Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
  • C08G59/3281—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing silicon
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
  • C08G65/16—Cyclic ethers having four or more ring atoms
  • C08G65/18—Oxetanes
• • 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
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes

Definitions

• This disclosure relates to an undercoat layer, a laminate, and an optical device made of a photocurable composition and its cured product.
• a hard coat layer is known to be provided on the surface of articles (substrates) for which transparency and aesthetics are important, such as displays for televisions, personal computers, and smartphones, and films for these displays, in order to improve abrasion resistance (i.e., the ability to prevent damage caused by abrasion or scratching).
• Non-Patent Document 1 when using a glass substrate as the substrate, methods such as using a silane coupling agent on the surface of the glass substrate or modifying the glass surface have been known to enhance adhesion between the hard coat layer and the glass substrate (for example, Non-Patent Document 1).
• the present disclosure aims to solve the above problems by providing a photocurable composition that has excellent adhesion to substrates and can be easily applied.
• a photocurable composition containing a first epoxy compound which is an organosiloxane containing two or more alicyclic epoxy groups, a second epoxy compound, and a third epoxy compound or an oxetane compound, in which the content of the first epoxy compound is 30 to 70 mass% based on the total amount of the curable compounds, has excellent adhesion to a substrate and can be easily applied.
• a first epoxy compound which is an organosiloxane containing two or more alicyclic epoxy groups
• a second epoxy compound and a third epoxy compound or an oxetane compound
• the present disclosure provides a photocurable composition that includes a first epoxy compound that is an organosiloxane containing two or more alicyclic epoxy groups, a second epoxy compound, and a third epoxy compound or an oxetane compound, and the content of the first epoxy compound is 30 to 70 mass % based on the total amount of the composition excluding the solvent.
• the present disclosure has excellent adhesion to the substrate, can be easily applied, and can also provide excellent scratch resistance when a hard coat layer is laminated thereon.
• the photocurable composition of the present disclosure preferably contains the first epoxy compound, the second epoxy compound, and the oxetane compound.
• the composition tends to have better adhesion to the substrate, easier application, and scratch resistance when a hard coat layer is laminated.
• the content of the second epoxy compound is preferably 20 to 60 mass% based on the total amount of the curable compound.
• the above composition tends to make it easier to apply to a substrate.
• the content of the oxetane compound is preferably 5 to 25% by mass based on the total amount of the curable compound. This composition tends to provide better adhesion to the substrate.
• the present disclosure also provides an undercoat layer that is a cured product made from the above-mentioned photocurable composition.
• the thickness of the undercoat layer is preferably 0.1 to 15 ⁇ m.
• the present disclosure also provides a laminate in which a substrate, the undercoat layer formed on at least one surface of the substrate, and a hard coat layer are laminated in this order.
• the substrate of the laminate is preferably a glass substrate.
• the hard coat layer of the laminate contains a curable polyorganosilsesquioxane resin as the curable resin.
• the hard coat layer surface of the laminate has a pencil hardness of 6H or more.
• the laminate has sufficient surface hardness and tends to have excellent scratch resistance.
• the undercoat layer and the hard coat layer in the laminate can exhibit sufficient adhesion.
• the present disclosure also provides a display device including the above laminate.
• the photocurable composition of the present disclosure has excellent adhesion to substrates and can be easily applied. Furthermore, in a laminate in which a hard coat layer is laminated on an undercoat layer formed from the above-mentioned photocurable composition, the undercoat layer and the hard coat layer exhibit excellent adhesion to each other, while the surface of the hard coat layer can be given sufficient surface hardness, resulting in excellent scratch resistance.
• (meth)acryloyl group means an acryloyl group and/or a methacryloyl group.
• (meth)acrylate means an acrylate and/or a methacrylate.
• the photocurable composition of the present disclosure comprises a first epoxy compound which is an organosiloxane containing two or more alicyclic epoxy groups, a second epoxy compound, and a third epoxy compound or an oxetane compound, and the content of the first epoxy compound is 30 to 70 mass % based on the total amount of the curable compounds.
• the photocurable composition includes a first epoxy compound which is an organosiloxane containing two or more alicyclic epoxy groups.
• the first epoxy compound is a compound having two or more alicyclic epoxy groups in a molecule and further having at least a siloxane skeleton constituted by a siloxane bond (Si-O-Si).
• the siloxane skeleton includes a cyclic siloxane skeleton, a linear or branched silicone (linear or branched polysiloxane), a cage-type or ladder-type polysilsesquioxane, and the like.
• a compound having a cyclic siloxane skeleton is preferable in terms of being able to achieve both ease of application to a substrate and adhesion.
• the first epoxy compound can be used alone or in combination of two or more types.
• the number of Si-O units forming the siloxane ring is preferably 2 to 12, and more preferably 4 to 8.
• the alicyclic epoxy group of the first epoxy compound means a cyclic olefin group that has been epoxidized within the molecule.
• An "epoxidized cyclic olefin group” is a group (monovalent group) formed by removing one hydrogen atom from a structure in which at least one of the carbon-carbon unsaturated bonds in a cyclic olefin (a cyclic aliphatic hydrocarbon in which at least one of the carbon-carbon bonds forming a ring is a carbon-carbon unsaturated bond) has been epoxidized.
• an epoxidized cyclic olefin group is a group that includes an aliphatic hydrocarbon ring structure and an epoxy group
• the epoxy group is an epoxy group composed of two adjacent carbon atoms and an oxygen atom that constitute the aliphatic hydrocarbon ring.
• Examples of the cyclic olefin group (before epoxidation) in the above epoxidized cyclic olefin group include cycloalkenyl groups such as cyclopropenyl groups (e.g., 2-cyclopropenyl groups), cyclobutenyl groups (e.g., 2-cyclobutenyl groups), cyclopentenyl groups (e.g., 2-cyclopentenyl groups, 3-cyclopentenyl groups), and cyclohexenyl groups (e.g., 2-cyclohexenyl groups, 3-cyclohexenyl groups); cycloalkadienyl groups such as 2,4-cyclopentadiene-1-yl groups, 2,4-cyclohexadiene-1-yl groups, and 2,5-cyclohexadiene-1-yl groups; and polycyclic groups such as dicyclopentenyl groups, dicyclohexenyl groups, and norbornenyl groups.
• the aliphatic hydrocarbon ring forming the cyclic olefin group in the above epoxidized cyclic olefin group may have one or more substituents bonded thereto.
• substituents include substituents having 0 to 20 carbon atoms (more preferably 0 to 10 carbon atoms), and more specifically, halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, etc.; hydroxy group; alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, isobutyloxy group, etc.
• alkenyloxy groups such as allyloxy group (preferably C 2-6 alkenyloxy group, more preferably C 2-4 alkenyloxy group); aryloxy groups (preferably C 6-14 aryloxy group) which may have a substituent such as a C 1-4 alkyl group, a C 2-4 alkenyl group, a halogen atom, a C 1-4 alkoxy group, etc.
• aralkyloxy groups preferably C 7-18 aralkyloxy groups
• acyloxy groups such as acetyloxy, propionyloxy, (meth)acryloyloxy and benzoyloxy (preferably C 1-12 acyloxy groups); mercapto groups; alkylthio groups such as methylthio and ethylthio (preferably C 1-6 alkylthio groups, more preferably C 1-4 alkylthio groups); alkenylthio groups such as allylthio (preferably C 2-6 alkenylthio groups, more preferably C 2-4 alkenylthio groups); arylthio groups such as phenylthio, tolylthio and naphthylthio, which may have a substituent such as a C 1-4 alkyl group, a C 2-4 alkenyl group, a
• the cyclic olefin group is preferably a cyclic olefin group having 5 to 12 carbon atoms, more preferably a cycloalkenyl group having 5 to 12 carbon atoms, and even more preferably a cyclohexenyl group.
• the epoxidized cyclic olefin group is preferably a group in which a cyclic olefin group having 5 to 12 carbon atoms has been epoxidized, more preferably a group in which a cycloalkenyl group having 5 to 12 carbon atoms has been epoxidized, and even more preferably a group in which a cyclohexenyl group has been epoxidized (cyclohexene oxide group).
• the first epoxy compound may have one type of epoxidized cyclic olefin group, or may have two or more types.
• the number of epoxidized cyclic olefin groups contained in the molecule of the first epoxy compound is not particularly limited as long as it is 2 or more, but 2 to 6 are preferable, 3 to 5 are more preferable, and 4 are even more preferable.
• Examples of the first epoxy compound include 2,4-di[2-(3- ⁇ oxabicyclo[4.1.0]heptyl ⁇ )ethyl]-2,4,6,6,8,8-hexamethyl-cyclotetrasiloxane, 4,8-di[2-(3- ⁇ oxabicyclo[4.1.0]heptyl ⁇ )ethyl]-2,2,4,6,6,8-hexamethyl-cyclotetrasiloxane, 2,4-di[2-(3- ⁇ oxabicyclo[4.1.0]heptyl ⁇ )ethyl]-6,8-dipropyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 4,8-di[2-(3- ⁇ oxabicyclo[4.1.0]heptyl ⁇ )ethyl]-2,6-di Propyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,8-tri[2-(3- ⁇ oxabicyclo[
• the content of the first epoxy compound in the photocurable composition of the present disclosure is preferably 30 to 70 mass %, more preferably 35 to 65 mass %, and even more preferably 40 to 60 mass %, based on the total amount of the curable compounds.
• the photocurable composition can be easily applied to a substrate, and furthermore, the coated substrate has excellent adhesion.
• the photocurable composition contains an epoxy compound other than the first epoxy compound (hereinafter, the other epoxy compound is referred to as a "second epoxy compound"). By containing the second epoxy compound, the photocurable composition can be easily applied to a substrate.
• the second epoxy compound may be an alicyclic epoxy compound other than the first epoxy compound, an aliphatic epoxy compound, an aromatic epoxy compound, etc. From the viewpoint of exhibiting ease of application to a substrate in combination with the first epoxy compound, it is preferable that the second epoxy compound is an alicyclic epoxy compound.
• R may be the same as the epoxidized cyclic olefin group described above.
• the two R may be the same or different.
• X represents a single bond or a linking group (a divalent group having one or more atoms; excluding groups containing a siloxane bond).
• the linking group include divalent hydrocarbon groups, carbonyl groups, ether bonds, ester bonds, carbonate groups, amide groups, and groups in which a plurality of these are linked.
• the divalent hydrocarbon groups include divalent aliphatic hydrocarbon groups, divalent alicyclic hydrocarbon groups, and groups in which a plurality of these are linked.
• divalent aliphatic hydrocarbon groups examples include linear or branched alkylene groups (e.g., alkylene groups having 1 to 6 carbon atoms), such as methylene groups, methylmethylene groups, dimethylmethylene groups, ethylene groups, propylene groups, trimethylene groups, and tetramethylene groups.
• divalent alicyclic hydrocarbon group examples include divalent cycloalkylene groups such as 1,2-cyclopentylene, 1,3-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, and 1,4-cyclohexylene.
• Examples of the compound represented by the above formula (a1) include compounds in which both R are cyclohexene oxide groups (particularly compounds in which the carbon atoms at the 4th positions of two cyclohexene oxide groups (the positions of the two carbon atoms forming the epoxy group are taken as the 1st and 2nd positions) are linked by a single bond or a divalent hydrocarbon group).
• alicyclic epoxy compound represented by the above formula (a1) include (3,4,3',4'-diepoxy)bicyclohexyl, bis(3,4-epoxycyclohexylmethyl)ether, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, 2,2-bis(3,4-epoxycyclohexane-1-yl)propane, 1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, bis(3,4-epoxycyclohexylmethyl)ether, and 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate.
• the other alicyclic epoxy compounds mentioned above also include compounds in which an epoxy group is directly bonded to an alicyclic ring via a single bond, such as the compound represented by the following formula (b1), and hydrogenated aromatic glycidyl ether epoxy compounds.
• R i is a group obtained by removing q -OH from a q-hydric alcohol, and p and q each represent a natural number.
• the q-hydric alcohol [R i -(OH)q] include polyhydric alcohols such as 2,2-bis(hydroxymethyl)-1-butanol (alcohols having 1 to 15 carbon atoms, etc.).
• q is preferably 1 to 6, and p is preferably 1 to 30.
• p in two or more groups in ( ) (within parentheses) may be the same or different.
• the above-mentioned hydrogenated aromatic glycidyl ether epoxy compounds include, for example, 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane, 2,2-bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]propane, and compounds obtained by hydrogenating bisphenol A type epoxy compounds such as polymers thereof (hydrogenated bisphenol A type epoxy compounds); bis[o,o-(2,3-epoxypropoxy)cyclohexyl]methane, bis[o,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[p,p-(2,3-epoxypropoxy)cyclohexyl]methane, Examples of such compounds include hydrogenated compounds of bisphenol F type epoxy compounds such as bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]methane, bis[3,5-dimethyl-4-(2,
• aliphatic epoxy compounds include glycidyl ethers of alcohols not having a q-valent cyclic structure (q is a natural number); glycidyl esters of mono- or polyvalent carboxylic acids [e.g., acetic acid, propionic acid, butyric acid, stearic acid, adipic acid, sebacic acid, maleic acid, itaconic acid, etc.]; epoxidized oils and fats having double bonds such as epoxidized linseed oil, epoxidized soybean oil, and epoxidized castor oil; and epoxidized polyolefins (including polyalkadienes) such as epoxidized polybutadiene.
• q-valent alcohols include polyether polyols
• the above-mentioned aromatic epoxy compounds include, for example, epi-bis-type glycidyl ether type epoxy resins obtained by a condensation reaction between bisphenols [e.g., bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc.] and epihalohydrin; high molecular weight epi-bis-type glycidyl ether type epoxy resins obtained by further addition reaction of these epi-bis-type glycidyl ether type epoxy resins with the above-mentioned bisphenols; phenols [e.g., phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol Examples of such epoxy resins include novolak alkyl type glycidyl ether epoxy resins obtained by condensing polyhydric alcohols obtained by condensing polyhydric alcohols [e.g., formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzalde
• the content of the second epoxy compound in the photocurable composition of the present disclosure is preferably 20 to 60 mass %, more preferably 25 to 55 mass %, and even more preferably 30 to 50 mass %, based on the total amount of the curable compound. Being within the above range makes it easy to apply the photocurable composition to a substrate.
• an oxetane compound is contained in addition to the first epoxy compound and the second epoxy compound.
• the oxetane compound is a compound having at least one oxetanyl group as a cationic polymerizable group in one molecule, and may be a compound having two or more oxetane groups.
• the oxetane compound may be used alone or in combination of two or more.
• oxetane compounds include, for example, trimethylene oxide, 3,3-bis(vinyloxymethyl)oxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane, 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxymethyl)oxetane, 3-ethyl-3-(chloromethyl)oxetane, 3,3-bis Examples include (chloromethyl)oxetane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, bis ⁇ [1-ethyl(3-oxetanyl)]methyl ⁇ ether, 4,4'-bis[(3-ethyl-3-o
• the content of the oxetane compound is preferably 5 to 25% by mass, and more preferably 10 to 20% by mass, based on the total amount of the curable compound. When the content of the oxetane compound is within the above range, it becomes easier to exhibit adhesion to the substrate.
• the photocurable composition may contain a third epoxy compound and a fourth epoxy compound, which will be described later, in addition to the oxetane compound.
• ⁇ Third Epoxy Compound> in addition to the first and second epoxy compounds, it is preferable to contain a third epoxy compound that does not fall under the first epoxy compound and is a component different from the second epoxy compound.
• the epoxy compound with a higher content is the second epoxy compound
• the epoxy compound with a lower content is the third epoxy compound.
• the third epoxy compound may be any epoxy compound that does not fall under the category of the first epoxy compound and is not used as the second epoxy compound.
• the second epoxy compound may be any of the compounds exemplified above.
• the third epoxy compound contains an aliphatic epoxy compound, particularly when the second epoxy compound contains an alicyclic epoxy compound.
• the aliphatic epoxy compound as the third epoxy compound, it becomes easier to exhibit adhesion to the substrate.
• the aliphatic epoxy compound those exemplified as the aliphatic epoxy compound for the second epoxy compound can be used.
• the content of the third epoxy compound is preferably 5 to 25 mass % relative to the total amount of the curable compound, and more preferably 7 to 20 mass %.
• the content of the third epoxy compound is within the above range, it becomes easier to exhibit adhesion to the substrate.
• the photocurable composition may further contain an epoxy compound other than the first to third epoxy compounds (hereinafter referred to as a "fourth epoxy compound").
• an epoxy compound other than the second and third epoxy compounds may be used that does not fall under the first epoxy compound.
• an epoxy compound other than the second and third epoxy compounds may be used that is exemplified as the second epoxy compound.
• the fourth epoxy compound is an epoxy compound with a smaller content than the second and third epoxy compounds.
• the fourth epoxy compound may be used alone or in combination of two or more.
• the photocurable composition preferably further contains a curing agent.
• a curing agent a publicly known or commonly used photocationic polymerization initiator can be used.
• the curing agents can be used alone or in combination of two or more kinds.
• photocationic polymerization initiators examples include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, and bromine salt compounds.
• sulfonium salt compounds is particularly preferred because they can form a cured product with excellent curing properties.
• anion portion of the photocationic polymerization initiator examples include [(Y) SB (Phf) 4-S ] (wherein Y represents a phenyl group or a biphenylyl group. Phf represents a phenyl group in which at least one hydrogen atom is substituted with at least one selected from a perfluoroalkyl group, a perfluoroalkoxy group, and a halogen atom.
• s is an integer of 0 to 3
• BF4 [(Rf)nPF6 -n ]
• Rf an alkyl group in which 80% or more of the hydrogen atoms are substituted with fluorine atoms
• n an integer of 0 to 5
• AsF6 SbF6
• pentafluorohydroxyantimonate and the like.
• photocationic polymerization initiators include (4-hydroxyphenyl)methylbenzylsulfonium tetrakis(pentafluorophenyl)borate, 4-(4-biphenylylthio)phenyl-4-biphenylylphenylsulfonium tetrakis(pentafluorophenyl)borate, 4-(phenylthio)phenyldiphenylsulfonium phenyltris(pentafluorophenyl)borate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium phenyltris(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium tris(pentafluoroethyl)trifluorophosphate, diphenyl[4-(phenylthio)phenyl
• the amount of the curing agent used is preferably 0.01 to 15 parts by mass, more preferably 0.03 to 10 parts by mass, even more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass, relative to the total amount (100 parts by mass) of all cationic curable compounds contained in the curable composition.
• the photocurable composition of the present disclosure may contain other compounds in addition to the above compounds.
• the other compounds include solvents, antioxidants, metal oxide particles, rubber particles, silicone-based or fluorine-based defoamers, silane coupling agents, fillers, plasticizers, antistatic agents, flame retardants, colorants, ultraviolet absorbers, ion adsorbents, pigments, and release agents.
• the content (mixture amount) of these various additives is preferably 5% by mass or less of the total amount (100% by mass) of the curable composition.
• an undercoat layer made of the cured product of the photocurable composition can be given.
• the undercoat layer can be obtained by applying the photocurable composition to at least one surface of a substrate and curing the composition.
• the substrate may be a single layer or multiple layers made of the same or different materials.
• the substrate may be a resin substrate, a glass substrate, a metal substrate, or the like, and is preferably a glass substrate from the viewpoint of adhesion with the undercoat layer.
• the undercoat layer can be formed by a conventional coating method.
• a conventional coating method for example, well-known methods such as dipping, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing, spray coating, gravure offset, and organic deposition can be used.
• the curing treatment include light irradiation using a mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, sunlight, an electron beam source, a laser light source, and an LED light source. It is preferable to irradiate in a range where the cumulative irradiation amount is, for example, 300 to 10,000 mJ/cm 2.
• a film previously coated on another substrate by the above-mentioned formation method may be transferred to the substrate using a transfer method such as adhesive transfer, thermal transfer, and UV transfer.
• annealing treatment to remove internal strain, for example by heating at a temperature of 100 to 200°C for about 30 minutes to 1 hour.
• the undercoat layer when the appearance of the undercoat layer is visually inspected after curing, it is preferable that the undercoat layer can be applied to the substrate without causing any repellency, and it is even more preferable that the undercoat layer surface is not rough and can be applied uniformly.
• the undercoat layer is scratched with a cutter blade at intervals of 1 mm to create a grid of 100 squares, which are then attached with adhesive tape and peeled off in a 90° direction.
• the surface of the undercoat layer is visually inspected to see whether it peels off from the adhesive tape, it is preferable that 90 or more squares remain, more preferably 95 or more squares, and especially preferably 100 squares remain.
• the substrate and undercoat layer can exhibit sufficient adhesion.
• the thickness of the undercoat layer is preferably 0.1 to 15 ⁇ m, and more preferably 1 to 10 ⁇ m.
• An embodiment of the present disclosure includes a laminate including the substrate, the undercoat layer, and a hard coat layer.
• the laminate can be produced by forming a hard coat layer on the undercoat layer formed on the substrate.
• the laminate structure may be formed on only one surface (one side) of the substrate, or on both surfaces (both sides).
• the laminate may have layers other than the undercoat layer and the hard coat layer, and it is preferable that the substrate, the undercoat layer, and the hard coat layer are laminated in this order from the viewpoint of exerting the adhesion of the laminate.
• the hard coat layer preferably contains a curable resin, and preferably contains a polyorganosilsesquioxane having a structural unit represented by the following formula (1) (hereinafter, may be referred to as "polyorganosilsesquioxane of the present disclosure") as the curable resin. That is, the curable composition for forming the hard coat layer (hereinafter, may be referred to as "hard coat agent”) preferably contains a polyorganosilsesquioxane having a structural unit represented by the following formula (1). As described later, the hard coat agent may contain other components such as a curing agent (particularly a photocationic polymerization initiator, a photoradical polymerization initiator), and an antioxidant. [In formula (1), R 1 represents a group containing an active energy ray-curable functional group.]
• the polyorganosilsesquioxane of the present disclosure is characterized by having a constitutional unit represented by the above formula (1).
• the polyorganosilsesquioxane of the present disclosure preferably has a constitutional unit represented by the following formula (I) (sometimes referred to as "T3 body") and a constitutional unit represented by the following formula (II) (sometimes referred to as "T2 body”).
• the polyorganosilsesquioxane of the present disclosure preferably has a constitutional unit represented by the formula (4) described below.
• the structural unit represented by the above formula (1) is a silsesquioxane structural unit (so-called T unit) generally represented by [RSiO 3/2 ].
• R in the above formula represents a hydrogen atom or a monovalent organic group, and the same applies below.
• the structural unit represented by the above formula (1) is formed by hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound (specifically, for example, a compound represented by the formula (a) described later).
• R 1 represents a group (monovalent group) containing an active energy ray-curable functional group. That is, the polyorganosilsesquioxane of the present disclosure is a photocationically curable compound (photocationically polymerizable compound) or a photoradical curable compound (photoradical polymerizable compound) having at least an active energy ray-curable functional group in the molecule.
• the "photocationically polymerizable functional group" in the group containing the active energy ray-curable functional group is not particularly limited as long as it has photocationic polymerizability, and examples thereof include an epoxy group, an oxetane group, a vinyl ether group, and a vinylphenyl group.
• the "photoradical polymerizable functional group” in the group containing the active energy ray-curable functional group is not particularly limited as long as it has photoradical polymerizability, and examples thereof include a (meth)acryloxy group, a (meth)acrylamide group, a vinyl group, and a vinylthio group.
• an epoxy group e.g., H or more
• an epoxy group is particularly preferred.
• the epoxy group-containing group includes, but is not limited to, known or commonly used groups having an oxirane ring. From the viewpoint of the curability of the hard coating agent and the scratch resistance and toughness of the cured product (coating film), a group represented by the following formula (1a), a group represented by the following formula (1b), a group represented by the following formula (1c), or a group represented by the following formula (1d) is preferred, more preferably a group represented by the following formula (1a) or a group represented by the following formula (1c), and even more preferably a group represented by the following formula (1a).
• R 1a represents a linear or branched alkylene group.
• the linear or branched alkylene group include linear or branched alkylene groups having 1 to 10 carbon atoms, such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and decamethylene.
• R 1a is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably an ethylene group, a trimethylene group, or a propylene group, and even more preferably an ethylene group or a trimethylene group, from the viewpoint of the scratch resistance and toughness of the cured product (coating film).
• R 1b represents a linear or branched alkylene group, and examples thereof include the same groups as R 1a .
• R 1b is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably an ethylene group, a trimethylene group, or a propylene group, and even more preferably an ethylene group or a trimethylene group.
• R 1c represents a linear or branched alkylene group, and examples thereof include the same groups as R 1a .
• R 1c is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably an ethylene group, a trimethylene group, or a propylene group, and even more preferably an ethylene group or a trimethylene group.
• R 1d represents a linear or branched alkylene group, and examples thereof include the same groups as R 1a .
• R 1d is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably an ethylene group, a trimethylene group, or a propylene group, and even more preferably an ethylene group or a trimethylene group.
• R 1 in formula (1) is preferably a group represented by the above formula (1a) in which R 1a is an ethylene group [particularly, a 2-(3',4'-epoxycyclohexyl)ethyl group].
• the above-mentioned groups containing an oxetane group include known or conventional groups having an oxetane ring, and are not particularly limited.
• the group may be an oxetane group itself, or a group in which a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms) is substituted with an oxetane group.
• a 3-oxetanyl group an oxetan-3-ylmethyl group, a 3-ethyloxetan-3-ylmethyl group, a 2-(oxetan-3-yl)ethyl group, a 2-(3-ethyloxetan-3-yl)ethyl group, a 3-(oxetan-3-ylmethoxy)propyl group, a 3-(3-ethyloxetan-3-ylmethoxy)propyl group, and the like are preferred.
• the above-mentioned groups containing a vinyl ether group include known or commonly used groups having a vinyl ether group, and are not particularly limited.
• the vinyl ether group itself and groups in which a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms) is substituted with a vinyl ether group.
• a hydrogen atom usually one or more, preferably one hydrogen atom
• an alkyl group preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms
• vinyloxymethyl groups, 2-(vinyloxy)ethyl groups, 3-(vinyloxy)propyl groups, etc. are preferred.
• the above-mentioned groups containing a vinylphenyl group include known or commonly used groups having a vinylphenyl group, and are not particularly limited.
• the vinylphenyl group itself and groups in which a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms) is substituted with a vinylphenyl group.
• a hydrogen atom usually one or more, preferably one hydrogen atom
• an alkyl group preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms
• 4-vinylphenyl, 3-vinylphenyl, 2-vinylphenyl, etc. are preferred.
• the above-mentioned group containing a (meth)acryloxy group includes known or conventional groups having a (meth)acryloxy group, and is not particularly limited.
• the group may be the (meth)acryloxy group itself, or a group in which a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms) is substituted with a (meth)acryloxy group.
• the above-mentioned group containing a (meth)acrylamide group includes known or conventional groups having a (meth)acrylamide group, and is not particularly limited.
• the group may be the (meth)acrylamide group itself, or a group in which a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms) is substituted with a (meth)acrylamide group.
• a 2-((meth)acrylamide)ethyl group, a 3-((meth)acrylamide)propyl group, etc. are preferred.
• the vinyl group-containing group includes known or commonly used groups having a vinyl group, and is not particularly limited.
• the vinyl group itself and a group in which a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms) is substituted with a vinyl group.
• a hydrogen atom usually one or more, preferably one hydrogen atom
• an alkyl group preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms
• vinyl groups vinyl methyl groups, 2-vinyl ethyl groups, 3-vinyl propyl groups, etc. are preferred.
• the above-mentioned vinylthio group-containing group includes known or commonly used groups having a vinylthio group, and is not particularly limited.
• the vinylthio group itself and a group in which a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms) is substituted with a vinylthio group.
• a vinylthiomethyl group, a 2-(vinylthio)ethyl group, a 3-(vinylthio)propyl group, etc. are preferred.
• R 1 in formula (1) is preferably a group containing an epoxy group or a group containing a (meth)acryloxy group, and in particular a group represented by the above formula (1a) in which R 1a is an ethylene group [particularly a 2-(3',4'-epoxycyclohexyl)ethyl group], a 3-(acryloxy)propyl group, or a 3-(methacryloxy)propyl group.
• the polyorganosilsesquioxane of the present disclosure may have only one type of structural unit represented by the above formula (1), or may have two or more types of structural units represented by the above formula (1).
• the polyorganosilsesquioxane of the present disclosure may have, as the silsesquioxane structural unit [RSiO 3/2 ], a structural unit represented by the following formula (2) in addition to the structural unit represented by formula (1) above.
• the structural unit represented by the above formula (2) is a silsesquioxane structural unit (T unit) generally represented by [RSiO 3/2 ]. That is, the structural unit represented by the above formula (2) is formed by hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound (specifically, for example, a compound represented by the formula (b) described later).
• R 2 in the above formula (2) represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group.
• the aryl group include a phenyl group, a tolyl group, and a naphthyl group.
• the aralkyl group include a benzyl group and a phenethyl group.
• Examples of the cycloalkyl group include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
• Examples of the alkyl group include a linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group, and an isopentyl group.
• Examples of the alkenyl group include a linear or branched alkenyl group such as a vinyl group, an allyl group, and an isopropenyl group.
• substituted aryl group, substituted aralkyl group, substituted cycloalkyl group, substituted alkyl group, and substituted alkenyl group include groups in which the hydrogen atom or part or all of the main chain skeleton in each of the above-mentioned aryl group, aralkyl group, cycloalkyl group, alkyl group, and alkenyl group is substituted with at least one selected from the group consisting of ether group, ester group, carbonyl group, siloxane group, halogen atom (fluorine atom, etc.), acrylic group, methacryl group, mercapto group, amino group, and hydroxyl group.
• R2 is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, and even more preferably a phenyl group.
• the ratio of each of the above-mentioned silsesquioxane constituent units (constituent units represented by formula (1) and constituent units represented by formula (2)) in the polyorganosilsesquioxane of the present disclosure can be appropriately adjusted by adjusting the composition of the raw material (hydrolyzable trifunctional silane) for forming these constituent units.
• the polyorganosilsesquioxane of the present disclosure may further have at least one siloxane structural unit selected from the group consisting of silsesquioxane structural units other than the structural units represented by the above formula (1) and the structural units represented by the formula (2), [RSiO 3/2 ], [R 3 SiO 1/2 ] structural units (so-called M units), [R 2 SiO 2/2 ] structural units (so-called D units), and [SiO 4/2 ] structural units (so-called Q units).
• examples of silsesquioxane structural units other than the structural units represented by the above formula (1) and the structural units represented by the formula (2) include, for example, structural units represented by the following formula (3).
• the ratio [T3 body/T2 body] is not particularly limited, but can be appropriately selected from a range of, for example, 5 or more (for example, 5 or more and 500 or less).
• the lower limit of the above ratio [T3 body/T2 body] is preferably 20, more preferably 21, more preferably 23, and even more preferably 25.
• the upper limit of the above ratio [T3 body/T2 body] is preferably 500, more preferably 100, more preferably 50, and even more preferably 40.
• the above ratio [T3/T2] is preferably 500 or less, compatibility with other components in the hard coating agent is improved and viscosity is also suppressed, making it easier to handle and easier to apply as a hard coating agent.
• the structural unit represented by the above formula (I) is represented by the following formula (I') in more detail.
• the structural unit represented by the above formula (II) is represented by the following formula (II').
• the three oxygen atoms bonded to the silicon atom shown in the structure represented by the following formula (I') are each bonded to another silicon atom (a silicon atom not shown in formula (I')).
• the two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (II') are each bonded to another silicon atom (a silicon atom not shown in formula (II')). That is, the above T3 body and T2 body are both structural units (T units) formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound.
• R a in the above formula (I) (R a in formula (I') is also the same) and R b in formula (II) (R b in formula (II') are also the same) each represent a group containing an active energy ray-curable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom.
• R a and R b include the same as R 1 in the above formula (1) and R 2 in the above formula (2).
• R a in formula (I) and R b in formula (II) each originate from a group (a group other than an alkoxy group and a halogen atom; for example, R 1 , R 2 , a hydrogen atom, etc. in the formulas (a) to (c) described below) bonded to a silicon atom in the hydrolyzable trifunctional silane compound used as a raw material for the polyorganosilsesquioxane of the present disclosure.
• R c in the above formula (II) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• alkyl group having 1 to 4 carbon atoms include a linear or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group.
• the alkyl group in R c in formula (II) is generally derived from an alkyl group that forms an alkoxy group (for example, an alkoxy group as X 1 to X 3 described below) in the hydrolyzable silane compound used as a raw material for the polyorganosilsesquioxane of the present disclosure.
• the ratio [T3 form/T2 form] in the polyorganosilsesquioxane of the present disclosure can be determined, for example, by 29 Si-NMR spectrum measurement.
• the silicon atom in the constitutional unit (T3 form) represented by the above formula (I) and the silicon atom in the constitutional unit (T2 form) represented by the above formula (II) show signals (peaks) at different positions (chemical shifts), so the ratio [T3 form/T2 form] can be determined by calculating the integral ratio of these respective peaks.
• the polyorganosilsesquioxane of the present disclosure has a structural unit represented by the above formula (1) and R 1 is a 2-(3',4'-epoxycyclohexyl)ethyl group
• the signal of the silicon atom in the structure represented by the above formula (I) (T3 body) appears at -64 to -70 ppm
• the signal of the silicon atom in the structure represented by the above formula (II) (T2 body) appears at -54 to -60 ppm.
• the ratio [T3 body/T2 body] can be obtained by calculating the integral ratio of the signal (T3 body) at -64 to -70 ppm and the signal (T2 body) at -54 to -60 ppm.
• R 1 is a group containing an active energy ray-curable functional group other than the 2-(3',4'-epoxycyclohexyl)ethyl group
• [T3 body/T2 body] can be obtained in the same manner.
• the 29 Si-NMR spectrum of the polyorganosilsesquioxane of the present disclosure can be measured, for example, using the following apparatus and conditions.
• Measuring device Product name "JNM-ECA500NMR” (manufactured by JEOL Ltd.)
• Solvent deuterated chloroform Number of measurements: 1800 Measurement temperature: 25°C
• T2 the ratio [T3/T2] of the polyorganosilsesquioxane of the present disclosure is within the above range (e.g., 5 or more and 500 or less), it means that a certain amount of T2 isomer is present relative to the T3 isomer in the polyorganosilsesquioxane of the present disclosure.
• T2 isomers include a constitutional unit represented by the following formula (4), a constitutional unit represented by the following formula (5), and a constitutional unit represented by the following formula (6).
• R 1 in the following formula (4) and R 2 in the following formula (5) are the same as R 1 in the above formula (1) and R 2 in the above formula (2), respectively.
• R c in the following formulas (4) to (6) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, as with R c in formula (II).
• the polyorganosilsesquioxane of the present disclosure may have any of the following silsesquioxane structures: cage type, incomplete cage type, ladder type, and random type, and may have a combination of two or more of these silsesquioxane structures.
• the ratio (total amount) of the structural unit represented by the above formula (1) and the structural unit represented by the above formula (4) to the total amount of siloxane structural units [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%) is not particularly limited, but is preferably 55 to 100 mol%, more preferably 65 to 100 mol%, and even more preferably 80 to 99 mol%.
• the ratio of each siloxane structural unit in the polyorganosilsesquioxane of the present disclosure can be calculated, for example, from the composition of the raw materials or NMR spectrum measurement.
• the ratio (total amount) of the structural units represented by the above formula (2) and the structural units represented by the above formula (5) to the total amount of siloxane structural units [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%) in the polyorganosilsesquioxane of the present disclosure is not particularly limited, but is preferably 0 to 70 mol%, more preferably 0 to 60 mol%, even more preferably 0 to 40 mol%, and particularly preferably 1 to 15 mol%.
• the proportions of the structural units represented by formula (1) and the structural units represented by formula (4) can be relatively increased, which improves the curability of the hard coat agent and tends to increase the scratch resistance and toughness of the cured product (coating film).
• the proportion (total amount) of the constituent units represented by the above formula (1), the constituent units represented by the above formula (2), the constituent units represented by the above formula (4), and the constituent units represented by the above formula (5) relative to the total amount of siloxane constituent units [total siloxane constituent units; total amount of M units, D units, T units, and Q units] (100 mol%) in the polyorganosilsesquioxane of the present disclosure is not particularly limited, but is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and even more preferably 80 to 100 mol%. By making the above proportion 60 mol% or more, the scratch resistance and toughness of the cured product (coating film) tend to be higher.
• the number average molecular weight (Mn) of the polyorganosilsesquioxane of the present disclosure is not particularly limited, but can be appropriately selected, for example, from the range of 1,000 to 50,000.
• the lower limit of the number average molecular weight is preferably 1,500, more preferably 1,800, and even more preferably 2,000.
• the upper limit of the number average molecular weight is preferably 50,000, more preferably 10,000, and even more preferably 8,000.
• the molecular weight dispersity (Mw/Mn) of the polyorganosilsesquioxane of the present disclosure is not particularly limited, but can be appropriately selected from the range of 1.0 to 4.0.
• the lower limit of the molecular weight dispersity is preferably 1.0, more preferably 1.1, and even more preferably 1.2.
• the upper limit of the molecular weight dispersity is preferably 4.0, more preferably 3.0, and even more preferably 2.5.
• the number average molecular weight and molecular weight dispersity of the polyorganosilsesquioxane of the present disclosure can be measured using the following apparatus and conditions.
• Measuring device Product name "LC-20AD” (manufactured by Shimadzu Corporation) Columns: Shodex KF-801 x 2, KF-802, and KF-803 (Showa Denko) Measurement temperature: 40°C Eluent: THF, sample concentration 0.1 to 0.2% by mass Flow rate: 1 mL/min
• Detector UV-VIS detector (product name "SPD-20A", manufactured by Shimadzu Corporation) Molecular weight: Standard polystyrene equivalent
• the 5% weight loss temperature (T d5 ) of the polyorganosilsesquioxane of the present disclosure in an air atmosphere is not particularly limited, but is preferably 330° C. or higher (for example, 330 to 450° C.), more preferably 340° C. or higher, and even more preferably 350° C. or higher.
• T d5 The 5% weight loss temperature of the polyorganosilsesquioxane of the present disclosure in an air atmosphere is not particularly limited, but is preferably 330° C. or higher (for example, 330 to 450° C.), more preferably 340° C. or higher, and even more preferably 350° C. or higher.
• the 5% weight loss temperature is 330° C. or higher, the scratch resistance and toughness of the cured product (coating film) tend to be further improved.
• the 5% weight loss temperature is controlled to 330° C. or higher.
• the 5% weight loss temperature is the temperature at which the weight before heating is reduced by 5% when heated at a constant heating rate, and is an index of heat resistance.
• the 5% weight loss temperature can be measured by TGA (thermogravimetric analysis) under conditions of an air atmosphere and a temperature rise rate of 5° C./min.
• the polyorganosilsesquioxane of the present disclosure can be produced by known or conventional methods for producing polysiloxanes, and is not particularly limited, but can be produced, for example, by a method of hydrolyzing and condensing one or more hydrolyzable silane compounds.
• a hydrolyzable trifunctional silane compound (a compound represented by the following formula (a)) as the essential hydrolyzable silane compound for forming the structural unit represented by the above formula (1).
• the polyorganosilsesquioxane of the present disclosure can be produced by a method of hydrolyzing and condensing a compound represented by the following formula (a), which is a hydrolyzable silane compound for forming a silsesquioxane constituent unit (T unit) in the polyorganosilsesquioxane of the present disclosure, and, if necessary, a compound represented by the following formula (b) and a compound represented by the following formula (c).
• a is a hydrolyzable silane compound for forming a silsesquioxane constituent unit (T unit) in the polyorganosilsesquioxane of the present disclosure
• the compound represented by the above formula (a) is a compound that forms a structural unit represented by formula (1) in the polyorganosilsesquioxane of the present disclosure.
• R 1 in formula (a) represents a group containing an active energy ray-curable functional group, like R 1 in formula (1).
• R 1 in formula (a) a group represented by the above formula (1a), a group represented by the above formula (1b), a group represented by the above formula (1c), or a group represented by the above formula (1d) is preferable, more preferably a group represented by the above formula (1a), a group represented by the above formula (1c), even more preferably a group represented by the above formula (1a), and particularly preferably a group represented by the above formula (1a), in which R 1a is an ethylene group [among which, a 2-(3',4'-epoxycyclohexyl)ethyl group].
• R 1 in formula (a) a 3-(acryloxy)propyl group and a 3-(methacryloxy)propyl group are also preferable.
• X 1 in the above formula (a) represents an alkoxy group or a halogen atom.
• the alkoxy group in X 1 include alkoxy groups having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, and an isobutyloxy group.
• the halogen atom in X 1 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
• X 1 is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group.
• the three X 1 may be the same or different from each other.
• the compound represented by the above formula (b) is a compound forming a structural unit represented by formula (2) in the polyorganosilsesquioxane of the present disclosure.
• R 2 in formula (b) is the same as R 2 in the above formula (2), and represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group.
• a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group is preferable, more preferably a substituted or unsubstituted aryl group, and even more preferably a phenyl group.
• X2 in the above formula (b) represents an alkoxy group or a halogen atom.
• Specific examples of X2 include those exemplified as X1 .
• X2 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
• the three X2 may be the same or different.
• the compound represented by the above formula (c) is a compound that forms a structural unit represented by formula (3) in the polyorganosilsesquioxane of the present disclosure.
• X3 in the above formula (c) represents an alkoxy group or a halogen atom.
• Specific examples of X3 include those exemplified as X1 .
• X3 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
• the three X3 may be the same or different.
• the hydrolyzable silane compound may be used in combination with hydrolyzable silane compounds other than the compounds represented by the above formulas (a) to (c).
• hydrolyzable silane compound examples include hydrolyzable trifunctional silane compounds other than the compounds represented by the above formulas (a) to (c), hydrolyzable monofunctional silane compounds that form M units, hydrolyzable difunctional silane compounds that form D units, and hydrolyzable tetrafunctional silane compounds that form Q units.
• the amount and composition of the hydrolyzable silane compound used can be adjusted as appropriate depending on the desired structure of the polyorganosilsesquioxane of the present disclosure.
• the amount of the compound represented by formula (a) used is not particularly limited, but is preferably 55 to 100 mol%, more preferably 65 to 100 mol%, and even more preferably 80 to 99 mol% relative to the total amount (100 mol%) of the hydrolyzable silane compound used.
• the amount of the compound represented by formula (b) used is not particularly limited, but is preferably 0 to 70 mol%, more preferably 0 to 60 mol%, even more preferably 0 to 40 mol%, and particularly preferably 1 to 15 mol%, based on the total amount (100 mol%) of the hydrolyzable silane compounds used.
• the ratio (total ratio) of the compound represented by formula (a) and the compound represented by formula (b) to the total amount (100 mol%) of the hydrolyzable silane compounds used is not particularly limited, but is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, and even more preferably 80 to 100 mol%.
• hydrolysis and condensation reactions of these hydrolyzable silane compounds can be carried out simultaneously or sequentially.
• the order in which the reactions are carried out is not particularly limited.
• the hydrolysis and condensation reaction of the hydrolyzable silane compound may be carried out in one step or in two or more steps.
• the polyorganosilsesquioxane of the present disclosure having the ratio [T3/T2] of less than 20 and/or the number average molecular weight of less than 2500 (hereinafter, sometimes referred to as "low molecular weight polyorganosilsesquioxane"), it is preferable to carry out the hydrolysis and condensation reaction in one step.
• the polyorganosilsesquioxane of the present disclosure having the ratio [T3/T2] of 20 or more and/or the number average molecular weight of 2500 or more (hereinafter, sometimes referred to as "high molecular weight polyorganosilsesquioxane")
• a low molecular weight polyorganosilsesquioxane is obtained by performing hydrolysis and condensation reactions of a hydrolyzable silane compound in one step, and the low molecular weight polyorganosilsesquioxane is further subjected to hydrolysis and condensation reactions to obtain a high molecular weight polyorganosilsesquioxane, but the method for producing polyorganosilsesquioxane of the present disclosure is not limited to this.
• a low molecular weight polyorganosilsesquioxane having the above ratio [T3 form/T2 form] of 5 or more and less than 20 and a number average molecular weight of 1,000 or more and less than 2,500 is obtained, and in the second stage, the low molecular weight polyorganosilsesquioxane is subjected to further hydrolysis and condensation reactions to obtain a high molecular weight polyorganosilsesquioxane having the above ratio [T3 form/T2 form] of 20 or more and 500 or less and a number average molecular weight of 2,500 or more and 50,000 or less.
• the hydrolysis and condensation reaction in the first stage can be carried out in the presence or absence of a solvent. Of these, it is preferable to carry out the reaction in the presence of a solvent.
• a solvent examples include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, and dioxane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; nitriles such as acetonitrile, propionitrile, and benzonitrile; and alcohols such as methanol, ethanol, is
• the amount of solvent used in the first stage hydrolysis and condensation reaction is not particularly limited, and can be adjusted appropriately depending on the desired reaction time, etc., within the range of 0 to 2,000 parts by mass per 100 parts by mass of the total amount of hydrolyzable silane compound.
• the first stage hydrolysis and condensation reaction is preferably carried out in the presence of a catalyst and water.
• the catalyst may be an acid catalyst or an alkali catalyst, but an alkali catalyst is preferred in order to suppress decomposition of active energy ray-curable functional groups such as epoxy groups.
• the acid catalyst examples include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; phosphate esters; carboxylic acids such as acetic acid, formic acid, and trifluoroacetic acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid; solid acids such as activated clay; and Lewis acids such as iron chloride.
• mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid
• phosphate esters carboxylic acids such as acetic acid, formic acid, and trifluoroacetic acid
• sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid
• solid acids such as activated clay
• Lewis acids such as iron chloride.
• alkali catalyst examples include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; hydroxides of alkaline earth metals such as magnesium hydroxide, calcium hydroxide, and barium hydroxide; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; carbonates of alkaline earth metals such as magnesium carbonate; hydrogen carbonates of alkali metals such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and cesium hydrogen carbonate; organic acid salts of alkali metals such as lithium acetate, sodium acetate, potassium acetate, and cesium acetate (e.g., acetates); magnesium acetate, Examples of the catalyst include organic acid salts of alkaline earth metals such as tungsten (e.g., acetates); alkoxides of alkali metals such as lithium methoxide, sodium methoxide, sodium e
• the amount of the catalyst used in the first stage hydrolysis and condensation reaction is not particularly limited, and can be appropriately adjusted within the range of 0.002 to 0.200 moles per mole of the total amount of hydrolyzable silane compounds.
• the amount of water used in the first stage hydrolysis and condensation reaction is not particularly limited, and can be adjusted appropriately within the range of 0.5 to 20 moles per mole of the total amount of hydrolyzable silane compound.
• the method of adding the water in the first stage hydrolysis and condensation reaction is not particularly limited, and the entire amount of water to be used (total amount used) may be added all at once or may be added gradually. When added gradually, it may be added continuously or intermittently.
• reaction conditions for the first stage hydrolysis and condensation reaction it is particularly important to select reaction conditions such that the above ratio [T3/T2] in the low molecular weight polyorganosilsesquioxane is 5 or more and less than 20.
• the reaction temperature for the first stage hydrolysis and condensation reaction is not particularly limited, but is preferably 40 to 100°C, more preferably 45 to 80°C. By controlling the reaction temperature within the above range, the above ratio [T3/T2] tends to be more efficiently controlled to 5 or more and less than 20.
• the reaction time for the first stage hydrolysis and condensation reaction is not particularly limited, but is preferably 0.1 to 10 hours, more preferably 1.5 to 8 hours.
• the first stage hydrolysis and condensation reaction can be performed under normal pressure, or under pressure or reduced pressure.
• the atmosphere in which the first stage hydrolysis and condensation reaction is performed is not particularly limited, and may be, for example, a nitrogen atmosphere, an inert gas atmosphere such as an argon atmosphere, or an air atmosphere in the presence of oxygen, but an inert gas atmosphere is preferable.
• the first stage hydrolysis and condensation reaction produces a low molecular weight polyorganosilsesquioxane.
• the low molecular weight polyorganosilsesquioxane may be separated and purified by, for example, washing with water, washing with an acid, washing with an alkali, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination of these separation methods.
• the low molecular weight polyorganosilsesquioxane obtained by the first stage hydrolysis and condensation reaction can be subjected to the second stage hydrolysis and condensation reaction to produce a high molecular weight polyorganosilsesquioxane.
• the second stage hydrolysis and condensation reaction can be performed in the presence or absence of a solvent.
• the solvents listed for the first stage hydrolysis and condensation reaction can be used.
• the solvent for the second stage hydrolysis and condensation reaction the low molecular weight polyorganosilsesquioxane containing the reaction solvent for the first stage hydrolysis and condensation reaction, the extraction solvent, etc., can be used as it is or after partially distilling off. Note that the solvent can be used alone or in combination of two or more types.
• the amount of the solvent used is not particularly limited, and can be adjusted appropriately depending on the desired reaction time, etc., within the range of 0 to 2,000 parts by mass per 100 parts by mass of low molecular weight polyorganosilsesquioxane.
• the second stage hydrolysis and condensation reaction is preferably carried out in the presence of a catalyst and water.
• the catalyst may be any of those listed for the first stage hydrolysis and condensation reaction.
• an alkali catalyst is preferred, and more preferred are alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and cesium hydroxide; and alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate.
• the catalyst may be used alone or in combination of two or more types.
• the catalyst may also be used in a state dissolved or dispersed in water, a solvent, or the like.
• the amount of the catalyst used in the second stage hydrolysis and condensation reaction is not particularly limited, and can be appropriately adjusted within the range of preferably 0.01 to 10,000 ppm, more preferably 0.1 to 1,000 ppm, relative to the low molecular weight polyorganosilsesquioxane (1,000,000 ppm).
• the amount of water used in the second stage hydrolysis and condensation reaction is not particularly limited, and can be adjusted appropriately within the range of preferably 10 to 100,000 ppm, and more preferably 100 to 20,000 ppm, relative to the low molecular weight polyorganosilsesquioxane (1,000,000 ppm). If the amount of water used is greater than 100,000 ppm, it tends to be difficult to control the ratio of high molecular weight polyorganosilsesquioxane [T3 form/T2 form] and the number average molecular weight within the specified range.
• the method of adding the water in the second stage hydrolysis and condensation reaction is not particularly limited, and the entire amount of water to be used (total amount used) may be added all at once or may be added gradually. When added gradually, it may be added continuously or intermittently.
• reaction conditions for the second stage hydrolysis and condensation reaction it is particularly important to select reaction conditions such that the ratio [T3/T2] in the high molecular weight polyorganosilsesquioxane is 20 or more and 500 or less, and the number average molecular weight is 2500 to 50000.
• the reaction temperature for the second stage hydrolysis and condensation reaction varies depending on the catalyst used and is not particularly limited, but is preferably 5 to 200°C, and more preferably 30 to 100°C. By controlling the reaction temperature within the above range, the ratio [T3/T2] and the number average molecular weight tend to be more efficiently controlled within the desired range.
• reaction time for the second stage hydrolysis and condensation reaction is not particularly limited, but is preferably 0.5 to 1000 hours, and more preferably 1 to 500 hours.
• reaction time for the second stage hydrolysis and condensation reaction is not particularly limited, but is preferably 0.5 to 1000 hours, and more preferably 1 to 500 hours.
• by carrying out the hydrolysis and condensation reactions within the above reaction temperature range, and sampling at appropriate times while monitoring the above ratio [T3/T2] and number average molecular weight it is possible to obtain a high molecular weight polyorganosilsesquioxane having the desired ratio [T3/T2] and number average molecular weight.
• the second stage hydrolysis and condensation reaction can be carried out under normal pressure, or under increased or reduced pressure.
• the atmosphere in which the second stage hydrolysis and condensation reaction is carried out is not particularly limited, and may be, for example, a nitrogen atmosphere, an inert gas atmosphere such as an argon atmosphere, or an air atmosphere in the presence of oxygen, but an inert gas atmosphere is preferred.
• the second stage hydrolysis and condensation reaction produces a high molecular weight polyorganosilsesquioxane.
• the high molecular weight polyorganosilsesquioxane may be separated and purified by, for example, washing with water, washing with an acid, washing with an alkali, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination of these separation methods.
• a hard coat agent containing the above-mentioned polyorganosilsesquioxane as an essential component can be applied and cured to form a cured product (coating film) with excellent scratch resistance and toughness.
• the polyorganosilsesquioxanes disclosed herein can be used alone or in combination of two or more types.
• the content (mixture amount) of the polyorganosilsesquioxane of the present disclosure in the hard coating agent is not particularly limited, but is preferably 70% by mass or more and less than 100% by mass, more preferably 80 to 99.8% by mass, and even more preferably 90 to 99.5% by mass, relative to the total amount (100% by mass) of the hard coating agent excluding the solvent.
• the content of the polyorganosilsesquioxane of the present disclosure 70% by mass or more, the scratch resistance and toughness of the cured product (coating film) tend to be further improved.
• a curing agent can be contained, which tends to allow the curing of the hard coating agent to proceed more efficiently.
• the ratio of the polyorganosilsesquioxane of the present disclosure to the total amount (100 mass%) of the photocationically curable compound or photoradically curable compound contained in the hard coat agent is not particularly limited, but is preferably 70 to 100 mass%, more preferably 75 to 98 mass%, and even more preferably 80 to 95 mass%.
• the hard coat agent preferably further contains a curing agent to promote the curing reaction caused by irradiation with activation energy rays.
• a curing agent to promote the curing reaction caused by irradiation with activation energy rays.
• the hard coat agent contains a photocationic polymerization initiator or a photoradical polymerization initiator as the curing agent, since this can shorten the curing time required to become tack-free.
• the photocationic polymerization initiator may be the same as that disclosed in the photocurable composition described above.
• the photoradical polymerization initiator is a compound that can initiate or accelerate the photoradical polymerization reaction of the photoradical curable compound, such as the polyorganosilsesquioxane disclosed herein.
• Examples of the photoradical polymerization initiator include 2-amino-2-benzoxanthone, such as benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyl disulfite, methyl orthobenzoylbenzoate, ethyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2-methyl-1-[4-(methyl)phenyl]-2-morpholinopropanone-1, 1-hydroxycyclohexyl phenyl ketone, and 2-dimethylamino-2-(4-morpholino)benzoyl-1-phenylpropane.
• 2-amino-2-benzoxanthone such as benzophenone
• Examples of the compound include aminobenzene derivatives such as tetra(t-butylperoxycarbonyl)benzophenone, benzil, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 4,4-bisdiethylaminobenzophenone, imidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole, halomethylated triazine compounds such as 2,6-bis(trichloromethyl)-4-(4-methoxynaphthalen-1-yl)-1,3,5-triazine, and halomethyloxadiazole compounds such as 2-trichloromethyl-5-(2-benzofuran 2-yl-ethenyl)-1,3,4-oxadiazole. If necessary, a photosensitizer can be added.
• imidazole compounds such as 2,2'-bis(2-chlorophenyl)
• the above curing agents can be used alone or in combination of two or more.
• the content (mixture amount) of the curing agent in the hard coat agent is not particularly limited, but is preferably 0.01 to 10.0 parts by mass, more preferably 0.05 to 5.0 parts by mass, and even more preferably 0.1 to 3.0 parts by mass, relative to the total amount (100 parts by mass; total amount of active energy ray curing compounds) of the polyorganosilsesquioxane of the present disclosure and the other active energy ray curing compounds described below.
• the content of the curing agent 0.01 parts by mass or more, the curing reaction can be efficiently and sufficiently progressed, and the scratch resistance and toughness of the cured product (coating film) tend to be further improved.
• the content of the curing agent 5.0 parts by mass or less the storage stability of the hard coat agent tends to be further improved and coloring of the cured product (coating film) tends to be suppressed.
• the hard coat agent may further contain an active energy ray curable compound other than the polyorganosilsesquioxane of the present disclosure (sometimes referred to as "other active energy ray curable compounds").
• active energy ray curable compounds include photocationically curable compounds other than the polyorganosilsesquioxane of the present disclosure (sometimes referred to as “other photocationically curable compounds”) and/or photoradical curable compounds other than the polyorganosilsesquioxane of the present disclosure (sometimes referred to as "other photoradical curable compounds”).
• the other photocationically curable compounds may be publicly known or commonly used photocationically curable compounds, and may include, but are not limited to, epoxy compounds other than the polyorganosilsesquioxanes disclosed herein, oxetane compounds, vinyl ether compounds, and the like.
• the other photocationically curable compounds may be used alone or in combination of two or more.
• the above epoxy compounds and oxetane compounds can be exemplified by the same compounds as those described above in the photocurable composition.
• the vinyl ether compound may be any known or conventional compound having one or more vinyl ether groups in the molecule, and is not particularly limited.
• the vinyl ether compound include, but are not limited to, 2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether), 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1,6-hexanediol divinyl ether, 1 ,8-octanediol divinyl ether, 1,4-cyclohexane
• an epoxy compound as another photocationically curable compound together with the polyorganosilsesquioxane of the present disclosure.
• the other photoradical curing compounds may be any known or commonly used photoradical curing compounds, and may include, but are not limited to, compounds having one or more photoradical polymerizable groups in one molecule, such as (meth)acrylic groups, (meth)acryloxy groups, (meth)acrylamino groups, vinyl ether groups, vinylaryl groups, and vinyloxycarbonyl groups, other than the polyorganosilsesquioxanes disclosed herein. Note that the other photoradical curing compounds in the hard coat agent may be used alone or in combination of two or more.
• Examples of compounds having one or more (meth)acrylic groups in one molecule include 1-buten-3-one, 1-penten-3-one, 1-hexen-3-one, 4-phenyl-1-buten-3-one, 5-phenyl-1-penten-3-one, and derivatives thereof.
• Examples of compounds having one or more (meth)acryloxy groups in one molecule include monomers or oligomers having one or more (meth)acryloxy groups in one molecule.
• Monomers having one or more (meth)acryloxy groups in one molecule include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, n-butoxyethyl (meth)acrylate, butoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and methoxypolyethylene glycol.
• oligomers having one or more (meth)acryloxy groups in one molecule include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyether (meth)acrylate oligomers, and polyester (meth)acrylate oligomers.
• urethane (meth)acrylate oligomers examples include polycarbonate-based urethane (meth)acrylates, polyester-based urethane (meth)acrylates, polyether-based urethane (meth)acrylates, and caprolactone-based urethane (meth)acrylates.
• Urethane (meth)acrylate oligomers can be obtained by reacting an isocyanate compound obtained by reacting a polyol with a diisocyanate with a (meth)acrylate monomer having a hydroxyl group.
• the polyols include polycarbonate diols, polyester polyols, polyether polyols, and polycaprolactone polyols.
• Epoxy (meth)acrylate oligomers can be obtained, for example, by the esterification reaction of the oxirane ring of low molecular weight bisphenol-type epoxy resin or novolac epoxy resin with acrylic acid.
• Polyether (meth)acrylate oligomers are obtained by first subjecting polyols to a dehydration condensation reaction to obtain polyether oligomers with hydroxyl groups at both ends, and then esterifying the hydroxyl groups at both ends with acrylic acid.
• Polyester (meth)acrylate oligomers can be obtained, for example, by condensing a polycarboxylic acid with a polyol to obtain a polyester oligomer having hydroxyl groups at both ends, and then esterifying the hydroxyl groups at both ends with acrylic acid.
• the weight average molecular weight of an oligomer having one or more (meth)acryloxy groups in one molecule is preferably 100,000 or less, and more preferably 500 to 50,000.
• Examples of compounds having one or more (meth)acrylamino groups in one molecule include 4-(meth)acrylmorpholine, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-n-butoxymethyl(meth)acrylamide, N-hexyl(meth)acrylamide, N-octyl(meth)acrylamide, and derivatives thereof.
• Examples of compounds having one or more vinyl ether groups in one molecule include 3,3-bis(vinyloxymethyl)oxetane, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol
• Examples of the vinyl ethers include methanol monovinyl ether, 1,2-cyclohexanedimethanol monovinyl ether
• Compounds that have one or more vinylaryl groups in one molecule include styrene, divinylbenzene, methoxystyrene, ethoxystyrene, hydroxystyrene, vinylnaphthalene, vinylanthracene, 4-vinylphenyl acetate, (4-vinylphenyl)dihydroxyborane, N-(4-vinylphenyl)maleimide, and derivatives thereof.
• Compounds having one or more vinyloxycarbonyl groups in one molecule include isopropenyl formate, isopropenyl acetate, isopropenyl propionate, isopropenyl butyrate, isopropenyl isobutyrate, isopropenyl caproate, isopropenyl valerate, isopropenyl isovalerate, isopropenyl lactate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl pivalate, vinyl octylate, vinyl monochloroacetate, divinyl adipate, vinyl acrylate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl benzoate, vinyl cinnamate, and derivatives thereof.
• the other active energy ray-curable compounds in the hard coat agent can be used alone or in combination of two or more.
• the content (mixture amount) thereof is not particularly limited, but is preferably 3 to 50 mass% relative to the total amount of the polyorganosilsesquioxane of the present disclosure and other active energy ray curable compounds (100 mass%; total amount of active energy ray curable compounds), more preferably 5 to 40 mass%, and even more preferably 7 to 30 mass%.
• the content of other active energy ray curable compounds 50 mass% or less the scratch resistance and toughness of the cured product (coating film) tend to be further improved.
• the content of other active energy ray curable compounds 3 mass% or more it may be possible to impart the desired performance (for example, fast curing property and viscosity adjustment for the hard coat agent) to the hard coat agent or the cured product (coating film).
• the hard coat agent contains a vinyl ether compound (particularly, a vinyl ether compound having one or more hydroxyl groups in the molecule), its content (mixture amount) is not particularly limited, but is preferably 0.01 to 10 mass% relative to the total amount of the polyorganosilsesquioxane of the present disclosure and other active energy ray curable compounds (100 mass%; total amount of active energy ray curable compounds), more preferably 0.05 to 9 mass%, and even more preferably 1 to 8 mass%.
• a vinyl ether compound particularly, a vinyl ether compound having one or more hydroxyl groups in the molecule
• its content is not particularly limited, but is preferably 0.01 to 10 mass% relative to the total amount of the polyorganosilsesquioxane of the present disclosure and other active energy ray curable compounds (100 mass%; total amount of active energy ray curable compounds), more preferably 0.05 to 9 mass%, and even more preferably 1 to 8 mass%.
• the surface hardness of the cured product (coating film) becomes higher, and even when the irradiation amount of active energy rays (e.g., ultraviolet rays) is reduced, a cured product (coating film) with a very high surface hardness tends to be obtained.
• the surface hardness of the cured product (coating film) tends to be particularly high.
• the hard coat agent preferably contains an antioxidant.
• the hard coat agent contains an antioxidant, the hardness of the cured product (coating film) tends to be further improved.
• antioxidant known or conventional antioxidants can be used, and examples include, but are not limited to, phenol-based antioxidants (phenol-based compounds), hindered amine-based antioxidants (hindered amine-based compounds), phosphorus-based antioxidants (phosphorus-based compounds), sulfur-based antioxidants (sulfur-based compounds), etc.
• phenol-based antioxidants include, for example, monophenols such as 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, and stearyl- ⁇ -(3,5-di-t-butyl-4-hydroxyphenyl)propionate; 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), and 3,9-bis[1,1-dimethyl-2- ⁇ -(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy ⁇ ethyl]2,4,8 , 10-tetraoxaspiro[5.5]undecane and other monophenols such as 2,
• hindered amine antioxidant examples include bis(1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidylsebacate, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine.
• Examples of the phosphorus-based antioxidants include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, tris(2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bis(octadecyl) phosphite, cyclic neopentane tetrayl bis(2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetrayl bis(2 ,4-di-t-butyl-4-methylphenyl)phosphite, bis[2-t-butyl-6-methyl-4-
• sulfur-based antioxidants examples include dodecanethiol, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate.
• the antioxidants preferably include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants, and more preferably, phenol-based antioxidants.
• the antioxidants may be used alone or in combination of two or more.
• the hard coat agent contains an antioxidant
• its content is not particularly limited, but is preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, relative to the total amount (100 parts by mass) of the active energy ray-curable compounds contained in the hard coat agent. If the antioxidant content is less than 0.05 parts by mass, the hardness of the cured product (coating film) may be insufficient. On the other hand, if the antioxidant content exceeds 5 parts by mass, the cured product (coating film) may be easily discolored.
• the hard coat agent preferably contains a compound having one or more thermally polymerizable functional groups and one or more photopolymerizable functional groups in one molecule (hereinafter, may be referred to as "compound A").
• compound A a compound having one or more thermally polymerizable functional groups and one or more photopolymerizable functional groups in one molecule.
• thermally polymerizable functional group possessed by compound A is not particularly limited as long as it is a functional group that imparts polymerizability to compound A by heat, but examples thereof include hydroxyl groups, epoxy groups, oxetanyl groups, vinyl ether groups, etc., and from the viewpoint of the surface hardness of the coating film of the present disclosure, hydroxyl groups and epoxy groups are preferred. Note that, when compound A has two or more thermally polymerizable functional groups, these thermally polymerizable functional groups may be the same or different.
• the "photopolymerizable functional group" possessed by compound A is not particularly limited as long as it is a functional group that imparts polymerizability to compound A by light (e.g., ultraviolet light), but examples include (meth)acryloyl groups and vinyl groups, and from the viewpoint of the surface hardness of the coating film of the present disclosure, (meth)acryloyl groups are preferred. Note that when compound A has two or more photopolymerizable functional groups, these photopolymerizable functional groups may be the same or different.
• the number of thermally polymerizable functional groups that compound A has in one molecule may be 1 or more, and is not particularly limited, but for example, 1 to 5 are preferred, more preferably 1 to 3, and even more preferably 1 or 2.
• the number of photopolymerizable functional groups that compound A has in one molecule may be 1 or more, and is not particularly limited, but for example, 1 to 5 are preferred, more preferably 1 to 3, and even more preferably 1 or 2.
• the functional group equivalent of the thermally polymerizable functional group of compound A is not particularly limited, but is preferably 50 to 500, more preferably 80 to 480, and even more preferably 120 to 450. If the functional group equivalent is less than 50, the hardness of the cured product (coating film) may be insufficient. On the other hand, if the functional group equivalent is more than 500, the surface hardness of the cured product (coating film) may decrease.
• the functional group equivalent of the photopolymerizable functional group of compound A is not particularly limited, but is preferably 50 to 500, more preferably 80 to 480, and even more preferably 120 to 450. If the functional group equivalent is less than 50, the hardness of the cured product (coating film) may be insufficient. On the other hand, if the functional group equivalent is more than 500, the surface hardness of the cured product (coating film) may decrease.
• compound A examples include 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl (meth)acrylate, tripropylene glycol diglycidyl ether di(meth)acrylate (a compound obtained by reacting both epoxy groups of tripropylene glycol diglycidyl ether with (meth)acrylic acid), tripropylene glycol diglycidyl ether half (meth)acrylate (a compound obtained by reacting one of the epoxy groups of tripropylene glycol diglycidyl ether with (meth)acrylic acid), bisphenol A epoxy di(meth)acrylate, ) acrylate (a compound obtained by reacting both epoxy groups of bisphenol A diglycidyl ether with (meth)acrylic acid), bisphenol A epoxy half (meth)acrylate (a compound obtained by reacting one epoxy group of bisphenol A diglycidyl ether with (meth)acrylic acid or a derivative thereof), bisphenol F epoxy di(meth)acrylate, bisphenol F
• compound A is preferably a compound having an epoxy group and/or a hydroxyl group as a thermally polymerizable functional group and a (meth)acryloyl group as a photopolymerizable functional group in one molecule, specifically, 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl (meth)acrylate, tripropylene glycol diglycidyl ether half (meth)acrylate, bisphenol A epoxy half (meth)acrylate, bisphenol F epoxy half (meth)acrylate, bisphenol S epoxy half (meth)acrylate, etc. are preferred.
• compound A can be used alone or in combination of two or more.
• Compound A can be produced by a known method, for example, by reacting a part of the thermally polymerizable functional groups of a compound having two or more thermally polymerizable functional groups (e.g., epoxy groups, hydroxyl groups) in one molecule with a carboxylic acid having a photopolymerizable functional group (e.g., acrylic acid, methacrylic acid, etc.) or a derivative thereof.
• a part of the thermally polymerizable functional groups of a compound having two or more thermally polymerizable functional groups e.g., epoxy groups, hydroxyl groups
• a carboxylic acid having a photopolymerizable functional group e.g., acrylic acid, methacrylic acid, etc.
• the content (mixture amount) of the compound A in the hard coat agent is not particularly limited, but is preferably 1.0 to 100 parts by mass, more preferably 1.3 to 75 parts by mass, and even more preferably 1.5 to 50 parts by mass, per 100 parts by weight of the total amount of the polyorganosilsesquioxane of the present disclosure and other active energy ray curable compounds (total amount of active energy ray curable compounds) in terms of solid content.
• the content of compound A 1 part by mass or more the hardness of the cured product (coating film) tends to be further improved.
• the surface hardness of the cured product (coating film) tends to be maintained.
• the hard coat agent preferably contains a fluorine-containing photopolymerizable resin.
• the fluorine-containing photopolymerizable resin is a resin (oligomer) having a fluorine-containing group such as a fluoroaliphatic hydrocarbon skeleton and a photopolymerizable functional group in the molecule.
• the hard coat agent contains a fluorine-containing photopolymerizable resin together with the polyorganosilsesquioxane and compound A of the present disclosure, the crosslink density of the coating film surface when cured can be effectively increased, and the cured product (coating film) has the property of improving the appearance such as the surface smoothness, and improving the surface hardness, scratch resistance, and stain resistance.
• the effect of the fluorine-containing photopolymerizable resin becomes remarkable when it is blended with compound A into the hard coat agent.
• the photopolymerizable functional group possessed by the fluorine-containing photopolymerizable resin may be the same as the "photopolymerizable functional group" possessed by the above-mentioned compound A, and from the viewpoint of the scratch resistance and stain resistance of the coating film of the present disclosure, a (meth)acryloyl group is preferred.
• these photopolymerizable functional groups may be the same or different.
• the number of photopolymerizable functional groups that the fluorine-containing photopolymerizable resin has in one molecule is not particularly limited as long as it is one or more, but for example, 1 to 5 are preferable, and 1 to 3 are more preferable.
• the "fluorine-containing group" of the fluorine-containing photopolymerizable resin is not particularly limited as long as it has a fluorine atom, and examples thereof include those having a fluoroaliphatic hydrocarbon skeleton.
• the fluoroaliphatic hydrocarbon skeleton include fluoro C 1-10 alkanes such as fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluoro t-butane, fluoropentane, and fluorohexane.
• fluoroaliphatic hydrocarbon skeletons may have at least some of the hydrogen atoms substituted with fluorine atoms, but perfluoroaliphatic hydrocarbon skeletons in which all hydrogen atoms are substituted with fluorine atoms are preferred, as this can improve the scratch resistance, slipperiness, and stain resistance of the coating film.
• the fluoroaliphatic hydrocarbon skeleton may form a polyfluoroalkylene ether skeleton, which is a repeating unit, via an ether bond.
• the fluoroaliphatic hydrocarbon group as a repeating unit may be at least one selected from the group consisting of fluoro C 1-4 alkylene groups such as fluoromethylene, fluoroethylene, fluoropropylene, and fluoroisopropylene.
• the repeating number (degree of polymerization) of the polyfluoroalkylene ether unit is, for example, 10 to 3,000, preferably 30 to 1,000, and more preferably 50 to 500.
• the fluorine-containing photopolymerizable resin may have a silicone-containing group in addition to the above-mentioned "photopolymerizable functional group" and "fluorine-containing group".
• the fluorine-containing photopolymerizable resin further has a silicone-containing group, the affinity with the polyorganosilsesquioxane of the present disclosure is improved, and the surface hardness, scratch resistance, and antifouling properties of the cured product (coating film) tend to be further improved.
• the silicone-containing group is a group having a polyorganosiloxane skeleton, and may be a polyorganosiloxane formed of M units, D units, T units, and Q units, but usually, a polyorganosiloxane formed of D units is preferably used.
• a polyorganosiloxane formed of D units is preferably used.
• the organic group of the polyorganosiloxane usually, a C 1-4 alkyl group or an aryl group is used, and a methyl group or a phenyl group (especially a methyl group) is commonly used.
• the number of repetitions of the siloxane unit is, for example, 2 to 3000, preferably 3 to 2000, and more preferably 5 to 1000.
• fluorine-containing photopolymerizable resins can be used alone or in combination of two or more.
• the content (mixture amount) of the fluorine-containing photopolymerizable resin in the hard coat agent is not particularly limited, but is, for example, 0.01 to 15 parts by mass, preferably 0.02 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and even more preferably 0.04 to 3 parts by mass, per 100 parts by weight of the total amount of the polyorganosilsesquioxane and other active energy ray curable compounds of the present disclosure (total amount of active energy ray curable compounds) in terms of solid content.
• the hard coat agent preferably contains a surface conditioner.
• a surface conditioner known or conventional compounds added for the purposes of defoaming, leveling, preventing popping, etc. can be used.
• defoaming agents, leveling agents, and anti-foaming agents can be, for example, aqueous or non-aqueous compounds whose main components are selected from polymers such as butadiene, acrylic, and olefin, or silicone-based main components such as silicone and fluorine-modified silicone.
• the content (mixture amount) of the surface conditioner in the hard coat agent is not particularly limited, but is, for example, 0.01 to 15 parts by mass, preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.2 to 3 parts by mass, per 100 parts by weight of the total amount of the polyorganosilsesquioxane and other active energy ray curable compounds of the present disclosure (total amount of active energy ray curable compounds) in terms of solid content.
• total amount of active energy ray curable compounds in terms of solid content.
• the hard coat agent may preferably further contain a solvent.
• a solvent there are no particular limitations on the solvent, so long as it can dissolve the polyorganosilsesquioxane of the present disclosure and additives used as necessary, and does not inhibit polymerization.
• the solvent used should be one that can provide a fluidity suitable for application to the hard coat layer and can be easily removed by heating at a temperature that can suppress the progress of polymerization. It is preferable to use one or more solvents with a boiling point (at 1 atmosphere) of 170°C or less (for example, aromatic solvents such as toluene, xylene, mesitylene, etc.; esters such as butyl acetate, etc.; ketones such as methyl isobutyl ketone, cyclohexanone, etc.; ethers such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.).
• aromatic solvents such as toluene, xylene, mesitylene, etc.
• esters such as butyl acetate, etc.
• ketones such as methyl isobutyl ketone, cyclohexanone, etc.
• ethers such as propylene glycol monomethyl ether, prop
• the solvent is preferably used in such a range that the concentration of non-volatile matter contained in the hard coating agent is, for example, about 5 to 100% by mass, preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass, in terms of excellent coatability.
• the amount added should be adjusted to an optimum amount that allows a suitable film thickness to be achieved, and is not limited to the above range. In other words, if too much solvent is used, the viscosity of the hard coating agent will tend to be low, making it difficult to form a coating film of a suitable thickness. On the other hand, if too little solvent is used, the viscosity of the hard coating agent will tend to be too high, making it difficult to apply it uniformly to the glass-substitute substrate.
• the hard coat agent may further contain, as optional components, inorganic fillers such as precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, boron nitride, etc.; inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes, organosilazanes, etc.; organic resin fine powders such as silicone resins, epoxy resins, fluororesins, etc.; conductive metal powders such as silver and copper, etc.; curing aids, stabilizers (light resistance stabilizers, heat stabilizers, heavy metal deactivators, etc.), ultraviolet absorbers (triazine-based ultraviolet absorbers, benzotriazine-based ultraviolet absorbers, etc.), and the like.
• inorganic fillers
• the composition may contain conventional additives such as sol-based UV absorbers, benzophenone-based UV absorbers, oxybenzophenone-based UV absorbers, salicylic acid ester-based UV absorbers, cyanoacrylate-based UV absorbers), flame retardants (phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants, etc.), flame retardant assistants, reinforcing materials (other fillers, etc.), nucleating agents, coupling agents (silane coupling agents, etc.), lubricants, waxes, plasticizers, release agents, impact resistance improvers, hue improvers, clarifying agents, rheology modifiers (flow improvers, etc.), processability improvers, colorants (dyes, pigments, etc.), antistatic agents, dispersants, surface modifiers (slip agents, etc.), matting agents, defoamers, foam inhibitors, defoamers, antibacterial agents, preservatives, viscosity modifiers, thickeners, photos
• the hard coat agent can be prepared by stirring and mixing the above components at room temperature or while heating as necessary, although there are no particular limitations to this.
• the hard coat agent can be used as a one-liquid composition in which the components are premixed and used as is, or as a multi-liquid (e.g., two-liquid) composition in which, for example, two or more components that have been stored separately are mixed in a predetermined ratio before use.
• the hard-coating agent is preferably liquid at room temperature (about 25°C), although there is no particular limitation. More specifically, the viscosity of the hard-coating agent at 25°C when diluted with 20% solvent [particularly, a hard-coating agent solution with a 20% methyl isobutyl ketone ratio] is preferably 300 to 20,000 mPa ⁇ s, more preferably 500 to 10,000 mPa ⁇ s, and even more preferably 1,000 to 8,000 mPa ⁇ s. By setting the viscosity at 300 mPa ⁇ s or more, the hard-coating agent tends to have a higher hardness (coating film).
• the hard-coating agent is easier to prepare and handle, and air bubbles tend not to remain in the hard-coating agent (coating film).
• the viscosity of the hard coating agent is measured using a viscometer (product name "MCR301", manufactured by Anton Paar) under conditions of an oscillation angle of 5%, a frequency of 0.1 to 100 (1/s), and a temperature of 25°C.
• the prepared hard coat agent is applied to the undercoat layer by a known or conventional method, followed by curing, to produce a laminate having a three-layer structure of a substrate, an undercoat layer, and a hard coat layer.
• the hard coat layer can be applied and cured by the same method as that exemplified for the undercoat layer.
• the cumulative irradiation amount is preferably about 1 to 5000 mJ/ cm2 .
• Specific curing conditions are not particularly limited, but for example, the hard coat agent is first heat-treated (pre-baked) at preferably 60° C. or higher, more preferably 120° C. or higher, and even more preferably 150° C. or higher, for preferably 10 seconds or more, more preferably 30 seconds or more, and even more preferably 60 seconds or more, then irradiated with ultraviolet light (irradiation conditions (irradiation amount): preferably 300 mJ/cm 2 or higher; irradiation intensity: 100 mW/cm 2 or higher), and finally, heat-treated (aged) preferably at 120° C. or higher for preferably 0.5 hours or more, thereby allowing the agent to be cured.
• the curing conditions are not limited to this range, and the pre-baking temperature, time, and aging temperature, time can be appropriately selected depending on the solvent used, and the ultraviolet irradiation conditions can also be appropriately selected depending on the curing agent used.
• the hard coating agent can be applied and cured to form a hard coating layer with high scratch resistance, surface hardness, and toughness.
• the laminate produced in this way has excellent adhesion while improving the surface hardness of the hard coating layer.
• the thickness of the hard coat layer is preferably 0.5 to 50 ⁇ m, more preferably 1 to 40 ⁇ m, and particularly preferably 3 to 30 ⁇ m. By having a surface hardness of 0.5 ⁇ m or more, it becomes easier to improve the surface hardness.
• the pencil hardness of the hard coat layer surface of the laminate is preferably 6H or more, more preferably 7H or more, and particularly preferably 8H or more.
• the pencil hardness can be evaluated according to the method described in JIS K5600-5-4 (750 g load). By having the pencil hardness of 6H or more, the laminate has sufficient surface hardness and tends to have excellent scratch resistance.
• the above laminate is scratched with a cutter blade at intervals of 1 mm from the hard coat layer side to create a grid of 100 squares, which are then attached with adhesive tape and peeled off at a 90° angle.
• 90 or more squares remain, more preferably 95 or more squares, and especially preferably 100 squares.
• An embodiment of the present disclosure includes a display device including the laminate.
• the laminate is arranged so that the hard coat layer constitutes the surface on the viewing side.
• the display device is not particularly limited, and examples thereof include organic EL display devices, inorganic EL display devices, and liquid crystal display devices.
• the display device has a hard coat layer surface with sufficient pencil hardness, so that the surface is less likely to be scratched.
• the display device can also be used as a flexible display that can be bent or rolled.
• Examples 1 to 6, Comparative Examples 1 to 9 A mixed solution having the compounding ratio shown in Table 1 was prepared and used as a photocurable composition.
• the photocurable composition obtained above was applied to the surface of a glass substrate (slide glass) using a wire bar #12 so that the thickness after curing was 10 ⁇ m, and then irradiated with ultraviolet light at an illuminance of 3000 mJ/cm 2 using an LED lamp. Then, the undercoat layer was prepared by heat treatment for 30 minutes in an oven at 150°C.
• Adhesion test According to JIS K5600-5-6, the surface of the undercoat layer was scratched with a cutter blade at intervals of 1 mm to create a grid of 100 squares, which were then attached with adhesive tape and peeled off in a 90° direction to visually check whether the coating surface adhered to the adhesive tape and then peeled off. If 90 or more squares were adhered, it was marked as ⁇ , and if less than 90 squares were adhered, it was marked as ⁇ .
• KR-470 Product name "KR-470” manufactured by Shin-Etsu Chemical Co., Ltd. (organosiloxane containing two or more alicyclic epoxy groups)
• A-1 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (alicyclic epoxy compound)
• A-2 3,4,3',4'-diepoxybicyclohexyl (alicyclic epoxy compound)
• YX7400N Product name "YX7400N” manufactured by Mitsubishi Chemical Corporation (aliphatic epoxy compound)
• Epolight 1600 Product name "Epolight 1600" 1,6-hexanediol glycidyl ether manufactured by Kyoei Chemical Co., Ltd.
• OXT-101 (aliphatic epoxy compound) OXT-101: Product name "OXT-101” manufactured by Toagosei Co., Ltd. (oxetane compound) CPI-101A: Product name "CPI-101A” manufactured by San-Apro Co., Ltd. (photopolymerization initiator)
• Production Example 1 (Production of polyorganosilsesquioxane)
• a 1000-milliliter flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube 277.2 millimoles (68.30 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3.0 millimoles (0.56 g) of phenyltrimethoxysilane, and 275.4 g of acetone were charged under a nitrogen stream, and the temperature was raised to 50°C.
• the epoxy group-containing low molecular weight polyorganosilsesquioxane obtained was confirmed by 1H-NMR and 29 Si-NMR.
• the molecular weight of the product was measured using a Shimadzu LC-20AD pump, a Shodex RI-504 detector, Shodex GPC KF-602 and KF-603 columns, a Shodex GPC KF-G guard column, THF solvent, and at 40° C.
• the ratio of T2 and T3 isomers in the product [T3/T2] was measured by 29Si -NMR spectrum measurement using a JEOL ECA500 (500 MHz).
• 200PA-E5 Product name "Epoxy Ester 200PA-E5", manufactured by Kyoeisha Chemical Co., Ltd. (a compound having one or more thermally polymerizable functional groups and one or more photopolymerizable functional groups in one molecule)
• Epolight 1600N Product name "Epolight 1600N” manufactured by Kyoeisha Chemical Co., Ltd. (other photocationic curing compound)
• Omnirad 127 Product name "Omnirad 127", manufactured by IGM Resins B.V. (photoradical polymerization initiator)
• CPI-310FG Product name "CPI-310FG", manufactured by San-Apro Co., Ltd.
• Adeka STAB AO-02 Product name "Adeka STAB AO-02", manufactured by ADEKA Corporation (antioxidant)
• FT602A Product name "Ftergent 602", manufactured by NEOS Corporation (fluorine-containing photopolymerizable resin)
• KY1203 Product name "KY1203", manufactured by Shin-Etsu Chemical Co., Ltd. (surface conditioner)
• MIBK methyl isobutyl ketone (solvent)
• MEK methyl ethyl ketone (solvent)
• Examples 7 to 12 On the undercoat layers prepared in Examples 1 to 6, the hard coat agent prepared in Production Example 1 was further coated using a wire bar #24 so that the thickness of the hard coat layer after curing was 20 ⁇ m, and then the coating was left in an oven at 80° C. for 1 minute, left in an oven at 120° C. for 2 minutes, and then irradiated with ultraviolet light at an illuminance of 300 mJ/cm 2 using a high-pressure mercury lamp. The hard coat agent was then cured by heat treatment for 60 minutes in an oven at 120° C., to prepare the laminates of Examples 7 to 12.
• Adhesion Test The surface of the hard coat layer of the laminate was subjected to an adhesion test similar to that performed on the undercoat layer described above. A score of 0 indicates that 90 or more particles were adhered, and a score of x indicates that less than 90 particles were adhered.
• the photocurable composition of the present disclosure contains a first epoxy compound, which is an organosiloxane containing two or more alicyclic epoxy groups, a second epoxy compound, and a third epoxy compound or an oxetane compound, and it was confirmed that the photocurable composition can be easily applied to a substrate and exhibits sufficient adhesion when the content of the organosiloxane containing two or more alicyclic epoxy groups is 30 to 70 mass% based on the total amount of the composition excluding the solvent (Examples 1 to 6). On the other hand, it was confirmed that when the first epoxy compound was not contained or was contained in an excessive amount, the coating property to the substrate was poor (Comparative Examples 2 to 5, 7).
• a first epoxy compound which is an organosiloxane containing two or more alicyclic epoxy groups, a second epoxy compound, and a third epoxy compound or an oxetane compound
• a photocurable composition wherein the content of the first epoxy compound is 30 to 70 mass % based on the total amount of the curable compounds.
• Appendix 2 The photocurable composition according to claim 1, comprising the first epoxy compound, the second epoxy compound, and the oxetane compound.
• Appendix 3 The photocurable composition according to claim 1 or 2, wherein the content of the second epoxy compound is 20 to 60 mass% based on the total amount of the curable compounds.
• Appendix 10 10. The laminate according to any one of claims 7 to 9, wherein the hard coat layer has a surface with a pencil hardness of 6H or more.
• Appendix 11 11. The laminate according to any one of claims 7 to 10, wherein 100 squares are formed in a lattice pattern at intervals of 1 mm on a surface of the hard coat layer, and when an adhesive tape is attached and peeled off in a 90° direction, 90 or more squares remain.
• Appendix 12 A display device comprising the laminate according to any one of claims 7 to 11.

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• 2022
  • 2022-12-19 JP JP2022202436A patent/JP2024087549A/ja active Pending
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