WO2023008493A1 - シラン化合物およびその製造方法、ポリオルガノシロキサン化合物、ハードコート組成物、ハードコーフィルムおよびその製造方法、ならびにディスプレイ - Google Patents

シラン化合物およびその製造方法、ポリオルガノシロキサン化合物、ハードコート組成物、ハードコーフィルムおよびその製造方法、ならびにディスプレイ Download PDF

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WO2023008493A1
WO2023008493A1 PCT/JP2022/028986 JP2022028986W WO2023008493A1 WO 2023008493 A1 WO2023008493 A1 WO 2023008493A1 JP 2022028986 W JP2022028986 W JP 2022028986W WO 2023008493 A1 WO2023008493 A1 WO 2023008493A1
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hard coat
compound
group
silane compound
general formula
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French (fr)
Japanese (ja)
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文康 石黒
寛人 高麗
聡子 小松
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Kaneka Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • 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
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

  • the present invention relates to a silane compound and a method for producing the same. Furthermore, the present invention relates to a polyorganosiloxane compound that is a condensate of a silane compound, a hard coat composition containing the polyorganosiloxane compound as a curable resin component, a hard coat film, and a method for producing the same. The present invention also relates to a display comprising the hard coat layer.
  • Curved displays and foldable displays are being developed, and studies are underway to replace the glass materials used for display cover windows and substrates with highly flexible plastic film materials. ing. Cover windows of flexible displays such as foldable displays are required to have various properties such as transparency, hardness, and bending resistance.
  • Patent Documents 1 to 3 disclose a polysiloxane-based hard coat material containing a polyorganosiloxane compound having an alicyclic epoxy group as a curable resin component.
  • a polyorganosiloxane compound having an alicyclic epoxy group is obtained by hydrolytic condensation of a silane compound (silane coupling agent) having an alicyclic epoxy group and an alkoxysilyl group.
  • Non-Patent Document 1 discloses "2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane" as a commercially available silane coupling agent having an alicyclic epoxy group.
  • Patent Documents 1 to 3 as specific examples of the hard coat material, a polyorganosiloxane compound obtained by hydrolytic condensation of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane is used as a curable resin component. disclosed.
  • Non-Patent Document 1 page 12 describes that a dialkoxy-type silane compound has better storage stability than a trialkoxy-type silane compound.
  • polyorganosiloxane compounds obtained by condensation of silane compounds with dialkoxy groups have a two-dimensional network of siloxane bonds and a low crosslink density, so that when used as a hard coat material, the mechanical strength is insufficient. Tend.
  • the first aspect of the present invention aims to provide a silane compound that has excellent storage stability and can be cured to form a film with excellent mechanical strength.
  • a hard coat material containing a polyorganosiloxane compound obtained by hydrolytic condensation of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane as a curable resin component is Exhibits high hardness.
  • these hard coat materials have room for improvement in the bending resistance of the cured product.
  • foldable displays There are two types of foldable displays: the type that folds so that the display surface faces inside, and the type that folds so that the display surface faces outside.
  • the hard coat film is used as a cover window of a foldable display that is folded so that the display surface faces outward, the hard coat film is bent so that the hard coat layer-formed surface faces outward when the device is folded.
  • a hard coat film having a hard coat layer containing a polyorganosiloxane compound obtained by hydrolytic condensation of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane as a curable resin component is arranged so that the hard coat layer is on the outside. Cracks tend to occur in the hard coat layer when bent.
  • a second aspect of the present invention aims to provide a hard coat material and a hard coat film capable of achieving both excellent surface hardness and bending resistance.
  • the silane compound of the present invention has a structure represented by general formula (1).
  • a polyorganosiloxane compound containing a structure represented by general formula (11) is obtained by hydrolytic condensation of this silane compound.
  • R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms
  • It is a monovalent hydrocarbon group selected from the group consisting of aralkyl groups having 7 to 12 carbon atoms.
  • R 1 is preferably a methyl group, an ethyl group or a propyl group.
  • a plurality of R 1 in the general formula (1) may be the same or different.
  • Y is a divalent organic group having a main chain of 5 or more atoms. Y may contain an ester bond.
  • the ratio of the structure represented by general formula (11) to the total amount of Si atoms is preferably 0.3 or more.
  • Method 1 Using an ester compound having an alicyclic epoxy group, an alcohol having a terminal —CH ⁇ CH 2 , and a trialkoxysilane as raw materials, the transesterification reaction between the ester compound and the alcohol, and the terminal —CH ⁇ CH 2 and the hydrosilylation reaction of trialkoxysilane with SiH.
  • a polyorganosiloxane compound obtained by hydrolytic condensation of a silane compound can be suitably used as a hard coat material.
  • a hard coat composition according to one embodiment of the present invention contains the above polyorganosiloxane compound and a photocationic polymerization initiator.
  • a hard coat composition containing a polyorganosiloxane compound is applied onto a transparent resin film and cured by irradiation with active energy rays to form a hard coat layer. A film is formed.
  • the hard coat film has a hard coat layer containing a cured polyorganosiloxane compound on at least one main surface of the transparent resin film.
  • the hard coat film may have a top coat layer on the hard coat layer.
  • the topcoat layer may contain a fluorine compound.
  • the hard coat layer is coated with a composition containing a compound having an alkoxysilyl group and a perfluoroalkyl group in the molecule, and the compound is condensed to form the top coat layer.
  • the silane compound of the present invention is inhibited from hydrolysis in the absence of a catalyst and has excellent storage stability.
  • the hard coat film of the present invention can have both excellent surface hardness and bending resistance, and can be suitably used as a cover window material for a foldable display that is folded so that the display surface faces outward.
  • FIG. 1 is a cross-sectional view of a hard coat film of one embodiment
  • FIG. 1 is a cross-sectional view of a hard coat film of one embodiment
  • FIG. 1 is a cross-sectional view of a hard coat film of one embodiment
  • Silane compound One aspect of the present invention is a silane compound represented by general formula (1).
  • R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 2 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms
  • It is a monovalent hydrocarbon group selected from the group consisting of aralkyl groups having 7 to 12 carbon atoms
  • x is 2 or 3.
  • Multiple R 1s may be the same or different.
  • Y in the general formula (1) is a divalent organic group having a main chain of 5 or more atoms.
  • silane compound (1) has two or three (—OR 1 ) in one molecule, and Si— OR 1 is hydrolyzable.
  • a polyorganosiloxane compound is produced by condensation after hydrolysis of Si—OR 1 .
  • R 1 is preferably an alkyl group having 3 or less carbon atoms (methyl group, ethyl group or propyl group), particularly preferably a methyl group or an ethyl group.
  • R 1 is most preferably a methyl group.
  • silane compounds in which R 1 is an ethyl group tend to have lower hydrolyzability of Si—OR 1 and superior stability during storage than silane compounds in which R 1 is a methyl group.
  • x in General formula (1) 3 is preferable.
  • the above silane compound is represented by the following general formula (9), wherein R 2 is don't have R 1 and Y in general formula (9) are the same as in general formula (1).
  • the large chain length of the divalent organic group Y connecting the Si atom and the alicyclic epoxy group (3,4-epoxycyclohexyl group) improves the storage stability of the trialkoxysilane compound.
  • Y in general formula (1) is a divalent organic group having a main chain of 5 or more atoms.
  • Y may be linear or branched.
  • Y may be a linear or branched alkylene group, and may contain atoms other than carbon in the main chain.
  • Y may be a heteroalkylene group and may contain an ether bond, an ester bond, an amide bond, a carbonyl group, an imino group, and the like.
  • the number of atoms in the main chain is the number of atoms forming a linear chain connecting Si atoms and 3,4-epoxycyclohexyl groups in general formula (1). That is, the silane compound of general formula (1) is a compound in which a Si atom and a 3,4-epoxycyclohexyl group are bonded via 5 or more atoms between them.
  • the silane compound of general formula (1) is a compound in which a Si atom and a 3,4-epoxycyclohexyl group are bonded via 5 or more atoms between them.
  • the silane compound (1) In the absence of a catalyst, the silane compound (1) is resistant to hydrolysis of Si—OR 1 and has excellent storage stability.
  • the trialkoxysilane-type compound represented by the general formula (9) is hardly hydrolyzed in the absence of a catalyst even in a high-temperature, high-humidity environment, and exhibits high reactivity in the presence of a catalyst.
  • the number of atoms in the main chain of the organic group Y is preferably 16 or less, more preferably 12 or less, still more preferably 10 or less, and may be 8 or less.
  • Silane compound (1) has a large amount of unreacted alkoxysilyl groups (residual ratio of alkoxysilyl groups) after being exposed to an environment at a temperature of 85° C. and a relative humidity of 85% for 20 hours, and exhibits excellent storage stability. .
  • the residual ratio of alkoxysilyl groups after exposure for 20 hours to an environment of 85° C. temperature and 85% relative humidity is preferably 30% or more, more preferably 50% or more, still more preferably 60% or more, or 70% or more. It may be 80% or more.
  • the silane compound (1) may have a residual ratio of alkoxysilyl groups of 30% or more after being exposed to an environment with a temperature of 85°C and a relative humidity of 85% for 96 hours.
  • the residual ratio of alkoxysilyl groups after exposing the silane compound to an environment with a temperature of 85° C. and a relative humidity of 85% for 96 hours can be 40% or more, 50% or more, or 60% or more.
  • Silane compound (1) has an alicyclic epoxy group (3,4-epoxycyclohexyl group) with a bulky structure, and a long chain ( Since it has a divalent organic group Y serving as a spacer (having 5 or more atoms in the main chain), it has a large molecular volume. Therefore, the access of water molecules to Si — OR 1 is restricted, and the frequency of intermolecular contact between Si—OR 1 is low. is considered to be high.
  • Y is a linear alkylene group
  • specific examples thereof include pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexa A decamethylene group and the like can be mentioned.
  • Y may be one in which some or all of the hydrogen atoms of methylene ( --CH.sub.2--) constituting linear alkylene are substituted with a substituent.
  • substituents include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, phenyl group, amino group, (meth)acrylic group, halogen, allyl group, vinyl group, mercapto group, carboxyl group, nitro group, sulfone group, hydroxy group and the like.
  • the divalent organic group Y may contain atoms other than carbon in its main chain.
  • Y contains an ester bond in general formula (1).
  • Examples of silane compounds in which Y contains an ester bond include structures of general formula (I) and general formula (II).
  • R 1 , R 2 and x in general formulas (I) to (V) are the same as in general formula (1).
  • R 4 and R 5 are divalent organic groups having a main chain of 3 or more carbon atoms, may be branched, and may contain atoms other than carbon in the main chain.
  • R 4 and R 5 are preferably linear alkylene having 3 to 10 carbon atoms or (poly)alkylene oxide having a main chain of 3 to 10 atoms.
  • Specific examples of (poly)alkylene oxides having a main chain of 3 to 10 atoms include -C 2 H 4 -OC 2 H 4 -, -C 3 H 6 -OC 2 H 4 -, -C 2 H 4 -OC 2 H 4 -OC 2 H 4 - and the like.
  • Examples of methods for synthesizing silane compounds in which Y contains an ester bond include a method utilizing transesterification and hydrosilylation.
  • Specific examples of methods for synthesizing silane compounds utilizing transesterification and hydrosilylation include Method 1 and Method 2 below.
  • silane compound represented by the general formula (IV) above can be synthesized by Method 1.
  • the silane compound represented by the above general formula (III) can be synthesized by Method 2.
  • the trialkoxysilane used as a raw material is represented by the general formula HSi(OR 1 ) 3 .
  • R 1 is the same as in general formula (1) and is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Multiple R 1s may be the same or different.
  • R 1 is preferably an alkyl group having 3 or less carbon atoms, particularly preferably a methyl group or an ethyl group. Trimethoxysilane, triethoxysilane and the like are preferably used as the trialkoxysilane.
  • An example of an ester compound having an alicyclic epoxy group used as a raw material in method 1 is methyl 3,4-epoxycyclohexane-1-carboxylate (CAS No. 41088-52-2).
  • Examples of alcohols having a double bond at the end used as raw materials in Method 1 include 2-propen-1-ol, 3-buten-1-ol, 4-penten-1-ol, 5-hexene-1- ol, 6-hepten-1-ol, 7-octen-1-ol, 8-nonen-1-ol, 9-decen-1-ol, ethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, etc. mentioned.
  • Examples of alcohols having an alicyclic epoxy group used as raw materials in method 2 include 3,4-epoxycyclohexylmethanol and 3,4-epoxycyclohexanol.
  • Examples of the ester compound having a double bond at the end used as a starting material in Method 2 include methyl 3-propenoate, methyl 4-pentenoate, methyl 5-hexenoate, methyl 6-heptenoate, and methyl 7-octenoate. , methyl 8-nonenoate, and methyl 9-decenoate.
  • transesterification catalysts include organotin compounds such as dibutyltin oxide; metal oxides such as magnesium oxide, lead oxide, zirconium oxide and zeolite; titanium tetraisopropoxide, aluminum triisopropoxide, lithium methoxide, sodium methoxy metal alkoxides such as sodium ethoxide, potassium t-butoxide; alkali metal amides such as lithium amide, sodium amide and potassium amide; magnesium hydroxide, lithium hydroxide, calcium hydroxide, sodium hydroxide and potassium hydroxide; metal hydroxides; metal carbonates such as magnesium carbonate, lithium carbonate, sodium carbonate and potassium carbonate; metal fatty acid salts such as potassium acetate, calcium laurate and sodium stearate; neutral or alkaline normal salts such as magnesium chloride; is mentioned.
  • the transesterification reaction it is preferable to flow an inert gas such as nitrogen during the reaction in order to distill off the alcohol that is produced.
  • the reaction temperature and reaction time for the transesterification reaction may be appropriately selected.
  • the transesterification reaction is performed by heating and stirring at 140° C. for 6 hours.
  • a catalyst known as a hydrosilylation catalyst can be selected as the catalyst for the hydrosilylation reaction.
  • hydrosilylation catalysts include platinum-olefin complexes, chloroplatinic acid, pure platinum, solid platinum supported on carriers (alumina, silica, carbon black, polymers, etc.), Pt(acac) 2 , platinum - vinylsiloxane complexes (e.g. Ptn ( ViMe2SiOSiMe2Vi )n , Pt[(MeViSiO) 4 ] m ), platinum-phosphine complexes (e.g.
  • Platinum-based catalysts such as platinum-phosphite complexes (eg, Pt[P(OPh) 3 ] 4 , Pt[P(OBu) 3 ] 4 ) are included.
  • Me is a methyl group
  • Bu is a butyl group
  • Vi is a vinyl group
  • Ph is a phenyl group
  • n and m are integers.
  • platinum-based hydrosilylation catalysts include the platinum-hydrocarbon complexes described in Ashby et al., US Pat. No. 3,159,601 and US Patent No. 3,159,662, and Lamoreaux et al., US Pat. and platinum alcoholate catalysts described therein.
  • non-platinum hydrosilylation catalysts examples include RhCl( PPh3 ) 3 , RhCl3 , Rh/ Al2O3 , RuCl3 , IrCl3 , FeCl3, AlCl3 , PdCl2.2H2O , NiCl2 , TiCl 4 , and the like.
  • the hydrosilylation catalyst may be used alone or in combination of two or more. From the viewpoint of catalytic activity, platinum-based catalysts are preferred, and among these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes, Pt(acac) 2 and the like are preferred.
  • the reaction temperature and reaction time for the hydrosilylation reaction may be selected as appropriate.
  • trimethoxysilane is used as the trialkoxysilane
  • the hydrosilylation reaction is performed, for example, by heating and stirring at 80° C. for 10 hours.
  • triethoxysilane is used as the trialkoxysilane
  • the hydrosilylation reaction is carried out, for example, by heating and stirring at 105° C. for 10 hours.
  • Method 1 and Method 2 the order of transesterification and hydrosilylation is not particularly limited.
  • an ester exchange reaction between an ester compound having an alicyclic epoxy group and an alcohol having a double bond at the end causes an alicyclic epoxy group and a terminal
  • a compound is synthesized in which a molecular chain having —CH ⁇ CH 2 in is linked via an ester bond.
  • Method 1 when the hydrosilylation reaction is first carried out, the hydrosilylation reaction between the alcohol having a terminal double bond and trialkoxysilane is first carried out to obtain the general formula HO--R 6 --Si(OR 1 )
  • the silane compound represented by 3 is obtained.
  • R6 is a divalent organic group.
  • a silane compound represented by the general formula (IV) is obtained by transesterification between this silane compound and an ester compound having an alicyclic epoxy group.
  • a silane compound represented by —R 7 —Si(OR 1 ) 3 is obtained.
  • R7 is a divalent organic group and R8 is an alkyl group.
  • a silane compound represented by the general formula (III) is obtained by transesterifying the ester moiety of this silane compound with an alcohol having an alicyclic epoxy group.
  • a silane compound having an Si atom and an alicyclic epoxy group (3,4-cyclohexyl group) via an ester bond in both cases where the transesterification reaction is carried out first and where the hydrosilylation reaction is carried out first. is obtained.
  • hydrosilyl It is preferred to carry out the conversion reaction.
  • the above silane compound (1) is excellent in storage stability, can be used as a silane coupling agent, and can also be used as an adhesive strength adjusting agent for adhesives and pressure-sensitive adhesives, and as a coating agent. Moreover, since the silane compound (1) has an alicyclic epoxy group and is polymerizable, it can also be used as a monomer component of a resin.
  • Silane compound (1) has excellent storage stability because hydrolysis is suppressed in the absence of a catalyst. produce compounds. That is, the silane compound (1) can also be used as a raw material for polyorganosiloxane compounds.
  • Polyorganosiloxane compound One aspect of the present invention relates to a polyorganosiloxane compound obtained by condensation of the above silane compound (1).
  • the silane compound (1) has two or three alkoxysilyl groups in one molecule, and since Si—OR 1 has hydrolyzability, the condensation of the silane compound (1) , a polyorganosiloxane compound is produced.
  • the polyorganosiloxane compound obtained by condensation of silane compound (1) contains a structure represented by general formula (11).
  • Y in general formula (11) is the same as in general formula (1) and is a divalent organic group having a main chain of 5 or more atoms. Y may contain an ester bond.
  • silane compound other than the silane compound (1) may be used in the synthesis of the polyorganosiloxane compound.
  • Examples of silane compounds other than silane compound (1) include silane compounds represented by the following general formula (2) (hereinafter sometimes referred to as "silane compound (2)").
  • silane compound (2) silane compounds represented by the following general formula (2) (hereinafter sometimes referred to as "silane compound (2)").
  • R 1 , R 2 and x in general formula (2) are the same as R 1 , R 2 and x in general formula (1).
  • R 3 in general formulas (2) and (12) is a monovalent organic group.
  • R 3 is a substituted or unsubstituted double bond-containing group, a substituted or unsubstituted cycloalkyl group-containing group, a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted alkyl group, A group having a glycidyl group, a group having an oxetanyl group, a hydrogen atom, or a monovalent organic group represented by the following general formula (3).
  • W is a divalent organic group having a main chain of 4 or less atoms, and W is bonded to the Si atom.
  • the silane compound (2) is represented by the general formula (2) in which R 3 is the general formula (3 ) is preferably a monovalent organic group represented by silane compound. That is, the silane compound (2) preferably has an alicyclic epoxy group (3,4-epoxycyclohexyl group).
  • Examples of the silane compound (2) in which R 3 is a monovalent organic group represented by general formula (3) include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4- epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyldimethylmethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propymethyl dimethoxysilane, 3-(3,4-epoxycyclohexyl)propyldimethylmethoxysilane, and the like.
  • the silane compound obtained by condensation is represented by the general formula (13). contains structures that
  • a silane compound that does not contain an alicyclic epoxy group may be used as the silane compound (2).
  • a silane compound containing an alicyclic epoxy group (a silane compound in which R3 is a monovalent organic group represented by the general formula ( 3 )) and a silane containing no alicyclic epoxy group. Both compounds may be used.
  • the silane compound containing no alicyclic epoxy group one having a glycidyl group is preferred.
  • silane compounds having a glycidyl group include those in which R 3 in general formula (2) is a glycidyloxyalkyl group.
  • the glycidyloxyalkyl group includes 3-glycidyloxypropyl group, 8-glycidyloxyoctyl group and the like.
  • x is preferably 3.
  • the polyorganosiloxane compound has a three-dimensional structure, and the hardness of the cured film (hard coat layer) obtained by curing the polyorganosiloxane compound tends to be improved.
  • a silane compound in which x is 1 may be used for the purpose of adjusting the molecular weight of the polyorganosiloxane compound obtained by condensation.
  • the amount of water is too small, the number of OR 1 groups remaining without hydrolysis is large, and the molecular weight of the polyorganosiloxane compound is small, so the hardness of the hard coat layer tends to be insufficient.
  • the amount of water is excessively large, the reaction rate of hydrolysis and condensation reactions is high, resulting in the formation of high-molecular-weight condensates, which tends to reduce the transparency and flexibility of the hard coat layer.
  • the weight average molecular weight of the polyorganosiloxane compound is preferably 500 or more. Also from the viewpoint of suppressing volatilization, the weight average molecular weight of the polyorganosiloxane compound is preferably 500 or more. On the other hand, if the molecular weight is excessively high, cloudiness may occur due to a decrease in compatibility with other compositions or the like. Therefore, the weight average molecular weight of the polyorganosiloxane compound is preferably 20,000 or less.
  • the molecular weight of the polyorganosiloxane compound can be controlled by selecting the amount of water used in the reaction and the type and amount of catalyst. For example, increasing the amount of water tends to increase the molecular weight.
  • the number of OR 1 groups remaining per silane compound unit in the polyorganosiloxane compound is small.
  • the average number of one OR group per one Si atom in the polyorganosiloxane compound is two or less.
  • the average number of one OR group per Si atom is preferably 1.5 or less, more preferably 1.0 or less.
  • the average number of OR groups per Si atom in the polyorganosiloxane compound is 0.01 or more, 0.05 or more, 0.1 or more, 0.2 or more, or 0.3 or more.
  • the polyorganosiloxane compound preferably has a large content of epoxy groups.
  • the residual rate of epoxy groups is preferably 20% or more, more preferably 40% or more, still more preferably 60% or more, and may be 80% or more, 90% or more, or 95% or more.
  • the residual ratio of OR 1 groups and the residual ratio of epoxy groups can be calculated by 1 H-NMR measurement.
  • the hydrolysis reaction and condensation reaction of the silane compound it is preferable to carry out the reaction under neutral or basic conditions from the viewpoint of suppressing the ring opening of the epoxy group.
  • hydrolysis and condensation reaction it is preferable to carry out a condensation reaction.
  • Neutral salt catalysts include salts composed of an acid and a base, and salts composed of an alkali metal or alkaline earth metal cation and a halogen anion are preferred.
  • Specific examples of neutral salts include lithium chloride, sodium chloride, potassium chloride, beryllium chloride, magnesium chloride, calcium chloride, lithium bromide, sodium bromide, potassium bromide, beryllium bromide, magnesium bromide, and calcium bromide.
  • the neutral salt catalyst may remain in the polyorganosiloxane compound.
  • the amount of neutral salts remaining in the polyorganosiloxane compound may be from 1 ppm to 10000 ppm, or from 50 ppm to 5000 ppm or from 100 ppm to 1000 ppm.
  • the polyorganosiloxane compound obtained by condensation of silane compound (1) contains a structure represented by general formula (11).
  • a hard coat layer formed by curing a polyorganosiloxane compound having a structure represented by general formula (11) can achieve both high surface hardness and excellent flex resistance. Moreover, a hard coat film having the hard coat layer tends to be less curled.
  • the ratio of the structure represented by general formula (11) to the total number of Si atoms in the polyorganosiloxane compound is preferably 0.3 or more, and 0.3 or more. It is more preferably 4 or more, more preferably 0.5 or more, and may be 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, or 0.95 or more.
  • the number of epoxy groups contained in one molecule of the polyorganosiloxane compound is as large as possible, and it is particularly preferable that the number of alicyclic epoxy groups is large.
  • the total ratio of the structure represented by the general formula (11) and the structure represented by the general formula (13) to the total number of Si atoms in the polyorganosiloxane compound is preferably 0.4 or more, and 0.5. It is more preferably 0.6 or more, and may be 0.7 or more, 0.8 or more, 0.9 or more, 0.95 or more, or 1.
  • the ratio of the structure represented by the general formula (13) to the total number of Si atoms in the polyorganosiloxane compound is preferably 0.5 or less, and 0.3 or less. It is more preferably 0.2 or less, and may be 0.1 or less, 0.05 or less, or 0.
  • the ratio of the structure represented by general formula (11) to the total of the structure represented by general formula (11) and the structure represented by general formula (13) is 0.5 or more. is preferred.
  • the ratio of the structure of general formula (11) to the sum of the structure of general formula (11) and the structure of general formula (13) is more preferably 0.7 or more, 0.8 or more, 0.9 or more, 0.95 It may be more than or equal to 1.
  • the higher the ratio the more excellent the bending resistance of the hard coat layer formed by curing the polyorganosiloxane compound tends to be.
  • the ratio of the structure of general formula (13) to the total of the structure of general formula (11) and the structure of general formula (13) is 0.05 or more, 0.1 or more, or 0 .2 or more.
  • the alkoxysilyl group —OR 1 participates in the reaction, but other functional groups attached to the Si atom do not react, except for side reactions such as ring opening of epoxy groups. Therefore, in the polyorganosiloxane compound obtained by condensation of the silane compound, the structure (11) portion of the silane compound (1) and the structure (12) portion of the silane compound (2) retain their structures before and after the reaction. ing.
  • the ratio of the structure of general formula (11) to the total number of Si atoms contained in the polyorganosiloxane compound is approximately equal to the ratio of the silane compound of general formula (1) to the total amount of silane compounds. That is, by adjusting the charge ratio of the silane compound when synthesizing the polyorganosiloxane compound, the polyorganosiloxane compound having the structure represented by the general formula (11) in the above ratio can be obtained.
  • the ratio of silane compound (1) to the total amount of silane compounds is preferably 0.3 or more, more preferably 0.4 or more, still more preferably 0.5 or more, 0.6 or more, 0.7 or more, or 0.8. It may be 0.9 or more, 0.95 or more, or 1.
  • the molar ratio of the silane compound (2) to the silane compound (1) is preferably 2 or less. is more preferably 0.4 or less, particularly preferably 0.2 or less, and may be 0.1 or less.
  • the hard coat layer When using a silane compound (2) having an alicyclic epoxy group, that is, a silane compound in which R 3 in general formula (2) is a monovalent organic group represented by general formula (3), the hard coat layer From the viewpoint of bending resistance, the molar ratio of the silane compound (2) to the total amount of the silane compounds is preferably 0.5 or less, more preferably 0.3 or less, further preferably 0.2 or less, and 0.1 or less or It may be 0.05 or less.
  • Hard coat composition One aspect of the present invention relates to a hardcoat composition that includes the polyorganosiloxane compound described above.
  • the above polyorganosiloxane compound can be used as a curable resin material for forming a hard coat layer because the alicyclic epoxy group in the structure of general formula (11) has photocurable properties.
  • the hard coat composition contains the above polyorganosiloxane compound as a curable resin component, and further contains a photocationic polymerization initiator.
  • the hardcoat composition may further include leveling agents, reactive diluents, photosensitizers, particles and other additives as solids (non-volatiles).
  • the content of the polyorganosiloxane compound in the hard coat composition is preferably 40 parts by weight or more with respect to the total 100 parts by weight of the solid content (non-volatile content). 50 parts by weight or more is more preferable, and 60 parts by weight or more is even more preferable.
  • a photocationic polymerization initiator is a compound (photoacid generator) that generates an acid upon irradiation with an active energy ray.
  • the acid generated from the photoacid generator promotes ring-opening and polymerization reaction of the epoxy groups of the polyorganosiloxane compound, forming intermolecular crosslinks and curing the hard coat material.
  • Photocationic polymerization initiators include strong acids such as toluenesulfonic acid, antimony hexafluoride, boron tetrafluoride, phosphorus hexafluoride, fluoroalkyl phosphorus fluoride, and fluoroalkyl gallium fluoride; sulfonium salts, ammonium salts, and phosphonium salts. , iodonium salts, selenium salts and other onium salts; iron-allene complexes; silanol-metal chelate complexes; sulfonic acid derivatives of; and organic halogen compounds. Among these, aromatic sulfonium salts and aromatic iodonium salts are preferred because of their high stability in the hard coat composition.
  • the content of the photocationic polymerization initiator in the hard coat composition is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the polyorganosiloxane compound. 0.2 to 2 parts by weight is more preferable.
  • the hard coat composition may contain a leveling agent.
  • a leveling agent a silicone-based leveling agent and a fluorine-based leveling agent are preferred. Inclusion of a leveling agent is expected to reduce the surface tension of the hard coat composition and improve the surface smoothness.
  • the content of the leveling agent in the hard coat composition is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, and 0.05 to 10 parts by weight, based on 100 parts by weight of the polyorganosiloxane compound. 1 part by weight is more preferred.
  • the hardcoat composition may contain a reactive diluent.
  • reactive diluents include cationically polymerizable compounds other than the above polyorganosiloxane compounds.
  • a compound having a cationic polymerizable functional group is used as the reactive diluent for cationic photopolymerization.
  • Cationically polymerizable functional groups of reactive diluents include epoxy groups, vinyl ether groups, oxetane groups, and alkoxysilyl groups. Among them, as the reactive diluent, one having an epoxy group is preferable because of its high reactivity with the epoxy group of the polyorganosiloxane compound.
  • the content of the reactive diluent in the hard coat composition is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, relative to 100 parts by weight of the polyorganosiloxane compound.
  • the hard coat composition may contain a photosensitizer for the purpose of improving the photosensitivity of the photocationic polymerization initiator (photoacid generator).
  • a photosensitizer there is a type that improves the photosensitivity of the photocationic polymerization initiator by absorbing light in the wavelength range that the photocationic polymerization initiator cannot absorb, and a type that has a large absorption wavelength range with the photocationic polymerization initiator. Although there is no difference, any type that improves the photosensitivity of the photocationic polymerization initiator may be used.
  • photosensitizers include anthracene derivatives, benzophenone derivatives, thioxanthone derivatives, anthraquinone derivatives, benzoin derivatives, naphthalene derivatives and the like.
  • the content of the photosensitizer in the hard coat composition is preferably 500 parts by weight or less, more preferably 100 parts by weight or less, and even more preferably 50 parts by weight or less with respect to 100 parts by weight of the photocationic polymerization initiator. .
  • the hard coat composition may contain particles for the purpose of adjusting film properties such as surface hardness and bending resistance.
  • particles organic particles, inorganic particles, organic-inorganic composite particles, etc. may be appropriately selected and used.
  • the particles may be surface-modified, and polymerizable functional groups may be introduced by surface modification.
  • the average particle diameter of the particles is, for example, about 5 nm to 10 ⁇ m. From the viewpoint of increasing the transparency of the hard coat layer, the average particle size is preferably 1000 nm or less, more preferably 500 nm or less, even more preferably 300 nm or less, and particularly preferably 100 nm or less.
  • the particle size can be measured by a laser diffraction/scattering type particle size distribution analyzer, and the volume-based median size is taken as the average particle size.
  • the content of the particles in the hard coat composition is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, relative to 100 parts by weight of the polyorganosiloxane compound.
  • the hard coat composition may be solventless or may contain a solvent. When the hard coat composition contains a solvent, it preferably does not dissolve the transparent resin film 1 as the substrate. On the other hand, the adhesion between the transparent resin film 1 and the hard coat layer 3 may be improved by using a solvent having sufficient solubility to swell the resin film.
  • the content of the solvent is preferably 500 parts by weight or less, more preferably 300 parts by weight or less, and even more preferably 100 parts by weight or less with respect to 100 parts by weight of the polyorganosiloxane compound.
  • the hard coat composition may contain additives such as inorganic pigments, organic pigments, surface conditioners, surface modifiers, plasticizers, dispersants, wetting agents, thickeners, antifoaming agents, and UV stabilizers. good.
  • the hard coat composition may also contain a thermoplastic, thermosetting or photocurable resin material other than the above polyorganosiloxane compound.
  • the hard coat composition may contain a radical polymerization initiator in addition to the photocationic polymerization initiator.
  • Hard coat film One aspect of the present invention is a hard coat film comprising a hard coat layer comprising a cured product of the above hard coat composition on a transparent resin film.
  • FIG. 1 is a cross-sectional view of a hard coat film according to one embodiment of the present invention.
  • the hard coat film 11 has a hard coat layer 3 on one main surface of the transparent resin film 1 .
  • the hard coat layer 3 is a cured product layer containing a cured product of the above polyorganosiloxane compound.
  • the hard coat film may have a top coat layer 5 on the hard coat layer 3 .
  • the hard coat film may have a hard coat layer on one side of the transparent resin film, or may have a hard coat layer on both sides of the transparent resin film.
  • the transparent resin film 1 is a resin substrate that serves as a base for forming the hard coat layer 3 .
  • the transparent resin film 1 is preferably transparent.
  • the total light transmittance of the transparent resin film 1 is preferably 80% or higher, more preferably 85% or higher, even more preferably 90% or higher.
  • the haze of the transparent resin film 1 is preferably 2% or less, more preferably 1% or less.
  • the thickness of the transparent resin film 1 is, for example, about 1 to 1000 ⁇ m.
  • the thickness of the transparent resin film 1 is preferably 5 to 500 ⁇ m, more preferably 10 to 200 ⁇ m, even more preferably 15 to 150 ⁇ m. If the thickness is too small, the hardness tends to be insufficient, and if the thickness is too large, the flexibility tends to be poor.
  • the resin material constituting the transparent resin film 1 includes polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylic resins such as polymethyl methacrylate (PMMA), and cellulose resins such as triacetyl cellulose (TAC).
  • polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN)
  • acrylic resins such as polymethyl methacrylate (PMMA)
  • cellulose resins such as triacetyl cellulose (TAC).
  • TAC triacetyl cellulose
  • polyesters such as PET, cellulosic resins such as TAC, and polyimides are preferable as resin materials because of their excellent transparency and mechanical strength.
  • the film base material is required to have excellent heat resistance and mechanical strength. Therefore, transparent polyimide is particularly preferable as the resin material for the transparent resin film.
  • General wholly aromatic polyimides are colored yellow or brown, but transparent polyimides with high visible light transmittance have been created by introducing alicyclic structures, bending structures, and fluorine substituents. can get.
  • the transparent resin film 1 may contain two or more resin materials.
  • the transparent resin film may contain a stabilizer such as an ultraviolet absorber and a radical trapping agent for the purpose of imparting weather resistance, and a dye or pigment such as a bluing agent for the purpose of adjusting color tone.
  • the transparent resin film 1 may have a single-layer structure or a multi-layer structure.
  • the transparent resin film may be a laminate in which a plurality of films are bonded together, and the surface of the film (the surface on which the hard coat layer 3 is formed and/or the surface on which the hard coat layer is not formed) is provided with an easy-adhesion layer, an antistatic layer, A functional layer such as an antireflection layer may be provided.
  • the thickness of the transparent resin film 1 is not particularly limited, and can be appropriately selected, for example, from the range of 1 to 1000 ⁇ m, preferably 5 to 500 ⁇ m, more preferably 10 to 200 ⁇ m, still more preferably 15 to 150 ⁇ m.
  • a hard coat layer 3 is formed by applying a hard coat composition onto the transparent resin film 1 and curing the composition.
  • the hard coat composition used for forming the hard coat layer 3 contains a polyorganosiloxane compound as a curable resin component.
  • a hard coat composition is applied onto the transparent resin film 1, and the solvent is removed by drying if necessary, followed by irradiation with active energy rays to cure the hard coat composition, thereby forming a hard coat on the transparent resin film 1.
  • Layer 3 is formed.
  • Examples of the method of applying the hard coat composition include roll coating such as bar coating, gravure coating and comma coating, die coating such as slot die coating and fountain die coating, spin coating, spray coating and dip coating.
  • the surface of the transparent resin film may be subjected to surface treatment such as corona treatment or plasma treatment.
  • an easy-adhesion layer or the like may be provided on the surface of the transparent resin film 1 .
  • Ultraviolet rays are preferable as active energy rays.
  • the cumulative irradiation dose of active energy rays is, for example, about 50 to 10000 mJ/cm 2 , and may be set according to the type and amount of the cationic photopolymerization initiator, the thickness of the film, and the like.
  • the curing temperature is not particularly limited, it is usually 150° C. or lower, and may be 100° C. or lower or 90° C. or lower.
  • the thickness of the hard coat layer 3 is preferably 0.5 ⁇ m or more, more preferably 2 ⁇ m or more, still more preferably 3 ⁇ m or more, and particularly preferably 5 ⁇ m or more.
  • the thickness of the hard coat layer 3 is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less. Mechanical properties such as surface hardness tend to improve as the thickness of the hard coat layer increases. On the other hand, when the thickness of the hard coat layer is excessively large, the flex resistance of the hard coat layer may decrease.
  • the total thickness of the transparent resin film 1 and the hard coat layer 3 is preferably 10-500 ⁇ m, more preferably 15-250 ⁇ m, even more preferably 20-200 ⁇ m. If the thickness is too small, the mechanical strength may be insufficient, and if the thickness is too large, the transparency and flexibility may be insufficient.
  • the ratio of the thickness D 1 of the transparent resin film 1 to the thickness D 3 of the hard coat layer 3: D 3 /D 1 is, for example, about 0.01-10.
  • a topcoat layer 5 may be provided on the surface layer of the hardcoat layer 3 .
  • the scratch resistance and antifouling properties are improved.
  • the fluorine compound that constitutes the topcoat layer contains one or more fluorine atoms in the molecule.
  • the fluorine compound preferably contains a perfluoroalkyl group.
  • Compounds containing a perfluoroalkyl group include perfluoroalkyl compounds, perfluoroalkyl ether compounds, perfluoroether compounds, perfluoropolyether compounds, and the like.
  • the fluorine compound constituting the topcoat layer is preferably a condensate of a compound having an alkoxysilyl group and a perfluoroalkyl group in the molecule, and the alkoxysilyl group is hydrolyzed and condensed to form a high molecular weight compound to form a film.
  • a perfluoroalkyl group is an alkyl group in which all hydrogen atoms are replaced with fluorine atoms, and is represented by CF 3 (CF 2 ) n —.
  • the alkoxysilyl group is preferably a trialkoxysilyl group, more preferably a triethoxysilyl group or a trimethoxysilyl group, and particularly preferably a trimethoxysilyl group.
  • a compound having an alkoxysilyl group and a perfluoroalkyl group in the molecule preferably has a fluoroalkyl ether structure, and is preferably an oligomer having a fluoroalkyl ether repeating unit.
  • fluoroalkyl ether structure examples include -(OC 4 F 8 )-, -(OC 3 F 6 )-, -(OC 2 F 4 )-, -(OCF 2 )- and the like.
  • the perfluoroalkyl group of the fluoroalkyl ether may be linear or branched, but is preferably linear from the viewpoint of scratch resistance.
  • the number average molecular weight of the oligomer is preferably 1,000 to 50,000, more preferably 3,000 to 20,000, even more preferably 5,000 to 10,000. If the number average molecular weight is less than 1,000, the scratch resistance may be poor, and if it is more than 50,000, it may be difficult to apply the composition.
  • the perfluoroalkyl group-containing compound may contain substituents other than perfluoroalkyl groups and repeating units other than fluoroalkyl ethers.
  • substituents include alkyl groups and fluoroalkyl groups obtained by substituting fluorine atoms for some of the hydrogen atoms of alkyl groups (that is, fluoroalkyl groups other than perfluoroalkyl groups).
  • the perfluoroalkyl group-containing compound preferably has a higher ratio of hydrogen atoms in the alkyl group substituted with fluorine.
  • the method of forming the topcoat layer 5 is not particularly limited, and includes roll coating such as bar coating, gravure coating and comma coating, die coating such as slot die coating and fountain die coating, wet methods such as spin coating, spray coating and dip coating; vacuum deposition. , sputtering, CVD, etc. can be used.
  • roll coating such as bar coating, gravure coating and comma coating
  • die coating such as slot die coating and fountain die coating
  • wet methods such as spin coating, spray coating and dip coating
  • vacuum deposition. sputtering, CVD, etc.
  • a wet method is preferred from the viewpoint of promoting hydrolysis.
  • a primer layer may be provided on the hard coat layer 3 and the top coat layer 5 may be formed thereon.
  • Materials for the primer layer include metal oxides such as silicon oxide, titanium oxide, aluminum oxide and zirconium oxide; and organic/inorganic hybrid materials, which are hydrolytic condensates of alkoxysilanes.
  • corona treatment is preferable because the treatment can be easily performed at atmospheric pressure.
  • the corona treatment density is preferably 1 W ⁇ min/m 2 or more, more preferably 10 W ⁇ min/m 2 or more, 30 W ⁇ min/m 2 or more, 100 W ⁇ min/m 2 or more, or 500 W ⁇ min/m 2 or more. 3000 W ⁇ min/m 2 or less is preferable, and 600 W ⁇ min/m 2 or less is more preferable. If the treatment density is too low, the effect of surface treatment on improving adhesion may be insufficient, and if the treatment density is too high, the hard coat layer may deteriorate.
  • the scratch-resistant layer is formed by a wet method
  • a composition obtained by diluting a compound (oligomer) having an alkoxysilyl group and a perfluoroalkyl group in the molecule with a solvent are perfluoroaliphatic hydrocarbons having 5 to 12 carbon atoms such as perfluorohexane, perfluoromethylcyclohexane and perfluoro-1,3-dimethylcyclohexane.
  • polyfluoroaromatic hydrocarbons such as bis(trifluoromethyl)benzene; perfluoropropylmethyl ether ( C3F7OCH3 ) , perfluorobutylmethylether ( C4F9OCH3 ) , perfluorobutylethylether (C 4 F 9 OC 2 H 5 ), perfluorohexylmethyl ether (C 2 F 5 CF(OCH 3 )C 3 F 7 ) and other hydrofluoroethers (HFE).
  • the perfluoroalkyl group and alkyl group of the hydrofluoroether may be linear or branched.
  • hydrofluoroether is preferred, and perfluorobutyl methyl ether ( C4F9OCH3 ) and perfluorobutylethyl ether ( C4F9OC2H5 ) are preferred.
  • the solvent may be a mixed solvent of two or more.
  • the composition contains perfluoroalkyl group-containing compounds typified by fluoroalkyl ether oligomers having no alkoxysilyl groups in the molecule, fluorine-based oils, and other additives such as silicone-based oils.
  • fluorine-based oils typified by fluorine-based oils, and other additives such as silicone-based oils.
  • silicone-based oils may contain The inclusion of fluorine oil or silicone oil may improve scratch resistance and antifouling properties.
  • the composition may contain catalysts such as acids, bases, and metal organic compounds. Containing a catalyst promotes the reaction between the alkoxysilyl groups and the functional groups on the surface of the hard coat layer, and may improve the adhesion of the top coat layer 5 to the hard coat layer 3 .
  • the composition may contain water. Since the presence of water hydrolyzes the alkoxysilyl groups, the reaction with the functional groups on the surface of the hard coat layer is promoted, and the adhesion of the top coat layer 5 to the hard coat layer 3 may be improved.
  • scratch resistant coating composition commercially available products such as "OPTOOL UD509" and “OPTOOL DSX-E” manufactured by Daikin Industries may be used. Solvents and additives may be added to commercially available coating compositions.
  • the solid content concentration of the compound (oligomer) having an alkoxysilyl group and a perfluoroalkyl group in the molecule in the composition is not particularly limited, but from the viewpoint of coating properties, it is preferably 20% by weight or less, more preferably 10% by weight or less. , more preferably 5% by weight or less, and may be 1% by weight or less or 0.5% by weight or less. If the solid content concentration is excessively high, the coating film may become cloudy.
  • Heating promotes condensation of the compound having an alkoxysilyl group and a perfluoroalkyl group in the alkoxysilyl group molecule.
  • the heating temperature is preferably 30° C. or higher, more preferably 60° C. or higher, and may be 100° C. or higher or 130° C. or higher.
  • the heating temperature is usually 170° C. or lower.
  • the thickness of the topcoat layer 5 is not particularly limited, it is preferably 1 nm or more, more preferably 5 nm or more, even more preferably 6 nm or more, and particularly preferably 10 nm or more.
  • the thickness of the scratch resistant layer is preferably 1000 nm or less, more preferably 100 nm or less, and may be 50 nm or less, 45 nm or less, 40 nm or less, 35 nm or less, or 30 nm or less. If the thickness of the scratch-resistant layer is too small, the scratch resistance and antifouling property may be insufficient, and if the thickness is too large, the coating film may become cloudy and the transparency may be lowered.
  • the alkoxysilyl group of the perfluoroalkyl compound is preferably hydrolyzed and condensed. If the hydrolysis and condensation are accelerated by heating or the like after application of the composition, the hydroxyl groups generated by hydrolysis of the alkoxysilyl groups are only the alkoxysilyl groups of other perfluoro compounds (hydroxyl groups generated by the hydrolysis thereof). It is possible to form a covalent bond through a condensation reaction with the functional group on the surface of the hard coat layer 3 . Therefore, it is considered that the perfluoroalkyl compound is firmly fixed to the hard coat layer 3 and the scratch resistance is improved.
  • a hard coat layer formed by curing a polyorganosiloxane compound having an epoxy group has a hydroxyl group (silanol group) generated by hydrolysis during condensation of a silane compound, and furthermore, the epoxy group during curing. It has a hydroxyl group generated with ring opening. These hydroxyl groups are capable of a condensation reaction with alkoxysilyl groups of perfluoroalkyl compounds.
  • the polyorganosiloxane compound that constitutes the hard coat layer is an organic compound containing Si atoms, similar to the alkoxysilyl group of the perfluoro compound, and has a high affinity with each other. Since the group or the like can condense with the alkoxysilyl group of the perfluoro compound, it is thought that the adhesion between the hard coat layer 3 and the top coat layer 5 is improved.
  • the hard coat film in which the hard coat layer 3 containing the cured product of the polyorganosiloxane compound having the structure represented by the general formula (1) is provided on the transparent resin film 1 has high surface hardness and resistance. Excellent flexibility.
  • the pencil hardness of the surface on which the hard coat layer 3 is formed is preferably HB or higher, more preferably H or higher, still more preferably 2H or higher, even more preferably 3H or higher, and may be 4H or higher.
  • the surface hardness tends to increase as the thickness of the hard coat layer 3 increases.
  • the mandrel diameter at which cracks did not occur in the hard coat layer (the mandrel in the test immediately before cracks occurred) (diameter) ⁇ is preferably small.
  • ⁇ is preferably 6 mm or less, more preferably 4 mm or less, and may be 3 mm or less or 2 mm or less.
  • the number of times of bending until the hard coat layer cracks is preferably 1000 times or more.
  • the bending endurance is more preferably 10,000 times or more, and may be 50,000 times or more, 100,000 times or more, or 200,000 times or more.
  • the bending resistance of the hard coat film is enhanced, and ⁇ tends to be small and the bending endurance number tends to be large.
  • the hard coat film has a small curl.
  • the hard coat film when the hard coat film is cut into a 3 cm square, it is preferred that it does not form a cylinder.
  • the average value of the lifting amount of the four vertices of the hard coat film is preferably 8 mm or less, more preferably 6 mm or less, and even more preferably 4 mm or less.
  • a polysiloxane-based hard coat layer formed by curing a polyorganosiloxane compound having an alicyclic epoxy group has excellent hardness, but tends to be inferior in flex resistance.
  • a polysiloxane-based hard coat layer formed by curing a polyorganosiloxane compound having a glycidyl group has excellent bending resistance, but tends to exhibit large cure shrinkage and curl.
  • a hard coat layer by curing the polyorganosiloxane compound having the structure represented by the general formula (11), a hard coat film having excellent bending resistance and less curling can be obtained. be done.
  • a polyorganosiloxane compound obtained by condensation of a silane compound containing an alicyclic epoxy group retains its alicyclic structure even after curing by ring-opening polymerization of the epoxy group. Curing tends to increase volume. Therefore, cure shrinkage is less likely to occur, which can contribute to the suppression of curling of the hard coat film. Moreover, since the alicyclic structure is more rigid than the chain structure, the hardness of the hard coat layer tends to be improved.
  • the polyorganosiloxane compound having the structure represented by the general formula (11) a specific Because of the presence of the organic group Y having a chain length of , the molecular structure has flexibility even after curing due to the reaction of the epoxy group. Therefore, it is considered that the hard coat layer composed of the cured product of the polyorganosiloxane compound exhibits excellent flex resistance. As described above, the greater the distance between the Si atom and the alicyclic epoxy group, that is, the greater the number of atoms constituting the main chain of the organic group Y as a spacer and the longer the chain length, the greater the bending resistance of the hard coat layer 3. tend to improve.
  • the total light transmittance of the hard coat film is preferably 80% or higher, more preferably 85% or higher, and even more preferably 88% or higher.
  • the haze of the hard coat film is preferably 1.5% or less, more preferably 0.9% or less, still more preferably 0.7% or less, and particularly preferably 0.5% or less.
  • the yellowness index (YI) of the hard coat film is preferably 10 or less, more preferably 8 or less, still more preferably 5 or less, even more preferably 4 or less, and particularly preferably 3 or less.
  • the hard coat film may have various functional layers. Examples of functional layers include antireflection layers, antiglare layers, antistatic layers, transparent electrodes, and the like.
  • a transparent pressure-sensitive adhesive layer may be attached to the surface of the transparent resin film 1 on which the hard coat layer is not formed. Moreover, a transparent pressure-sensitive adhesive layer may be attached to the hard coat film.
  • the above hard coat film has high hardness, it can be suitably used as a cover window material arranged on the outermost surface of the image display device. Since the hard coat film has excellent bending resistance, it can be suitably used as a cover window for a foldable display (foldable display). Applicable.
  • Table 1 shows the wet heat test results (methoxy group residual ratio) of the methoxysilane compounds
  • Table 2 shows the wet heat test test results (ethoxy group residual ratio) of the ethoxysilane compounds.
  • KBM-303 which is a silane compound in which a 3,4-epoxycyclohexyl group and a Si atom are bonded via an ethylene group (the number of atoms in the main chain is 2), has a methoxy group residual rate of 25%. Met.
  • silane compounds 1 to 5 in which a 3,4-epoxycyclohexyl group and a Si atom are bonded via a divalent organic group containing an ester bond and having a main chain of 5 to 10 atoms had a residual ratio of methoxy groups of 50% or more, and exhibited excellent moist heat resistance (storage stability).
  • silane compounds 1 to 5 the greater the number of atoms in the main chain of the divalent organic group between the 3,4-epoxycyclohexyl group and the Si atom, the higher the residual ratio of methoxy groups (improved heat and humidity resistance). A tendency was observed, and silane compounds 3 to 5 had a residual ratio of methoxy groups exceeding 80%.
  • T3585 which is a silane compound in which a 3,4-epoxycyclohexyl group and a Si atom are bonded via an ethylene group (the number of atoms in the main chain is 2), has a residual ethoxy group rate of 34%. rice field.
  • silane compounds 6 to 8 in which a 3,4-epoxycyclohexyl group and a Si atom are bonded via a divalent organic group containing an ester bond and having a main chain of 5 or more atoms are , the residual ratio of ethoxy groups was 50% or more, and excellent moist heat resistance (storage stability) was exhibited.
  • the percentage of residual methoxy groups and the percentage of residual epoxy groups calculated from the 1 H-NMR spectrum measured using 400 MHz-NMR manufactured by Bruker and using deuterated acetone as a solvent were 6.7% and 98%, respectively.
  • Polyorganosiloxane compound 5 had a residual methoxy group ratio of 4.1% and an epoxy group residual ratio of 91%.
  • Polyorganosiloxane compound 14 had a residual ratio of methoxy groups of 4.6% and a residual ratio of epoxy groups of 95% or more.
  • Polyorganosiloxane compound 15 had a residual ratio of methoxy groups of 4.3% and a residual ratio of epoxy groups of 95% or more.
  • TAHMBP 1,1′-biphenyl]-4,4′-diyl)ester
  • CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • ODPA 4,4′-oxydiphthalic dianhydride
  • Example 1 (Preparation of hard coat composition) Polyorganosiloxane compound 1 was diluted to 50% with propylene glycol monomethyl ether. With respect to 100 parts by weight of the polyorganosiloxane compound, 2 parts by weight of a propylene carbonate 50% solution of a photocationic polymerization initiator (manufactured by San-Apro "CPI-101A") as a solid content, a silicone leveling agent (manufactured by BYK “BYK- 300”) was blended as a solid content to obtain a hard coat composition.
  • a photocationic polymerization initiator manufactured by San-Apro "CPI-101A
  • a silicone leveling agent manufactured by BYK "BYK- 300
  • a solution obtained by diluting a fluorine-based coating agent (“OPTOOL UD509” manufactured by Daikin) with hydrofluoroether (“NOVEC7200” manufactured by 3M) to 0.1% by weight was applied onto the primer layer so that the dry film thickness was 10 nm. It was applied using a coater and heated at 150° C. for 10 minutes to form a topcoat layer to obtain a hardcoat film having a hardcoat layer and a topcoat layer on one side of the transparent polyimide film.
  • OPTOOL UD509 fluorine-based coating agent
  • NOVEC7200 hydrofluoroether
  • Examples 2 to 14 Comparative Examples 1 to 3> Polyorganosiloxane compounds 2 to 15 were used instead of polyorganosiloxane compound 1 in the preparation of the hard coat composition.
  • “CPI-310FG” manufactured by San-Apro Co., Ltd. was used as the cationic photopolymerization initiator.
  • the thickness of the hard coat layer was set to 20 ⁇ m.
  • a hard coat film having a hard coat layer, a primer layer and a top coat layer on one side of the transparent polyimide film was obtained in the same manner as in Example 1 except for these changes.
  • ⁇ Bending resistance (dynamic bending test)> A strip having a width of 25 mm was cut from the hard coat film. The short side of this test piece is attached to a U-shaped expansion test jig (manufactured by Yuasa System Equipment), and a planar body no-load U-shaped expansion test (manufactured by Yuasa System Equipment) is performed in an environment with a temperature of 23 ° C and a relative humidity of 55%. "DMLHB-FS-C”), a repeated bending test was performed with the hard coat layer forming surface facing outward under the conditions of a bending radius of 3.0 mm, a bending angle of 180°C, and a bending speed of 1 time/second.
  • DMLHB-FS-C a repeated bending test was performed with the hard coat layer forming surface facing outward under the conditions of a bending radius of 3.0 mm, a bending angle of 180°C, and a bending speed of 1 time/second.
  • the bending resistance was evaluated according to the following criteria based on the number of times of bending until the hard coat layer cracked (the number of times of bending resistance).
  • E 150,000 times or more and less than 200,000 times of bending resistance
  • F 100,000 times or more and less than 150,000 times of bending resistance
  • X bending endurance is less than 1,000 times
  • the hard coat film was cured at 25°C for 1 month, cut into 3 cm squares, and placed on a horizontal table with the concave surface of the hard coat film facing upward. The heights from the stand to the four corners of the film were measured, and the average value was taken as the amount of curl. The amount of curl when the hard coat layer-formed surface was facing upward and was concave was given a positive value.
  • Table 3 shows the composition of the hard coat layer (molar ratio of the silane compound used in synthesizing the polyorganosiloxane compound), the thickness of the hard coat layer, and the evaluation results of the hard coat films of Examples and Comparative Examples.
  • the hard coat film of Comparative Example 3, which contains polyorganosiloxane compound 15 (see Synthesis Example 23) obtained by condensation of KBM-4803, which is a silane compound having a glycidyloxy group, as a curable resin component has excellent bending resistance. However, the curl was large and the handleability was poor.
  • the hard coat films of Examples 1 to 14 had excellent bending resistance compared to Comparative Examples 1 and 2, and curling was suppressed compared to Comparative Example 3.
  • a hard coat film containing a polyorganosiloxane compound having a spacer with a specific chain length between the Si atom and the alicyclic epoxy group as a curable resin component has excellent scratch resistance and a hard coat. It can be seen that it is possible to achieve both bending resistance when bent outward, and that the curl is small and the handling is excellent.

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