Classifications

• • 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
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
• • 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
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
• • 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
  • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
• • 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

Definitions

• This disclosure relates to a method for producing a laminate with a hard coat layer.
• a hard coat layer may be formed using a hard coat agent.
• Multifunctional acrylates are widely used as hard coat agents.
• Patent Document 1 discloses a method for manufacturing an optical recording medium substrate by providing a guide groove and a preformat signal made of a curable resin on a glass substrate using the 2P method, characterized in that, before providing the guide groove and the preformat signal made of a curable resin on the glass substrate, the surface of the glass substrate is subjected to UV/O_3 cleaning and/or plasma cleaning, and then treated with a silane coupling agent.
• the objective of this disclosure is to provide a highly efficient method for producing a laminate with a hard coat layer that achieves high adhesion between the substrate and the hard coat layer even when the primer layer formation time is shortened.
• a method for producing a laminate with a hard coat layer comprising the steps of: A primer coating step of coating the substrate with a primer containing a silane coupling agent, an organic solvent, and water; a drying step of drying the primer to form the primer layer; a hard-coat agent application step of applying a hard-coat agent onto the primer layer; a curing step of curing the hard-coating agent to form a hard-coating layer; in that order,
• the content x (mass%) of the silane coupling agent relative to the primer is 1 ⁇ x ⁇ 15, a total content y (mass%) of the organic solvent and the water in the primer is 85 ⁇ y ⁇ 99; and a content ratio z of the organic solvent to the silane coupling agent (organic solvent/silane coupling agent) is z ⁇ 36, and a content ratio u of the organic solvent to the water (organic solvent/water) is 1/5 ⁇ u ⁇ 5/1 in mass ratio.
• a method for producing a laminate with a hard coat layer ⁇ 2> The method for producing a laminate with a hard coat layer according to ⁇ 1>, wherein the silane coupling agent is at least one selected from the group consisting of a silane coupling agent having an amino group, a silane coupling agent having a (meth)acryloyl group, and a silane coupling agent having a glycidyl group.
• the organic solvent is at least one selected from the group consisting of alcohol-based solvents, ketone-based solvents, ether-based solvents, and nitrile-based solvents.
• ⁇ 4> The method for producing a laminate with a hard coat layer according to any one of ⁇ 1> to ⁇ 3>, wherein a remaining mass ratio in a cross-cut peel test performed based on JIS K5600-5-6 by adhering the substrate and the hard coat layer is 60 to 100%.
• ⁇ 5> The method for producing a laminate with a hard coat layer according to any one of ⁇ 1> to ⁇ 4>, wherein the substrate is at least one selected from the group consisting of a glass substrate, a polyimide resin substrate, a thiourethane resin substrate, a polyamide resin substrate, a cyclopolyolefin resin substrate, and a polyolefin resin substrate.
• ⁇ 6> The method for producing a laminate with a hard coat layer according to any one of ⁇ 1> to ⁇ 5>, wherein the substrate is a glass substrate.
• ⁇ 7> The method for producing a laminate with a hard coat layer according to any one of ⁇ 1> to ⁇ 6>, further comprising a plasma treatment step of subjecting the substrate to a plasma treatment prior to the primer application step.
• ⁇ 8> The method for producing a laminate with a hard coat layer according to any one of ⁇ 1> to ⁇ 7>, wherein the drying step is carried out at a temperature of 50° C. to 150° C. for 1 minute to 20 minutes.
• ⁇ 9> The method for producing a laminate with a hard coat layer according to any one of ⁇ 1> to ⁇ 8>, wherein the hard coat agent contains a curable composition containing a silsesquioxane derivative.
• the present disclosure is not limited to the following embodiments.
• the components including element steps, etc.
• the numerical range indicated using “to” includes the numerical values before and after "to” as the minimum and maximum values, respectively.
• the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range.
• the upper or lower limit of the numerical range may be replaced with a value shown in the examples. Also, in this specification, a combination of two or more preferred aspects is a more preferred aspect.
• the method for producing a laminate with a hard coat layer is a method for producing a laminate with a hard coat layer, which comprises a substrate, a primer layer, and a hard coat layer in this order, and includes a primer coating step of coating a substrate with a primer containing a silane coupling agent, a drying step of drying the primer to form a primer layer, a hard coat agent coating step of coating a hard coat agent on the primer layer, and a curing step of curing the hard coat agent to form a hard coat layer, in this order.
• the amount of the primer component is set within a predetermined range.
• the method for producing a laminate with a hard coat layer according to the present disclosure, even if the time for forming the primer layer is shortened, the adhesion between the substrate and the hard coat layer is high, resulting in a highly efficient method for producing a laminate with a hard coat layer. This is because the use of a primer having this composition is believed to promote the hydrolysis reaction of the run coupling agent in the primer as well as condensation with the substrate surface.
• Primer application process In the primer application step, a primer is applied to the substrate.
• the primer contains a silane coupling agent, an organic solvent and water.
• silane coupling agent examples include silane coupling agents having a silicon atom in one molecule and having an alkoxy group and an organic functional group (functional groups such as a vinyl group, an epoxy group, a methacryloyl group, an acryloyl group, an amino group, etc.).
• silane coupling agent from the viewpoint of increasing the hardness of the hard coat layer, a silane coupling agent having two or more functionalities is preferable.
• silane coupling agent at least one selected from the group consisting of a silane coupling agent having an amino group, a silane coupling agent having a (meth)acryloyl group, and a silane coupling agent having a glycidyl group is preferable.
• silane coupling agent examples include -aminopropyltrimethoxysilane, ⁇ -methacryloyloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, ⁇ -acryloyloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyltriethoxysilane, ⁇ -methacryloyloxypropyltriethoxysilane, and ⁇ -acryloyloxypropyltriethoxysilane.
• the organic solvent may be a water-soluble solvent that dissolves the silane coupling agent.
• the organic solvent from the viewpoint of liquid stability and drying property, at least one selected from the group consisting of alcohol-based solvents, ketone-based solvents, ether-based solvents, and nitrile-based solvents is preferable.
• Specific examples of the organic solvent include methanol, ethanol, acetone, propylene glycol monomethyl ether, tetrahydrofuran, acetonitrile, 2-propanol, methyl isobutyl ketone, and methyl ethyl ketone.
• water examples include distilled water, ion-exchanged water, ultrafiltered water, and pure water.
• the amount of each component in the primer is set to the following range from the viewpoint of increasing the adhesion between the substrate and the hard coat layer even if the time for forming the primer layer is shortened.
• the content x (mass %) of the silane coupling agent relative to 100 mass % of the primer is preferably 1 ⁇ x ⁇ 15, more preferably 2 ⁇ x ⁇ 11, and further preferably 2.2 ⁇ x ⁇ 11.
• the total content y (mass %) of the organic solvent and water in the primer is preferably 85 ⁇ y ⁇ 99, more preferably 89 ⁇ y ⁇ 98, and even more preferably 89 ⁇ y ⁇ 97.8.
• the content ratio z (mass %) of the organic solvent relative to the primer is preferably z ⁇ 36, more preferably z ⁇ 35, and further preferably z ⁇ 30.
• the content ratio u of the organic solvent to water (organic solvent/water) is preferably 1/5 ⁇ u ⁇ 5/1, more preferably 1/4 ⁇ u ⁇ 5/1, and further preferably 1/3 ⁇ u ⁇ 5/1, in terms of mass ratio.
• the primer can be applied by any of the well-known application methods (such as a bar coater method, a Mayer bar coater method, an applicator method, a doctor blade method, a roll coater method, a die coater method, a comma coater method, a gravure coat method, a microgravure coat method, a roll brush method, a spray coat method, an air knife coat method, an impregnation method, a curtain coat method, and an inkjet method).
• a bar coater method such as a bar coater method, a Mayer bar coater method, an applicator method, a doctor blade method, a roll coater method, a die coater method, a comma coater method, a gravure coat method, a microgravure coat method, a roll brush method, a spray coat method, an air knife coat method, an impregnation method, a curtain coat method, and an inkjet method.
• the substrate is not particularly limited, and examples thereof include substrates made of wood, metal, inorganic materials, plastics, paper, fibers, fabrics, and the like.
• metals include copper, silver, iron, aluminum, silicon, silicon steel, stainless steel, etc.
• inorganic materials include metal oxides such as aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, zinc oxide, indium tin oxide, and gallium oxide, metal nitrides such as aluminum nitride, gallium nitride, and silicon nitride, ceramics such as silicon carbide and boron nitride, mortar, concrete, and glass, etc.
• plastics include acrylic resins such as polymethyl methacrylate, polyester resins such as polyethylene terephthalate, polyvinyl chloride resins, polycarbonate resins, epoxy resins, polyamide resins such as nylon and aramid, fluororesins such as polyimide resins, polyamideimide resins, and tetrafluoroethylene resins, polyolefin resins such as cross-linked polyethylene resins, vinylidene chloride resins, acrylonitrile-butadiene-styrene (ABS) resins, polystyrene resins, polyacrylonitrile resins, cycloolefin polymers (COP), cycloolefin copolymers (COC), acetate resins, polyarylates, cellophane, norbornene resins, acetylcellulose resins such as triacetylcellulose (TAC), composite resins such as polychloroprene, polyphenylene sulfide, polys, poly
• the fibers include natural fibers, regenerated fibers, semi-synthetic fibers, metal fibers, glass fibers, carbon fibers, ceramic fibers, and known chemical fibers.
• the fabric may be a woven fabric or a nonwoven fabric, and can be produced, for example, using the above-mentioned fibers. These materials may be used alone, or two or more of them may be used in combination, mixture, or composite.
• At least one selected from the group consisting of glass substrates, polyimide resin substrates, thiourethane resin substrates, polyamide resin substrates, cyclopolyolefin resin substrates, and polyolefin resin substrates is preferred, with glass substrates being preferred.
• adhesion between a glass substrate and a hard coat layer formed from a hard coat agent containing a silsesquioxane derivative tends to be low.
• a primer layer between the glass substrate and the hard coat layer adhesion between the glass substrate and the hard coat layer is increased even when a hard coat layer is provided on the glass substrate.
• the shape of the substrate is not particularly limited, and examples include plate-like, sheet-like, film-like, rod-like, spherical, fibrous, powder-like, lenticular, and other regular or irregular shapes.
• a plasma treatment step of subjecting the substrate to plasma treatment may be included prior to the primer application step.
• the substrate surface is cleaned and hydrophilized. This further enhances the adhesion between the substrate and the hard coat layer due to the primer layer, making it easier to increase the hardness of the hard coat layer.
• the plasma treatment may be performed under known conditions (vacuum plasma treatment, atmospheric pressure plasma treatment, etc.).
• the plasma treatment includes corona discharge treatment, glow discharge treatment, and arc discharge treatment.
• the primer is dried to form a primer layer.
• the drying step for example, from the viewpoint of shortening the time required for forming the primer layer while suppressing a decrease in adhesion between the substrate and the hard coat layer, it is preferable to dry the primer at a temperature of 50° C. to 150° C. for 1 minute to 20 minutes.
• the thickness of the primer layer is preferably 0.01 to 10 ⁇ m, and more preferably 0.05 to 1 ⁇ m.
• a hard-coat agent is applied onto the primer layer.
• the hard coat agent contains, for example, a curable composition containing a polymerizable compound. If necessary, it may contain various components (hereinafter, also referred to as "other components").
• polymerizable compound examples include silsesquioxane derivatives, (meth)acrylate compounds, compounds having an ethylenically unsaturated group, epoxy compounds (compounds having an epoxy group), compounds having an oxetanyl group (oxetanyl group-containing compounds), and compounds having a vinyl ether group (vinyl ether compounds).
• silsesquioxane derivatives are more preferable from the viewpoints of heat resistance, weather resistance, and hardness.
• silsesquioxane Derivatives examples include well-known silsesquioxane derivatives (for example, silsesquioxane derivatives having a T unit having three O 1/2 per silicon atom).
• the silsesquioxane derivative may be a silsesquioxane derivative having, in addition to the T unit, at least one unit selected from the group consisting of an M unit having one O 1/2 per silicon atom, a D unit having two O 1/2 per silicon atom, and a Q unit having four O 1/2 (two oxygen atoms) per silicon atom.
• the silsesquioxane derivative is preferably a silsesquioxane derivative having a reactive group (such as a glycidyl group, an oxetanyl group, or a (meth)acryloyl group).
• a reactive group such as a glycidyl group, an oxetanyl group, or a (meth)acryloyl group.
• the silsesquioxane derivative represented by the following formula (1) or formula (2) is preferred.
• R 1 and R 2 each independently represent an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or an aralkylene group having 7 to 12 carbon atoms;
• R 3 is an alkyl group having 1 to 6 carbon atoms;
• R 4 and R 5 each independently represent a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms;
• R 6 is an organic group having 2 to 12 carbon atoms having at least one of an ethylenically unsaturated bond and a carbon-carbon triple bond;
• R 7 and R 8 each independently represent an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to
• R 1 to R 8 in formula (1) may each independently be partially substituted with a substituent or a halogen atom.
• R 1 to R 8 may each independently be partially substituted with an alkyl group, an aryl group, an aralkyl group, a vinyl group, an epoxy group, an oxetanyl group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an ammonium group, a thiol group, an isocyanurate group, a ureido group, an isocyanate group, a carboxy group, an acid anhydride group, or a halogen atom.
• R 1 to R 8 may each independently be unsubstituted.
• R 1 to R 3 or R 6 to R 8 (preferably R 1 to R 3 and R 6 to R 8 ) may be unsubstituted.
• structural units that the silsesquioxane derivative of formula (1) may contain are referred to as structural units (a) to (g) as follows.
• the silsesquioxane derivative of formula (1) contains at least one of the structural units (b) and (c) among the structural units (a) to (g) described above, and optionally contains at least one of the structural units (a), (d), (e), (f), and (g).
• t, u, v, w, x, y, and z represent the molar ratio of the structural units (a) to (g).
• t, u, v, w, x, y, and z represent the relative molar ratio of the structural units (a) to (g) that the silsesquioxane derivative represented by formula (1) may contain.
• the molar ratio can be determined from the NMR (nuclear magnetic resonance) analysis value of the silsesquioxane derivative represented by formula (1).
• the reaction rate of each raw material of the silsesquioxane derivative is clear or the yield is 100%, it can be determined from the amount of the raw material charged.
• the molar ratio of each of the structural units of a silsesquioxane derivative may be calculated by subjecting a sample dissolved in deuterated chloroform or the like to 1 H-NMR analysis, and, if necessary, further subjecting the sample to 29 Si-NMR analysis.
• the structure of the original silsesquioxane derivative may be estimated from the ratio of the constituent units by decomposing the compound into constituent units using an alkali or the like.
• the molar ratio of each of the structural units of the silsesquioxane derivative may be determined by a combination of known techniques such as mass spectrometry and IR (infrared absorption spectroscopy) analysis.
• Each of the structural units (b) to (g) in formula (1) may be of only one type, or may be of two or more types.
• the order of arrangement in formula (1) indicates the composition of the structural units, and does not mean the order of arrangement of the silsesquioxane derivative. Therefore, the condensation form of the structural units in the silsesquioxane derivative of formula (1) does not necessarily have to be the order of arrangement in formula (1).
• the structural units (a) to (g) will be described in detail below.
• the structural unit (a) is a Q unit having four O 1/2 's (two oxygen atoms) per silicon atom.
• the Q unit means a unit having four O 1/2 's per silicon atom.
• the proportion of the structural unit (a) in the silsesquioxane derivative of formula (1) is not particularly limited.
• the molar ratio (t/(t+u+v+w+x+y+z)) of the structural unit (a) to all structural units is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0, from the viewpoint of the viscosity of the silsesquioxane derivative and the hardness of the hard coat layer.
• a molar ratio of 0 means that the corresponding structural unit is not contained, and the same applies below.
• the structural unit (b) is a T unit having three O 1/2 (1.5 oxygen atoms) per silicon atom, and an acryloyloxy group bonded to the silicon atom via R 1.
• the T unit means a unit having three O 1/2 per silicon atom.
• R 1 is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or an aralkylene group having 7 to 12 carbon atoms.
• R 1 is preferably an alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms, and more preferably an alkylene group having 1 to 10 carbon atoms.
• the alkylene group having 1 to 10 carbon atoms is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and even more preferably a propylene group.
• the alkylene group having 1 to 10 carbon atoms may be linear or branched.
• the cycloalkylene group having 3 to 10 carbon atoms is preferably a cycloalkylene group having 3 to 6 carbon atoms, and more preferably a cycloalkylene group having 4 to 6 carbon atoms.
• the cycloalkylene group having 3 to 10 carbon atoms may be branched.
• the ratio of the structural unit (b) in the silsesquioxane derivative of formula (1) is not particularly limited.
• the molar ratio (u/(t+u+v+w+x+y+z)) of the structural unit (b) in all structural units is preferably 0.2 to 0.99, more preferably 0.3 to 0.9, even more preferably 0.3 to 0.7, and particularly preferably 0.45 to 0.65, from the viewpoints of the hardness of the hard coat layer, the cure shrinkage rate of the silsesquioxane derivative, storage stability, and UV curability.
• the molar ratio of the structural unit (b) to all structural units may be 0.
• u>v is satisfied, and it is more preferable that the molar ratio of structural unit (b) (u/(t+u+v+w+x+y+z))>the molar ratio of structural unit (c) (v/(t+u+v+w+x+y+z)))+0.05 is satisfied, and it is particularly preferable that the molar ratio of structural unit (b) (u/(t+u+v+w+x+y+z))>the molar ratio of structural unit (c) (v/(t+u+v+w+x+y+z)))+0.10 is satisfied.
• the structural unit (c) is a T unit which has three O 1/2 (1.5 oxygen atoms) per silicon atom and in which an acryloyloxy group (such as a methacryloyloxy group) in which a hydrogen atom has been substituted with R 3 is bonded to the silicon atom via R 2 .
• R2 is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or an aralkylene group having 7 to 12 carbon atoms. Preferred aspects of R2 are the same as those of R1 in the structural unit (b).
• R3 is an alkyl group having 1 to 6 carbon atoms.
• alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, with a methyl group and an ethyl group being preferred, and a methyl group being more preferred.
• the ratio of the structural unit (c) in the silsesquioxane derivative of formula (1) is not particularly limited.
• the molar ratio (v/(t+u+v+w+x+y+z)) of the structural unit (c) in all structural units is preferably 0 to 0.8, more preferably 0.05 to 0.7, even more preferably 0.2 to 0.7, and particularly preferably 0.35 to 0.55, from the viewpoints of the hardness of the hard coat layer, the cure shrinkage rate of the silsesquioxane derivative, storage stability, and UV curability.
• the molar ratio of the structural unit (c) to all structural units may be 0.
• At least one of u and v is a positive number, and from the viewpoint of the hardness of the hard coat layer, it is preferable that u and v are each independently a positive number.
• the total molar ratio ((u+v)/(t+u+v+w+x+y+z)) of the structural units (b) and (c) to all structural units is preferably 0.3 to 1, more preferably 0.5 to 1, even more preferably 0.7 to 1, and particularly preferably 0.9 to 1, from the viewpoints of the hardness of the hard coat layer as well as the cure shrinkage rate, storage stability, UV curability, and viscosity of the silsesquioxane derivative.
• the structural unit (d) is a T unit having three O 1/2 (1.5 oxygen atoms) per silicon atom, and R 4 is bonded to the silicon atom.
• R4 is a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
• the saturated or unsaturated alkyl group having 1 to 20 carbon atoms may be linear or branched.
• the saturated or unsaturated alkyl group having 1 to 20 carbon atoms is preferably a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, and more preferably a saturated alkyl group having 1 to 10 carbon atoms.
• saturated alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. From the viewpoint of the heat resistance and hardness of the hard coat layer, methyl or ethyl groups are preferred, and methyl groups are more preferred.
• Examples of unsaturated alkyl groups having 1 to 10 carbon atoms include vinyl groups, 2-propenyl groups, and ethynyl groups.
• the saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms may be branched.
• the saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms is preferably a saturated or unsaturated cycloalkyl group having 4 to 6 carbon atoms.
• the aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms.
• aryl groups having 6 to 20 carbon atoms include phenyl groups, groups in which one or more hydrogen atoms of a phenyl group are substituted with an alkyl group having 1 to 10 carbon atoms, and naphthyl groups. From the viewpoint of the heat resistance and hardness of the hard coat layer, phenyl groups are preferred.
• the aralkyl group having 7 to 20 carbon atoms is preferably an aralkyl group having 7 to 10 carbon atoms.
• Examples of aralkyl groups having 7 to 20 carbon atoms include groups in which one hydrogen atom of an alkyl group having 1 to 10 carbon atoms is substituted with an aryl group such as a phenyl group.
• Examples include benzyl groups and phenethyl groups, and from the viewpoint of the heat resistance and hardness of the hard coat layer, benzyl groups are preferred.
• examples of R4 include a 3-glycidoxypropyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, a 3-(3-ethyloxetan-3-yl)methoxypropyl group, a 3-hydroxypropyl group, a 3-aminopropyl group, a 3-dimethylaminopropyl group, a 3-hydroxypropyl group, a 3-aminopropyl hydrochloride, a 3-dimethylaminopropyl hydrochloride, a p-styryl group, an N-2-(aminoethyl)-3-aminopropyl group, an N-phenyl-3-aminopropyl group, an N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl hydrochloride, a 3-ure
• the ratio of the structural unit (d) in the silsesquioxane derivative of formula (1) is not particularly limited.
• the molar ratio of the structural unit (d) to all structural units (w/(t+u+v+w+x+y+z)) is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0, from the viewpoint of the hardness of the hard coat layer.
• the structural unit (e) is a D unit having two O 1/2 (one oxygen atom) per silicon atom and two R 5 bonded to the silicon atom.
• the D unit means a unit having two O 1/2 per silicon atom.
• R5 is a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
• multiple R5s may be the same or different.
• the preferred embodiments of R5 are the same as R4 in the structural unit (d).
• the proportion of the structural unit (e) in the silsesquioxane derivative of formula (1) is not particularly limited.
• the molar ratio of the structural unit (e) to all structural units (x/(t+u+v+w+x+y+z)) is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0, from the viewpoint of the hardness of the hard coat layer.
• x is preferably a positive number.
• the structural unit (f) is an M unit having one O 1/2 (0.5 oxygen atoms) per silicon atom, and one R 6 and two R 5 bonded to the silicon atom.
• the M unit means a unit having one O 1/2 per silicon atom.
• R 6 is an organic group having 2 to 12 carbon atoms and at least one of an ethylenically unsaturated bond and a carbon-carbon triple bond.
• organic groups having 2 to 12 carbon atoms and an ethylenically unsaturated bond include vinyl groups, orthostyryl groups, methstyryl groups, parastyryl groups, acryloyloxymethyl groups, methacryloyloxymethyl groups, 2-acryloyloxyethyl groups, 2-methacryloyloxyethyl groups, 3-acryloyloxypropyl groups, 3-methacryloyloxypropyl groups, 8-acryloyloxyoctyl groups, 8-methacryloyloxyoctyl groups, and 8-methacryloyloxyoctyl groups.
• alkyl group examples include octyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 3-butenyl, 1-pentenyl, 4-pentenyl, 3-methyl-1-butenyl, 1-phenylethenyl, 2-phenylethenyl, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 3-butynyl, 1-pentynyl, 4-pentynyl, 3-methyl-1-butynyl, and phenylbutynyl.
• vinyl, 2-propenyl, orthostyryl, metastyryl, and parastyryl groups are preferred, and vinyl groups are more preferred.
• R 7 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. In the structural unit (f), multiple R 7s may be the same or different.
• alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. From the viewpoint of the heat resistance and hardness of the hard coat layer, methyl or ethyl groups are preferred, and methyl groups are more preferred.
• aryl groups having 6 to 10 carbon atoms include phenyl groups, groups in which one or more hydrogen atoms of a phenyl group are substituted with an alkyl group having 1 to 4 carbon atoms, and naphthyl groups. From the viewpoint of the heat resistance and hardness of the hard coat layer, phenyl groups are preferred.
• Examples of aralkyl groups having 7 to 10 carbon atoms include groups in which one hydrogen atom of an alkyl group having 1 to 4 carbon atoms is substituted with an aryl group such as a phenyl group.
• Examples include benzyl groups and phenethyl groups, and from the viewpoint of the heat resistance and hardness of the hard coat layer, benzyl groups are preferred.
• the ratio of the structural unit (f) in the silsesquioxane derivative of formula (1) is not particularly limited.
• the molar ratio of the structural unit (f) to all structural units (y/(t+u+v+w+x+y+z)) is preferably 0.5 or less, more preferably 0.3 or less, and even more preferably 0.1 or less, from the viewpoints of the hardness of the hard coat layer as well as the cure shrinkage rate, storage stability, and UV curability of the silsesquioxane derivative.
• the structural unit (g) is an M unit having one O 1/2 (0.5 oxygen atoms) per silicon atom and having three R 8s bonded to the silicon atom.
• R8 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. In the structural unit (g), multiple R8s may be the same or different. Preferred aspects of R8 are the same as R7 in the structural unit (f).
• the proportion of the structural unit (g) in the silsesquioxane derivative of formula (1) is not particularly limited.
• the molar ratio of the structural unit (g) to all structural units (z/(t+u+v+w+x+y+z)) is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0, from the viewpoint of the hardness of the hard coat layer.
• the silsesquioxane derivative of formula (1) may further contain (R 9 O 1/2 ) as a structural unit not containing Si (hereinafter, also referred to as structural unit (h)).
• R9 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• the alkyl group having 1 to 6 carbon atoms may be either an aliphatic group or an alicyclic group, and may be either linear or branched. Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
• the structural unit (h) is an alkoxy group, which is a hydrolyzable group contained in the silicon compound described below, or an alkoxy group formed by the substitution of an alcohol contained in the reaction solvent for a hydrolyzable group in the silicon compound, and may be one that remains in the molecule without being hydrolyzed or polycondensed, or may be a hydroxyl group that remains in the molecule after hydrolysis without being polycondensed.
• t, x, and z are 0, and w and y are each independently 0 or a positive number, and it is more preferable that t, w, x, y, and z are 0.
• formula (1) from the viewpoints of the hardness of the hard coat layer as well as the cure shrinkage rate, storage stability, and UV curability of the silsesquioxane derivative, it is preferable that 0 ⁇ y/(u+v+w) ⁇ 0.5 is satisfied, it is more preferable that 0 ⁇ y/(u+v+w) ⁇ 0.3 is satisfied, and it is even more preferable that 0 ⁇ y/(u+v+w) ⁇ 0.1 is satisfied.
• u and v are each independently a positive number.
• u and v satisfy 0 ⁇ v/u ⁇ 1, more preferably 0.1 ⁇ v/u ⁇ 1, even more preferably 0.2 ⁇ v/u ⁇ 1, and particularly preferably 0.3 ⁇ v/u ⁇ 1.
• R CE is each independently a group having a cyclic ether structure
• R 21 is each independently an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or an aralkylene group having 7 to 12 carbon atoms
• R 22 and R 23 are each independently a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms
• R 24 is each independently an organic group having 2 to 12 carbon atoms and a cyclic ether structure
• R 25 and R 26 are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atom
• R CE and R 21 to R 26 may each independently be partially substituted with a substituent or a halogen atom.
• R CE and R 21 to R 26 may each independently be partially substituted with an alkyl group, an aryl group, an aralkyl group, a vinyl group, an epoxy group, an oxetanyl group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an ammonium group, a thiol group, an isocyanurate group, a ureido group, an isocyanate group, a carboxy group, an acid anhydride group, or a halogen atom.
• R 21 to R 26 may each independently be unsubstituted.
• R CE , R 21 or R 24 to R 26 (preferably R 1 and R 24 to R 26 ) may be unsubstituted.
• structural units that the silsesquioxane derivative of formula (2) may contain are referred to as structural units (2a) to (2f) as follows.
• the silsesquioxane derivative of formula (2) contains the structural unit (2b) of the structural units (2a) to (2f) described above, and optionally contains at least one of the structural units (2a), (2c), (2d), (2e), and (2f).
• u, v, w, x, y, and z represent the molar ratio of the structural units (2a) to (2f).
• u, v, w, x, y, and z represent the relative molar ratio of the structural units (2a) to (2f) that the silsesquioxane derivative represented by formula (2) may contain.
• the molar ratio can be determined from the NMR (nuclear magnetic resonance) analysis value of the silsesquioxane derivative of formula (2).
• the reaction rate of each raw material of the silsesquioxane derivative is clear or the yield is 100%, it can be determined from the amount of the raw material charged.
• the molar ratio of each of the structural units of a silsesquioxane derivative may be calculated by subjecting a sample dissolved in deuterated chloroform or the like to 1 H-NMR analysis, and, if necessary, further subjecting the sample to 29 Si-NMR analysis.
• the structure of the original silsesquioxane derivative may be estimated from the ratio of the constituent units by decomposing the compound into constituent units using an alkali or the like.
• the molar ratio of each of the structural units of the silsesquioxane derivative may be determined by a combination of known techniques such as mass spectrometry and IR (infrared absorption spectroscopy) analysis.
• Each of the structural units (2b) to (2f) in formula (2) may be of only one type, or may be of two or more types.
• the order of arrangement in formula (2) indicates the composition of the structural units, and does not mean the order of arrangement of the silsesquioxane derivative. Therefore, the condensation form of the structural units in the silsesquioxane derivative of formula (2) does not necessarily have to be the order of arrangement in formula (2).
• the structural units (2a) to (2f) will be described in detail below.
• the structural unit (2a) is a Q unit having four O 1/2 's (two oxygen atoms) per silicon atom. Note that the Q unit refers to a unit having four O 1/2 's per silicon atom.
• the proportion of the structural unit (2a) in the silsesquioxane derivative of formula (2) is not particularly limited.
• the molar ratio (u/(u+v+w+x+y+z)) of the structural unit (2a) to all structural units is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0, from the viewpoint of the viscosity of the silsesquioxane derivative and the hardness of the hard coat layer.
• a molar ratio of 0 means that the corresponding structural unit is not contained, and the same applies below.
• the structural unit (2b) is a T unit having three O 1/2 (1.5 oxygen atoms) per silicon atom, and a group having a cyclic ether structure bonded to the silicon atom via R 21.
• the T unit refers to a unit having three O 1/2 per silicon atom.
• R and C are each preferably a group having an oxetane structure and/or a group having an epoxy structure, and more preferably a group having an oxetane structure.
• R CE is each independently a group bonded to R 21 via an oxygen atom.
• R CE may have only one cyclic ether structure or two or more cyclic ether structures. From the viewpoint of the hardness of the hard coat layer as well as the cure shrinkage rate of the silsesquioxane derivative, however, it is preferable that R CE have only one cyclic ether structure. Specific examples of R CE include a 3-ethyl-3-oxetanylmethoxy group, a glycidyloxy group, a 3-methyl-3-oxetanylmethoxy group, and a 3-oxetanylmethoxy group.
• R 21 is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or an aralkylene group having 7 to 12 carbon atoms.
• R 21 is preferably an alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms, and more preferably an alkylene group having 1 to 10 carbon atoms.
• the alkylene group having 1 to 10 carbon atoms is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and even more preferably a propylene group.
• the alkylene group having 1 to 10 carbon atoms may be linear or branched.
• the cycloalkylene group having 3 to 10 carbon atoms is preferably a cycloalkylene group having 3 to 6 carbon atoms, and more preferably a cycloalkylene group having 4 to 6 carbon atoms.
• the cycloalkylene group having 3 to 10 carbon atoms may be branched.
• the ratio of the structural unit (2b) in the silsesquioxane derivative of formula (2) is not particularly limited.
• the molar ratio of the structural unit (2b) to all structural units (v/(u+v+w+x+y+z)) is preferably 0.3 to 1, more preferably 0.5 to 1, even more preferably 0.7 to 1, and particularly preferably 0.9 to 1, from the viewpoints of the hardness of the hard coat layer as well as the cure shrinkage rate, storage stability, and UV curability of the silsesquioxane derivative.
• the structural unit (2c) is a T unit having 3 O 1/2 (1.5 oxygen atoms) per silicon atom, and R 22 bonded to the silicon atom.
• R 22 is a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
• the saturated or unsaturated alkyl group having 1 to 20 carbon atoms may be linear or branched.
• the saturated or unsaturated alkyl group having 1 to 20 carbon atoms is preferably a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, and more preferably a saturated alkyl group having 1 to 10 carbon atoms.
• saturated alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. From the viewpoint of the heat resistance and hardness of the hard coat layer, methyl or ethyl groups are preferred, and methyl groups are more preferred.
• Examples of unsaturated alkyl groups having 1 to 10 carbon atoms include vinyl groups, 2-propenyl groups, and ethynyl groups.
• the saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms may be branched.
• the saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms is preferably a saturated or unsaturated cycloalkyl group having 4 to 6 carbon atoms.
• the aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms.
• aryl groups having 6 to 20 carbon atoms include phenyl groups, groups in which one or more hydrogen atoms of a phenyl group are substituted with an alkyl group having 1 to 10 carbon atoms, and naphthyl groups. From the viewpoint of the heat resistance and hardness of the hard coat layer, phenyl groups are preferred.
• the aralkyl group having 7 to 20 carbon atoms is preferably an aralkyl group having 7 to 10 carbon atoms.
• Examples of aralkyl groups having 7 to 20 carbon atoms include groups in which one hydrogen atom of an alkyl group having 1 to 10 carbon atoms is substituted with an aryl group such as a phenyl group.
• Examples include benzyl groups and phenethyl groups, and from the viewpoint of the heat resistance and hardness of the hard coat layer, benzyl groups are preferred.
• examples of R 22 include a 3-glycidoxypropyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, a 3-(3-ethyloxetan-3-yl)methoxypropyl group, a 3-hydroxypropyl group, a 3-aminopropyl group, a 3-dimethylaminopropyl group, a 3-hydroxypropyl group, a 3-aminopropyl hydrochloride, a 3-dimethylaminopropyl hydrochloride, a p-styryl group, an N-2-(aminoethyl)-3-aminopropyl group, an N-phenyl-3-aminopropyl group, an N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl hydrochloride, a 3-ure
• the ratio of the structural unit (2c) in the silsesquioxane derivative of formula (2) is not particularly limited.
• the molar ratio of the structural unit (2c) to all structural units (w/(u+v+w+x+y+z)) is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0, from the viewpoint of the hardness of the hard coat layer.
• the structural unit (2d) is a D unit having two O 1/2 (one oxygen atom) per silicon atom, and two R 23 bonded to the silicon atom.
• the D unit means a unit having two O 1/2 per silicon atom.
• R 23 is a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
• multiple R 23s may be the same or different.
• Preferred aspects of R 23 are the same as R 22 in the structural unit (2c).
• the proportion of the structural unit (2d) in the silsesquioxane derivative of formula (2) is not particularly limited.
• the molar ratio (x/(u+v+w+x+y+z)) of the structural unit (2d) in all structural units is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0, from the viewpoint of the hardness of the hard coat layer.
• x is preferably a positive number.
• the structural unit (2e) is an M unit having one O 1/2 (0.5 oxygen atoms) per silicon atom, and one R 24 and two R 25 bonded to the silicon atom.
• the M unit means a unit having one O 1/2 per silicon atom.
• each R 24 is independently an organic group having a cyclic ether structure and having 2 to 12 carbon atoms. It is preferable that R 24 is R CE -R 21 - in the structural unit (2b). In addition, preferred embodiments are the same as the preferred embodiments of R CE and R 21 in the structural unit (2b).
• R 25 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. In the structural unit (2e), multiple R 25s may be the same or different.
• alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. From the viewpoint of the heat resistance and hardness of the hard coat layer, methyl or ethyl groups are preferred, and methyl groups are more preferred.
• aryl groups having 6 to 10 carbon atoms include phenyl groups, groups in which one or more hydrogen atoms of a phenyl group are substituted with an alkyl group having 1 to 4 carbon atoms, and naphthyl groups. From the viewpoint of the heat resistance and hardness of the hard coat layer, phenyl groups are preferred.
• Examples of aralkyl groups having 7 to 10 carbon atoms include groups in which one hydrogen atom of an alkyl group having 1 to 4 carbon atoms is substituted with an aryl group such as a phenyl group.
• Examples include benzyl groups and phenethyl groups, and from the viewpoint of the heat resistance and hardness of the hard coat layer, benzyl groups are preferred.
• the ratio of the structural unit (2e) in the silsesquioxane derivative of formula (2) is not particularly limited.
• the molar ratio (y/(u+v+w+x+y+z)) of the structural unit (2e) to all structural units is preferably 0.5 or less, more preferably 0.3 or less, and even more preferably 0.1 or less, from the viewpoints of the hardness of the hard coat layer as well as the cure shrinkage rate, storage stability, and UV curability of the silsesquioxane derivative.
• the structural unit (2f) is an M unit having one O 1/2 (0.5 oxygen atoms) per silicon atom and three R 26s bonded to the silicon atom.
• R 26 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. In the structural unit (2f), multiple R 26s may be the same or different. Preferred aspects of R 26 are the same as R 25 in the structural unit (2e).
• the ratio of the structural unit (2f) in the silsesquioxane derivative of formula (2) is not particularly limited.
• the molar ratio of the structural unit (2f) to all structural units (z/(u+v+w+x+y+z)) is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0, from the viewpoint of the hardness of the hard coat layer.
• the silsesquioxane derivative of formula (2) may further contain (R 7 O 1/2 ) as a structural unit not containing Si (hereinafter, also referred to as structural unit (g)).
• R7 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• the alkyl group having 1 to 6 carbon atoms may be either an aliphatic group or an alicyclic group, and may be either linear or branched. Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
• the structural unit (g) is an alkoxy group, which is a hydrolyzable group contained in the silicon compound described below, or an alkoxy group formed by the substitution of an alcohol contained in the reaction solvent for a hydrolyzable group in the silicon compound, and may be one that remains in the molecule without being hydrolyzed or polycondensed, or may be a hydroxyl group that remains in the molecule after hydrolysis without being polycondensed.
• u, y, and z are 0, and w and x are each independently 0 or a positive number, and it is more preferable that u, w, x, y, and z are 0.
• the weight average molecular weight (hereinafter also referred to as "Mw") of the silsesquioxane derivative is not particularly limited, and may be, for example, 300 to 30,000, 500 to 15,000, 700 to 10,000, or 1,000 to 5,000.
• the weight average molecular weight (Mw) of the silsesquioxane derivative refers to a value obtained by converting the molecular weight measured by GPC (gel permeation chromatography) using polystyrene as a standard substance.
• the weight average molecular weight (Mw) of the silsesquioxane derivative was measured as follows: Specifically, separation was performed by gel permeation chromatography (HLC-8320GPC, manufactured by Tosoh Corporation, hereinafter abbreviated as "GPC") in a tetrahydrofuran solvent at 40°C using a GPC column "TSK gel SuperMultiporeHZ-M” (manufactured by Tosoh Corporation), and the molecular weight in terms of standard polystyrene was calculated from the retention time.
• GPC gel permeation chromatography
• the viscosity of the silsesquioxane derivative at 25°C is preferably 10 mPa ⁇ s to 50,000 mPa ⁇ s, more preferably 100 mPa ⁇ s to 40,000 mPa ⁇ s, even more preferably 1,000 mPa ⁇ s to 30,000 mPa ⁇ s, and particularly preferably 2,000 mPa ⁇ s to 20,000 mPa ⁇ s.
• the viscosity at 25° C. refers to a value measured using an E-type viscometer (a cone-plate type viscometer, for example, TVE22H type viscometer manufactured by Toki Sangyo Co., Ltd.).
• the silsesquioxane derivative can be produced by a known method.
• a method for producing a silsesquioxane derivative is disclosed in detail in International Publication WO 2013/031798 and the like as a method for producing a polysiloxane.
• R n SiX p represents an integer of 0 to 3
• p represents an integer of 1 to 4
• n+P 4
• R represents a group bonded to a silicon atom in the silsesquioxane derivative via a carbon atom
• X represents a hydrolyzable group
• preferred examples of R include groups bonded to the silicon atom in the silsesquioxane derivative of formula (1) via a carbon atom (H 2 C ⁇ CHCOO—R 1 —, H 2 C ⁇ C(R 3 )COO—R 2 —, R 4 to R 8 , etc.).
• preferred examples of X include groups bonded to the silicon atom in the silsesquioxane derivative of formula (2) via a carbon atom (such as R CE -R 21 - and R 22 to R 26 ).
• Preferred examples of X include an alkoxy group, a silyloxy group, or a halogen atom, and more preferred examples of X are an alkoxy group or a silyloxy group.
• the hydrolysis step it is preferable to carry out not only hydrolysis of the organosilicon compound but also hydrolysis and polycondensation reaction of the organosilicon compound and, if necessary, other silicon compounds.
• the organosilicon compound and, if necessary, other silicon compounds may be subjected to hydrolysis and polycondensation reactions to obtain a silsesquioxane derivative as an intermediate product, and then the obtained intermediate product may be further subjected to hydrolysis and polycondensation reactions with the organosilicon compound and the like.
• the method for producing the silsesquioxane derivative of formula (1) or formula (2) preferably includes a distillation step in which the organosilicon compound is subjected to hydrolysis and polycondensation reaction in the presence of a reaction solvent, and then the reaction solvent, by-products, residual monomers, water, etc., in the reaction solution are distilled off.
• organosilicon compound used in the method for producing the silsesquioxane derivative of formula (1) will be described below.
• organosilicon compounds examples of those having an acryloyl group include (3-acryloyloxypropyl)trimethoxysilane, (3-acryloyloxypropyl)triethoxysilane, (8-acryloyloxyoctyl)trimethoxysilane, and (3-acryloyloxypropyl)trichlorosilane.
• examples of compounds having a methacryloyl group include (3-methacryloyloxypropyl)trimethoxysilane, (3-methacryloyloxypropyl)triethoxysilane, (8-methacryloyloxyoctyl)trimethoxysilane, and (3-methacryloyloxypropyl)trichlorosilane.
• Organosilicon compounds that give two structural units (f) upon hydrolysis include 1,3-divinyltetramethyldisiloxane, 1,3-bis(p-styryl)tetramethyldisiloxane, 1,3-bis(3-acryloyloxypropyl)tetramethyldisiloxane, 1,3-bis(3-methacryloyloxypropyl)tetramethyldisiloxane, etc., as well as methoxydimethylvinylsilane, ethoxydimethylvinylsilane, chlorodimethylvinylsilane, dimethylvinylsilanol, (3-acryloyloxypropyl)dimethylmethoxysilane, (3-methacryloyloxypropyl)dimethylmethoxysilane, p-styryldimethylmethoxysilane, ethynyldimethylmethoxysilane, etc.
• Silicon compounds that give the structural unit (a) upon hydrolysis include, for example, tetramethoxysilane, tetraethoxysilane, etc.
• organosilicon compound used in the method for producing the silsesquioxane derivative of formula (2) will be described below.
• organosilicon compounds examples of those having an oxetanyl group include (3-ethyl-3-oxetanylmethoxypropyl)trimethoxysilane, (3-ethyl-3-oxetanylmethoxypropyl)triethoxysilane, (3-methyl-3-oxetanylmethoxypropyl)trimethoxysilane, and (3-oxetanylmethoxypropyl)trichlorosilane.
• examples of compounds having an epoxy group include (glycidyloxypropyl)trimethoxysilane, (glycidyloxypropyl)triethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.
• Organosilicon compounds that give two structural units (2e) upon hydrolysis include 1,3-bis(3-ethyl-3-oxetanylmethoxypropyl)tetramethyldisiloxane, 1,3-bis(glycidyloxypropyl)tetramethyldisiloxane, etc., as well as methoxydimethylvinylsilane, ethoxydimethylvinylsilane, chlorodimethylvinylsilane, dimethylvinylsilanol, (3-acryloyloxypropyl)dimethylmethoxysilane, (3-methacryloyloxypropyl)dimethylmethoxysilane, p-styryldimethylmethoxysilane, ethynyldimethylmethoxysilane, etc.
• Silicon compounds that give the structural unit (2a) upon hydrolysis include, for example, tetramethoxysilane, tetraethoxysilane, etc.
• organosilicon compound used in both the methods for producing the silsesquioxane derivatives of the formula (1) and the formula (2) will be described below.
• organosilicon compound in which n is 3 and p is 1 include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, cyclohexyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane, ethynyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxy
• silane examples include trimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, tris(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropyltrimethoxysilane, 3-ethyl-3-[ ⁇ 3-(trimethoxysilyl)propoxy ⁇ methyl]oxetane, and 3-ethyl-3-[ ⁇ 3-(triethoxysilyl)propoxy ⁇ methyl]oxetane.
• organosilicon compounds in which n is 2 and p is 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldidiethoxysilane, propylmethyldimethoxysilane, octylmethyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, benzylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, vinylmethyldimethoxysilane, allylmethyldimethoxysilane, p-styrylmethyldimethoxysilane, ethynylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane,
• silane include 3-glycidoxypropylmethyldimethoxysilane, N-2-(aminoethyl)-3-a
• organosilicon compound in which n is 1 and p is 3 examples include hexamethyldisiloxane, trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, and dimethylphenylmethoxysilane.
• the alcohol is an alcohol in the narrow sense represented by the general formula R-OH, and is a compound having no functional groups other than an alcoholic hydroxyl group.
• the alcohol is not particularly limited, and examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, 2-methyl-2-butanol, 3-methyl-2-butanol, cyclopentanol, 2-hexanol, 3-hexanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2-ethyl-2-butanol, 2,3-dimethyl-2-butanol, and cyclohexanol.
• secondary alcohols such as 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, 3-methyl-2-butanol, cyclopentanol, 2-hexanol, 3-hexanol, 3-methyl-2-pentanol, and cyclohexanol are preferred.
• these alcohols may be used alone or in combination of two or more.
• the organic solvent used in the hydrolysis step may be an alcohol alone or may be a mixed solvent with at least one auxiliary solvent.
• the auxiliary solvent may be either a polar solvent or a non-polar solvent, or a combination of both.
• organic solvents for alcohol gargles include xylene, toluene, methyl ethyl ketone, methyl isobutyl ketone, and propylene glycol monomethyl ether.
• the hydrolysis and condensation reactions in the hydrolysis step proceed in the presence of water.
• water in the hydrolysis step, it is preferable to add water in an amount of 1.5 to 30 molar equivalents based on the total amount of hydrolyzable groups possessed by the organosilicon compound to carry out hydrolysis, and then to carry out condensation.
• the amount of water added in the hydrolysis step is, from the viewpoints of the cure shrinkage rate, hardness, storage stability, and curl suppression property during curing of the resulting silsesquioxane derivative, preferably 1.7 to 8 molar equivalents, more preferably 1.9 to 7 molar equivalents, even more preferably 2.0 to 7 molar equivalents, particularly preferably 2.2 to 7 molar equivalents, and most preferably 2.4 to 6 molar equivalents, relative to the total amount of hydrolyzable groups possessed by the organosilicon compound.
• the amount of water added in the hydrolysis step is, from the viewpoints of the cure shrinkage rate, hardness, storage stability, and curl suppression property during curing of the resulting silsesquioxane derivative, preferably 2 to 8 molar equivalents, more preferably 2.2 to 7 molar equivalents, and particularly preferably 2.4 to 6 molar equivalents, relative to the total amount of hydrolyzable groups possessed by the organosilicon compound.
• the hydrolysis and polycondensation reaction of silicon compound may be carried out without catalyst or with catalyst.
• catalyst preferred are inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid; organic acids such as formic acid, acetic acid, oxalic acid and paratoluenesulfonic acid; base catalysts such as ammonia, tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and more preferred are acid catalysts.
• the amount of the catalyst used is preferably an amount corresponding to 0.01 mol % to 20 mol %, and more preferably an amount corresponding to 0.1 mol % to 10 mol %, based on the total amount (mol) of silicon atoms contained in the silicon compound.
• the stability of the produced silsesquioxane derivative of formula (1) or formula (2) can be improved.
• the distillation can be performed under normal pressure or reduced pressure, at room temperature or under heating, or under cooling.
• the method for producing a silsesquioxane derivative may include a neutralization step for neutralizing the catalyst prior to the distillation step. It may also include a step for removing the salt produced by neutralization by washing with water, etc.
• the silsesquioxane derivative represented by formula (1) may contain a side chain functional group derived from the silicon compound used as a raw material in the production, which is ring-opened by the addition of an acid or the like to an oxetanyl group or an epoxy group, or may contain a hydroxyalkyl group generated by decomposition of an organic group having a (meth)acryloyl group, or may contain a group in which an acid or the like is added to an unsaturated hydrocarbon group or the like.
• Specific examples thereof include those in which a part of formula (1) contains a structure represented by the following formula (A) and/or a structure represented by formula (B).
• the content ratio is 50 mol% or less of the amount corresponding to the original organic group having an oxetanyl group or an epoxy group, the original organic group having a (meth)acryloyl group, or the original organic group having an unsaturated hydrocarbon group derived from the silicon compound as a raw material, and there is no problem in carrying out the present disclosure, and it is preferably 30 mol% or less, and more preferably 10 mol% or less.
• T units are exemplified, but similar D units, M units, etc. may also be used.
• the silsesquioxane derivative represented by formula (2) may contain a side chain functional group derived from the silicon compound used as a raw material in the production, which is a group formed by adding an acid or the like to a cyclic ether structure to open the ring, or may contain a hydroxyalkyl group formed by decomposing an organic group having a cyclic ether structure, or may contain a group formed by adding an acid or the like to an unsaturated hydrocarbon group.
• Specific examples thereof include those in which a structure represented by the following formula (2a) and/or a structure represented by formula (2b) is included as a part of formula (2).
• the content ratio of the organic group having the original oxetane structure or epoxy structure, the organic group having the original (meth)acryloyl group, or the organic group having the original unsaturated hydrocarbon group derived from the silicon compound as a raw material is 50 mol% or less without causing any problems in implementing the present disclosure, and is preferably 30 mol% or less, and more preferably 10 mol% or less.
• T units are exemplified, but similar D units, M units, etc. may also be used.
• the hard coat agent may or may not contain a polymerizable compound other than the silsesquioxane derivative (hereinafter also referred to as "other polymerizable compound").
• the other polymerizable compound is not particularly limited as long as it is a compound capable of undergoing a polymerization reaction in the presence of a silsesquioxane derivative and a polymerization initiator.
• Examples of the other polymerizable compound include silsesquioxane derivatives other than the silsesquioxane derivative represented by formula (1), (meth)acrylate compounds, compounds having an ethylenically unsaturated group, epoxy compounds (compounds having an epoxy group), compounds having an oxetanyl group (compounds containing an oxetanyl group), compounds having a vinyl ether group (vinyl ether compounds), etc.
• (meth)acrylate compound examples include compounds having one (meth)acryloyl group (hereinafter also referred to as “monofunctional (meth)acrylate”) and compounds having two or more (meth)acryloyl groups (hereinafter also referred to as “polyfunctional (meth)acrylate”).
• Examples of monofunctional (meth)acrylates include Alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; Monofunctional (meth)acrylates having an alicyclic group, such as cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and tricyclodecanemethylol (meth)acrylate; Monofunctional (meth)acrylates having an aromatic group, such as benzyl (meth)acrylate and phenyl (meth)acrylate; (meth)acrylates of alkylene oxide adducts of phenol derivatives, such as (meth)acrylates of phenol ethylene oxide adducts, (meth)acrylates of phenol propylene oxide adducts, (meth)acryl
• polyfunctional (meth)acrylate examples include polyethylene glycol di(meth)acrylates such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate; Polypropylene glycol di(meth)acrylates such as dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and tetrapropylene glycol di(meth)acrylate;
• di(meth)acrylate examples include 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-modified neopentyl glycol di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified bisphenol A di(meth)acrylate, ethylene oxide-modified hydrogenated bisphenol A di(meth)acrylate, trimethylolpropan
• a urethane (meth)acrylate can also be used.
• the urethane (meth)acrylate include a compound obtained by addition reaction of an organic polyisocyanate with a hydroxyl group-containing (meth)acrylate, and a compound obtained by addition reaction of an organic polyisocyanate with a polyol and a hydroxyl group-containing (meth)acrylate.
• the monofunctional (meth)acrylates, polyfunctional (meth)acrylates, etc. may be used alone or in combination of two or more kinds, or different kinds may be used in combination.
• polyol examples include low molecular weight polyols, polyether polyols, polyester polyols, and polycarbonate polyols.
• Low molecular weight polyols include ethylene glycol, propylene glycol, neopentyl glycol, cyclohexanedimethylol, and 3-methyl-1,5-pentanediol.
• polyether polyol examples include polypropylene glycol and polytetramethylene glycol.
• polyester polyols include reaction products of these low molecular weight polyols and/or polyether polyols with acid components such as dibasic acids such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid, and terephthalic acid, or anhydrides thereof. These may be used alone or in combination of two or more kinds, or different kinds may be used in combination.
• organic polyisocyanate examples include tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
• hydroxyl group-containing (meth)acrylate examples include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; and hydroxyl group-containing polyfunctional (meth)acrylates such as pentaerythritol tri(meth)acrylate, di(meth)acrylate of an adduct of 3 moles of alkylene oxide with isocyanuric acid, and dipentaerythritol penta(meth)acrylate. These may be used alone or in combination of two or more kinds, or different kinds may be used in combination.
• hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate
• hydroxyl group-containing polyfunctional (meth)acrylates such as pentaerythritol tri(me
• the compound having an ethylenically unsaturated group is a compound having one ethylenically unsaturated group in one molecule other than the (meth)acrylate compounds.
• the ethylenically unsaturated group include compounds having a (meth)acryloyl group, a maleimide group, a (meth)acrylamide group, or a vinyl group ((meth)acrylic acid, a Michael addition type dimer of acrylic acid, N-(2-hydroxyethyl)citraconimide, N,N-dimethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, etc.). These may be used alone or in combination of two or more.
• Examples of the epoxy compound include a monofunctional epoxy compound and a polyfunctional epoxy compound.
• Examples of the oxetanyl group-containing compound include monofunctional oxetane compounds and polyfunctional oxetane compounds.
• Examples of the vinyl ether compound include a monofunctional vinyl ether compound and a polyfunctional vinyl ether compound. As these compounds, for example, compounds described in JP-A-2011-42755 may be used.
• the content of the polymerizable compound is preferably from 1 to 95% by mass, and more preferably from 10 to 80% by mass, based on the total amount of the hard coat agent.
• the curable composition contained in the hard coat agent may contain a polymerization initiator.
• a polymerization initiator a well-known polymerization initiator is used depending on the type of the silsesquioxane derivative.
• a photopolymerization initiator and a thermal polymerization initiator can be used.
• a photoradical polymerization initiator or a thermal radical polymerization initiator can be used as the polymerization initiator.
• silsesquioxane derivative of the formula (2) when used as the silsesquioxane derivative, for example, a photocationic polymerization initiator or a thermal cationic polymerization initiator can be used as the polymerization initiator.
• Photoradical polymerization initiators include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and diethoxy.
• Acetophenone compounds such as diacetophenone, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone] and 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl ⁇ -2-methyl-propan-1-one; benzophenone compounds such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4'-methyldiphenyl sulfide; methylbenzoyl formate, oxyphenyl ⁇ -Ketoester compounds such as acetic acid 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester and oxyphenylacetic acid 2-[2-hydroxyethoxy]ethyl ester; phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)pheny
• thermal radical polymerization initiator examples include peroxides and azo initiators.
• peroxides include hydrogen peroxide; inorganic peroxides such as sodium persulfate, ammonium persulfate, and potassium persulfate; 1,1-bis(t-butylperoxy)2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-dimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, and 2,2-bis(4,4-dimethylcyclohexane).
• inorganic peroxides such as sodium persulfate, ammonium persulfate, and potassium persulfate
• t-butylperoxycyclohexyl)propane 1,1-bis(t-butylperoxy)cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluoylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t -hexyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxyacetate, 2,2-bis(t-butylperoxy)butane, t-butyl peroxybenzoate, n-butyl-4
• azo initiator examples include azo compounds such as 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, and azodi-t-butane. These may be used alone or in combination of two or more.
• a redox reaction by combining a peroxide with a redox polymerization initiation system using a reducing agent such as ascorbic acid, sodium ascorbate, sodium erythorbate, tartaric acid, citric acid, a metal salt of formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite, or ferric chloride.
• a reducing agent such as ascorbic acid, sodium ascorbate, sodium erythorbate, tartaric acid, citric acid, a metal salt of formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite, or ferric chloride.
• Examples of the photocationic polymerization initiator include onium salts such as iodonium salts, sulfonium salts, diazonium salts, selenium salts, pyridinium salts, ferrocenium salts, and phosphonium salts. Among these, iodonium salts and sulfonium salts are preferred.
• examples of the counter anion include BF 4 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , PF 6 ⁇ , and B(C 6 F 5 ) 4 ⁇ .
• Examples of the iodonium salt include (tricumyl)iodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis(pentafluorophenyl)borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis(dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate,
• Examples of iodonium tetrafluoroborate include bis(dodecylphenyl)iodonium tetrakis(pent
• the iodonium salt may be a commercially available product.
• Specific examples of the iodonium salt include "UV9380C” (product name) manufactured by Mentive Performance Materials Japan, "PHOTOINITIATOR2074" (product name) manufactured by Solvay Japan, and "WPI-116" (product name) and “WPI-113” (product name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
• sulfonium salt examples include bis[4-(diphenylsulfonio)phenyl]sulfide.bishexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide.bishexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfide.bistetrafluoroborate, bis[4-(diphenylsulfonio)phenyl]sulfide.tetrakis(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenylsulfonium.hexafluorophosphate, diphenyl-4-(phenylthio)phenylsulfonium.hexafluoroantimonate, diphenyl-4-(phenylthio)phenylsulfonium.tetrafluoroborate, diphen
• triphenylsulfonium hexafluorophosphate triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide bishexafluorophosphate, bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide bishexafluoroantimonate, bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide bistetrafluoroborate, bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]
• sulfonium salts can also be used, and specific examples thereof include “CYRACURE UVI-6990” (trade name), "CYRACURE UVI-6992” (trade name), and “CYRACURE UVI-6974” manufactured by Dow Chemical Japan, "ADEKAOPTOMER SP-150” (trade name), “ADEKAOPTOMER SP-152” (trade name), “ADEKAOPTOMER SP-170” (trade name), and “ADEKAOPTOMER SP-172” (trade name) manufactured by ADEKA Corporation, and "WPAG-370” (trade name) and “WPAG-638” (trade name) manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.
• diazonium salt examples include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate.
• thermal cationic polymerization initiator examples include sulfonium salts, phosphonium salts, quaternary ammonium salts, etc. Among these, sulfonium salts are preferred.
• the counter anion in the thermal cationic polymerization initiator examples include AsF 6 ⁇ , SbF 6 ⁇ , PF 6 ⁇ , and B(C 6 F 5 ) 4 ⁇ .
• sulfonium salt examples include triphenylsulfonium boron tetrafluoride, triphenylsulfonium antimony hexafluoride, triphenylsulfonium arsenic hexafluoride, tri(4-methoxyphenyl)sulfonium arsenic hexafluoride, and diphenyl(4-phenylthiophenyl)sulfonium arsenic hexafluoride.
• commercially available sulfonium salts can also be used.
• ADEKAOPTON CP-66 product name
• ADEKAOPTON CP-77 product name
• SAN-AID SI-60L product name
• SAN-AID SI-80L product name
• SAN-AID SI-100L product name
• Examples of the phosphonium salt include ethyltriphenylphosphonium antimony hexafluoride and tetrabutylphosphonium antimony hexafluoride.
• Examples of the quaternary ammonium salt include N,N-dimethyl-N-benzylanilinium antimony hexafluoride, N,N-diethyl-N-benzylanilinium boron tetrafluoride, N,N-dimethyl-N-benzylpyridinium antimony hexafluoride, N,N-diethyl-N-benzylpyridinium trifluoromethanesulfonate, N,N-dimethyl-N-(4-methoxybenzyl)pyridinium antimony hexafluoride, N,N-diethyl-N-(4-methoxybenzyl)pyridinium antimony hexafluoride, N,N-diethyl-
• the content of the polymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass, per 100 parts by mass of the silsesquioxane derivative.
• Other components that may be contained in the hard coating agent are not particularly limited, and examples thereof include solvents, resins, silicones, monomers, fillers, surfactants, antistatic agents (e.g., conductive polymers), leveling agents, photosensitizers, ultraviolet absorbers, antioxidants, heat resistance improvers, stabilizers, lubricants, pigments, dyes, plasticizers, suspending agents, adhesion imparting agents, nanoparticles, nanofibers, nanosheets, and the like.
• solvents e.g., solvents, resins, silicones, monomers, fillers, surfactants, antistatic agents (e.g., conductive polymers), leveling agents, photosensitizers, ultraviolet absorbers, antioxidants, heat resistance improvers, stabilizers, lubricants, pigments, dyes, plasticizers, suspending agents, adhesion imparting agents, nanoparticles, nanofibers, nanosheets, and the like.
• the hard coat agent may contain a silane-based reactive diluent such as tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes, monoalkoxysilanes, and disiloxanes.
• a silane-based reactive diluent such as tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes, monoalkoxysilanes, and disiloxanes.
• the hard coat agent may or may not contain a solvent.
• the solvent include various organic solvents such as aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, chlorinated hydrocarbon solvents, alcohol solvents, ether solvents, amide solvents, ketone solvents, ester solvents, and cellosolve solvents.
• the hard coating agent can be applied by any of the well-known coating methods (such as a bar coater method, a Mayer bar coater method, an applicator method, a doctor blade method, a roll coater method, a die coater method, a comma coater method, a gravure coating method, a microgravure coating method, a roll brush method, a spray coating method, an air knife coating method, an impregnation method, a curtain coating method, and an inkjet method).
• a bar coater method such as a bar coater method, a Mayer bar coater method, an applicator method, a doctor blade method, a roll coater method, a die coater method, a comma coater method, a gravure coating method, a microgravure coating method, a roll brush method, a spray coating method, an air knife coating method, an impregnation method, a curtain coating method, and an inkjet method.
• the hard coat agent is cured to form a hard coat layer.
• the hard coat agent is cured by at least one of irradiation with active energy rays (such as ultraviolet light) and heating, thereby curing the hard coat agent to form a hard coat layer.
• the curing method and curing conditions are selected depending on whether the polymerizable compound of the hard-coating agent is active energy ray curable and/or heat curable.
• the curing conditions e.g., the type of light source and the amount of light irradiation in the case of active energy ray curable, and the heating temperature and heating time in the case of heat curable
• preferred curing conditions will be described when a silsesquioxane derivative is used as the polymerizable compound of the hard coat agent.
• the hard-coating agent When the hard-coating agent is an active energy ray-curable hard-coating agent, the hard-coating agent may be cured by irradiating the agent with active energy rays using a known active energy ray irradiation device, etc.
• the active energy rays include electron beams, ultraviolet rays, visible light, and X-rays, and the like. Light is preferred, and ultraviolet rays are more preferred from the viewpoint of being able to use inexpensive devices.
• ultraviolet irradiation devices include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, extra high pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, chemical lamps, black light lamps, microwave excited mercury lamps, and light emitting diodes (LEDs).
• UV ultraviolet
• LEDs light emitting diodes
• the light irradiation intensity to the hard coating agent may be selected depending on the purpose, application, etc., and the light irradiation intensity in the light wavelength region effective for activating the active energy ray polymerization initiator (referred to as a photopolymerization initiator in the case of photocurable type) (depending on the type of photopolymerization initiator, light with a wavelength of 220 nm to 460 nm is preferably used) is preferably 0.1 mW/cm 2 to 1000 mW/cm 2 .
• the irradiation energy should be appropriately set depending on the type of active energy rays, the compounding composition of the hard coating agent, etc.
• the light irradiation time may also be selected depending on the purpose, use, etc., and it is preferable that the light irradiation time is set so that the integrated light amount expressed as the product of the light irradiation intensity in the light wavelength region and the light irradiation time is 10 mJ/cm 2 to 7,000 mJ/cm 2.
• the integrated light amount is more preferably 200 mJ/cm 2 to 5,000 mJ/cm 2 , and even more preferably 500 mJ/cm 2 to 4,000 mJ/cm 2.
• a substrate having a portion that is shaded when irradiated with light may be impregnated with a hard-coating agent, and then the substrate may be irradiated with light to first cure the hard-coating agent in the portion exposed to light, and then heat may be applied to cure the hard-coating agent in the portion not exposed to light, thereby performing two-step curing.
• substrates having complex shapes such as cloth, fiber, powder, porous, and uneven shapes, and may also be substrates having a shape in which two or more of these shapes are combined.
• the curing method and curing conditions are not particularly limited.
• the curing temperature is preferably 80° C. to 200° C., more preferably 100° C. to 180° C., and even more preferably 110° C. to 150° C.
• the curing temperature may be constant or may be increased. A combination of increasing and decreasing the temperature may also be used.
• the curing time is appropriately selected depending on the type of the thermal polymerization initiator of the hard coating agent, the content ratio of other components, etc., and is preferably 10 to 360 minutes, more preferably 30 to 300 minutes, and even more preferably 60 to 240 minutes.
• the thickness of the hard coat layer is preferably from 0.5 to 100 ⁇ m, and more preferably from 1 to 70 ⁇ m.
• the laminate with a hard coat layer of the present disclosure has high adhesion between the substrate and the hard coat layer. Specifically, it is preferable that no cracks occur even when the laminate is repeatedly subjected to a 180° bending test with a curvature radius of 5 mm 50,000 times with the hard coat layer facing inward. As a result, the adhesion between the substrate and the hard coat layer is high, and the hard coat layer has high hardness.
• An aqueous solution was prepared by mixing 35% hydrochloric acid (1.0 g, 9.6 mmol as hydrogen chloride) and pure water (150.7 g) separately.
• the aqueous solution prepared in the mixture was added dropwise from the dropping funnel over about 1 hour while stirring the reaction solution, and then the mixture was left to stand overnight at room temperature.
• the amount of water added was 2.8 times the molar amount of the total amount of hydrolyzable groups in the raw material organosilicon compound. Thereafter, the reaction solution was heated to 60°C while the solvent in the reaction solution was distilled off under reduced pressure to obtain 170 g of a colorless, transparent liquid silsesquioxane derivative (S1).
• the synthesized silsesquioxane derivative had a viscosity of 6,270 mPa ⁇ s at 25°C and a weight average molecular weight (Mw) of 2,010.
• a primer was prepared by adding methanol (MeOH) or acetone as an organic solvent, acetic acid as a pH adjuster, and pure water as water to 3-aminopropyltrimethoxysilane ("KBM-903" manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane ("KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd.), or N-2-(aminoethyl)-3-aminopropyltrimethoxysilane ("KBM-603" manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, and stirring the mixture with a planetary centrifugal mixer.
• the ratio of the components was as shown in Table 1.
• a slide glass (“S1225" manufactured by Matsunami Glass Industry Co., Ltd.) was subjected to a corona discharge treatment, and then the above primer was applied using a No. 8 bar coater, and the substrate was dried by heating at the temperature and time shown in Table 1 to form a primer layer having a thickness of 1 ⁇ m or less. Then, a photocurable hard coat agent was applied using a No. 8 bar coater, and the substrate was heated in a fan oven at 60° C. for 5 minutes to evaporate the solvent, and then cured by irradiating with ultraviolet light under the following conditions to form a hard coat layer having a thickness of 5 ⁇ m. In addition, in Examples 1, 6, 7, and 11 and Comparative Examples 1 and 2, laminates were also produced that were not subjected to the corona discharge treatment.
• UV irradiation conditions Lamp: High pressure mercury lamp (ECS-4011GX, manufactured by iGraphics Co., Ltd.) Lamp height: 10cm Conveyor speed: 5.75 m/min Accumulated light amount per pass: 360 mJ/cm 2 (UV-A, measured value using UV POWER PUCK II manufactured by EIT) Atmosphere: Air Number of passes: 10
• Comparative Examples 1 and 2 show that extending the drying time of the primer improves the adhesion between the substrate and the hard coat layer, whereas shortening the drying time of the primer deteriorates the adhesion between the substrate and the hard coat layer. From Examples 1 to 10, it can be seen that when the composition of the primer is within an appropriate range, the adhesion between the substrate and the hard coat layer is improved even if the drying time of the primer is shortened. From Examples 11 and 12, it can be seen that even if the type of organic solvent in the primer is changed, the adhesion between the substrate and the hard coat layer is improved.
• Laminates were prepared in the same manner as in Example 1, except that in Example 1 shown in Table 1, the substrate was changed to a polyimide resin sheet ("Upilex” manufactured by UBE Corporation), a polyamide resin film ("Nylon 6” manufactured by TP Giken Co., Ltd.), or a thiourethane resin film ("MR-8” manufactured by Mitsui Chemicals Co., Ltd.) as shown in Table 2. Furthermore, as shown in Table 2, laminates were also prepared in which no primer layer was formed between the substrate and the hard coat layer. Then, the above-mentioned cross-cut peel test was carried out on the obtained laminates.

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