Electron Spectroscopic for Chemical Analysis) manufactured by Ulvac-PHI under the conditions of a photoelectron extraction angle of 45 ° and a measurement range of 300 ⁇ m square. The element extractability was measured, and the solvent extractability was calculated by the following formula.
• the element derived from the copolymer [%] represents the content [%] of the element contained only in the copolymer with respect to all the detected elements. Examples 1 to 9 and 11 and Comparative Examples 1 to 3 are F. In Example 10, the content [%] was calculated by using N as an element only in the copolymer.
• the thickness of the mixed layer forming composition M-1 was changed with respect to the hard coat film (A) dried and semi-cured after applying the hard coat layer forming composition. After coating and drying, the repellency of the cured hard coat film was evaluated according to the following criteria.
• a mixed layer forming composition is prepared by adding MEK to the mixed layer forming composition M-1 and diluting the solid content concentration to 1/10.
• the thickness was 3.0 ⁇ m, the mixed layer forming composition M-1 was used without being diluted.
• the thickness of the mixed layer is 0.1 ⁇ m
• the thickness of the mixed layer is 0.5 ⁇ m
• the thickness of the mixed layer is 3.0 ⁇ m
• D Evaluated the hard coat film with a mixed layer thickness of 6.0 ⁇ m.
• C Repelling is observed when the mixed layer thickness is 0.5 ⁇ m, but there is no repelling at 3 ⁇ m.
• D Repelling is observed at a mixed layer thickness of 3 ⁇ m
• Pencil hardness It was measured according to JIS K 5600-5-4 (1999) and evaluated in the following three stages. A: Pencil hardness is 6H or more B: Pencil hardness is 5H C: Pencil hardness is 4H or less
• the composition for forming a hard coat layer containing the modifier of the present invention can be applied on the substrate without any problem, and as shown in Table 2, the surface condition of the hard coat layer was good.
• the solvent extractability of the modifier was excellent, and thus the recoat property was excellent.
• the surface condition of the hard coat layer is poor, or repelling occurs when the mixed layer forming composition is applied on the hard coat layer, thereby forming a mixed layer. The result was that it was not possible.
• Examples 1 to 10 using the compound (A) (polyorganosiloxane) as a curable component in the hard coat layer are excellent in pencil hardness, scratch resistance, and repeated bending resistance, and as a flexible hard coat film. It was found that the performance of was excellent.

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