Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
  • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
• • 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
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/47—Levelling agents
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/14—Protective coatings, e.g. hard coatings
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
• • 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

Definitions

• the present invention relates to a composition for forming a hard coat layer, a film, a laminate, a polarizing plate, and an image display device.
• Image display devices such as liquid crystal display devices and organic EL display devices typically use optical control films such as polarizing plates to eliminate problems such as external light reflection and background glare, and to improve image visibility.
• fluorine-based additives are generally added to the curable resin composition that forms the hard coat layer (see, for example, Patent Document 1), and these fluorine-based additives ensure the leveling of the surface of the resulting cured film.
• PFAS perfluoroalkyl compounds and polyfluoroalkyl compounds
• the problem to be solved by the present invention is to provide a composition for forming a hard coat layer that can form a hard coat layer having excellent smoothness.
• Another problem to be solved by the present invention is to provide a laminate and a polarizing plate that are provided with a hard coat layer that has excellent smoothness.
• a composition for forming a hard coat layer comprising an active energy ray-curable compound and a silicone-containing polymer
• the silicone-containing polymer is a composition for forming a hard coat layer that is a random copolymer having, as polymerization components, at least a polymerizable monomer (a1) having a group represented by the following general formula (a) and a weight average molecular weight in the range of 100 to 4,000, and a polymerizable monomer (a2) having one or more groups selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, a group containing a polyoxyalkylene chain, and a group containing a polyester chain:
• R 11 each independently represents an alkyl group having 1 to 6 carbon atoms or a group represented by —OSi(R 14 ) 3 (each R 14 independently
• composition for forming a hard coat layer wherein the polymerizable monomer (a1) is a compound represented by the following general formula (a1-1) and/or a compound represented by the following general formula (a1-2):
• R 11 , R 12 , R 13 and x are the same as R 11 , R 12 , R 13 and x in formula (a), respectively;
• R 15 is a hydrogen atom or a methyl group;
• L1 is a divalent organic group.
• the silicone-containing polymer contained in the composition for forming a hard coat layer of the present invention (hereinafter, may be simply referred to as the "silicone-containing polymer of the present invention") is a random copolymer having, as at least polymerization components, a polymerizable monomer (a1) having a group represented by the following general formula (a) and having a weight average molecular weight in the range of 100 to 4,000, and a polymerizable monomer (a2) having one or more selected from the group consisting of an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 18 carbon atoms, a group containing a polyoxyalkylene chain, and a group containing a polyester chain:
• R 11 each independently represents an alkyl group having 1 to 6 carbon atoms or a group represented by —OSi(R 14 ) 3 (each R 14 independently represents an alkyl group having 1 to 3 carbon atoms); R 12 is independently an alkyl group having 1 to 6 carbon atoms, R 13 is an alkyl group having 1 to 12 carbon atoms; x indicates the number of repetitions.
• the silicone-containing polymer of the present invention can function as a leveling agent, and by forming it into a random copolymer having polymerizable monomer (a1) and polymerizable monomer (a2) as at least the polymerization components, the silicone portion does not cause cissing in the coating film, preventing the occurrence of coating film defects.
• the term "polymerizable monomer” refers to a compound having a polymerizable unsaturated group
• the polymerizable monomer (a1) is preferably a compound represented by the following general formula (a1-1) and/or a compound represented by the following general formula (a1-2).
• R 11 , R 12 , R 13 and x are the same as R 11 , R 12 , R 13 and x in formula (a), respectively;
• R 15 is a hydrogen atom or a methyl group;
• L1 is a divalent organic group.
• the polymerizable monomer (a1) can be produced by a known method, and a commercially available product may also be used. Specific examples of the polymerizable monomer (a1) include ⁇ -(3-methacryloyloxy)propylpolydimethylsiloxane, 3-(methacryloyloxy)propyltris(trimethylsiloxy)silane, and 3-acryloyloxypropyltris(trimethylsiloxy)silane.
• the polymerizable monomer (a1) constituting the silicone-containing polymer of the present invention may be one type alone, or two or more types.
• the lower limit of the content of the polymerizable monomer (a1) in the polymerization components is, for example, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 30% by mass or more, or 40% by mass or more.
• the upper limit of the content of the polymerizable monomer (a1) is not particularly limited, but is, for example, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or less than 50% by mass.
• a preferred combination of the content of the polymerizable monomer (a1) in the polymerization components is in the range of 10 to 90% by mass.
• the content of the polymerizable monomer (a1) can be adjusted by the raw material charge ratio of the polymerizable monomer (a1) when producing the silicone-containing polymer.
• the alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (a2) may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, and a hexadecyl group.
• the alkyl group having 1 to 18 carbon atoms contained in the polymerizable monomer (a2) is preferably an alkyl group having 1 to 6 carbon atoms.
• the group containing a (poly)oxyalkylene chain contained in polymerizable monomer (a2) is a monovalent group containing a repeating oxyalkylene moiety or a divalent linking group containing a repeating oxyalkylene moiety.
• Examples of polymerizable monomers (a2) having an alkyl group with 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloyl group include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, s-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl ( Examples of suitable alkyl esters of (meth)acrylic acid having 1 to 18 carbon atoms include alkyl est
• Examples of polymerizable monomers (a2) having a phenylalkyl group having 7 to 18 carbon atoms or a phenoxyalkyl group having 7 to 18 carbon atoms and in which the polymerizable unsaturated group is a (meth)acryloyl group include benzyl (meth)acrylate, phenoxymethyl (meth)acrylate, and 2-phenoxyethyl (meth)acrylate.
• Examples of polymerizable monomers (a2) having an alkyl group having 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a vinyl ether group include alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether; and cycloalkyl vinyl ethers.
• alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl
• polymerizable monomers (a2) having an aromatic group with 6 to 18 carbon atoms examples include styrene, ⁇ -methylstyrene, p-methylstyrene, and p-methoxystyrene.
• Examples of polymerizable monomers (a2) having an alkyl group with 1 to 18 carbon atoms and in which the polymerizable unsaturated group is a maleimide group include methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, and cyclohexylmaleimide.
• Examples of the polymerizable monomer (a2) having a group containing a polyoxyalkylene chain and in which the polymerizable unsaturated group is a (meth)acryloyl group include polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polytrimethylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, poly(ethylene glycol-propylene glycol) mono(meth)acrylate, polyethylene glycol-polypropylene glycol mono(meth)acrylate, poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate, polyethylene glycol-polytetramethylene glycol Methylene glycol mono(meth)acrylate, poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate, polypropylene glycol-polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol-1,2-but
• poly(ethylene glycol-propylene glycol) means a random copolymer of ethylene glycol and propylene glycol
• polyethylene glycol-polypropylene glycol means a block copolymer of ethylene glycol and propylene glycol
• the polymerizable monomer (a2) is preferably at least one selected from the group consisting of compounds represented by the following general formula (a2-1), compounds represented by the following general formula (a2-2), compounds represented by the following general formula (a2-3), compounds represented by the following general formula (a2-4), and compounds represented by the following general formula (a2-5), and more preferably at least one selected from the group consisting of compounds represented by the following general formula (a2-1), compounds represented by the following general formula (a2-2), compounds represented by the following general formula (a2-3), and compounds represented by the following general formula (a2-4): These compounds exhibit high compatibility when the silicone-containing polymer of the present invention is used as a leveling agent.
• the m n's in the parentheses may be the same or different.
• the q p's in the parentheses may be the same or different.
• the q p's in the parentheses may be the same or different.
• the polymerizable monomer (a2) can be produced by a known method.
• Commercially available polymerizable monomers (a2) having a group containing a polyoxyalkylene chain and in which the polymerizable unsaturated group is a (meth)acryloyl group include "NK ESTER M-20G,”"NK ESTER M-40G,””NK ESTER M-90G,””NK ESTER M-230G,””NK ESTER AM-90G,””NK ESTER AMP-10G,””NK ESTER AMP-20G,” and “NK ESTER AMP-60G” manufactured by Shin-Nakamura Chemical Co., Ltd., and "BLEMMER PE-90,””BLEMMERPE-200,””BLEMMERPE-350,” and “BLEMMER PME-100” manufactured by NOF Corporation.
• the polymerizable monomer (a2) constituting the silicone-containing polymer of the present invention may be one type alone, or two or more types.
• the silicone-containing polymer of the present invention preferably does not contain a block copolymer in which a block having a structure derived from the polymerizable monomer (a1) and a block having a structure derived from the polymerizable monomer (a2) are linked together, and more preferably does not contain a block having a structure derived from the polymerizable monomer (a1) and/or a block having a structure derived from the polymerizable monomer (a2).
• the production of block polymers generally requires a metal catalyst, and the resulting block polymer contains unavoidable metal impurities.
• the silicone-containing polymer of the present invention is preferably a free-radical random copolymer that can be produced without the use of a metal catalyst.
• block copolymers generally requires complicated management. Specifically, adding the monomer that will form the second block when the polymerization rate of the first block is low can result in insufficient blocking, while adding the monomer that will form the second block when the polymerization rate of the first block is high can result in deactivation of the active terminals, preventing the polymerization reaction from proceeding sufficiently. In addition, measures must be taken to prevent the inclusion of substances that cause polymerization deactivation, such as oxygen, which inhibits blocking.
• the silicone-containing polymers of the present invention are also advantageous in that production management is not complicated.
• the silicone-containing polymer of the present invention may contain at least the polymerizable monomer (a1) and the polymerizable monomer (a2) as polymerization components, and may also contain other polymerizable monomers as polymerization components other than the polymerizable monomer (a1) and the polymerizable monomer (a2), as long as the effects of the present invention are not impaired.
• the silicone-containing polymer of the present invention is preferably a copolymer consisting essentially of polymerizable monomer (a1) and polymerizable monomer (a2), and more preferably a copolymer consisting only of polymerizable monomer (a1) and polymerizable monomer (a2).
• consisting essentially of refers to a case where the total content of polymerizable monomer (a1) and polymerizable monomer (a2) in the polymerization components is 75% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, or 99% by mass or more.
• the number average molecular weight (Mn) of the silicone-containing polymer of the present invention is preferably in the range of 1,000 to 100,000, more preferably in the range of 2,000 to 50,000, and even more preferably in the range of 2,000 to 20,000.
• the weight average molecular weight (Mw) of the silicone-containing polymer of the present invention is preferably in the range of 2,000 to 500,000, more preferably in the range of 3,000 to 100,000, and even more preferably in the range of 5,000 to 50,000.
• the upper limit of the weight average molecular weight (Mw) of the silicone-containing polymer of the present invention is preferably less than 10,000.
• the silicone-containing polymer of the present invention can also be produced by living polymerization, such as living radical polymerization or living anionic polymerization, using at least polymerizable monomer (a1) and polymerizable monomer (a2) as polymerization components.
• living polymerization such as living radical polymerization or living anionic polymerization, using at least polymerizable monomer (a1) and polymerizable monomer (a2) as polymerization components.
• Ligand compounds capable of coordinating to the transition metal of the above transition metal compounds include compounds having a ligand containing one or more nitrogen atoms, oxygen atoms, phosphorus atoms, or sulfur atoms that can coordinate to the transition metal via a ⁇ bond, compounds having a ligand containing two or more carbon atoms that can coordinate to the transition metal via a ⁇ bond, and compounds having a ligand that can coordinate to the transition metal via a ⁇ bond or ⁇ bond.
• the active energy ray-curable compound is a resin (polymer)
• examples of the active energy ray-curable resin include polyester resins, (meth)acrylic resins, urethane resins, (meth)acrylic urethane resins, amide resins, silicone resins, silicate resins, epoxy resins, melamine resins, and oxetane resins.
• (meth)acrylic resins, (meth)acrylic urethane resins, and epoxy resins are preferred because they have high hardness, can be cured with ultraviolet light, and are excellent in productivity, and (meth)acrylic resins and (meth)acrylic urethane resins are more preferred.
• active energy ray-curable acrylic monomers examples include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, EO-modified pentaerythritol tetra(meth)acrylate, PO-modified pentaerythritol tetra(meth)acrylate, and pentaerythritol tri(meth)acrylate.
• the active energy ray-curable acrylic monomer is preferably pentaerythritol tetra(meth)acrylate, EO-modified pentaerythritol tetra(meth)acrylate, PO-modified pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, or tricyclodecane dimethanol di(meth)acrylate.
• the active energy ray-curable compounds used may be one type alone, or two or more types may be used in combination.
• the content of the active energy ray-curable compound is, for example, in the range of 10 to 99 mass % of the solid content of the composition for forming a hard coat layer, and preferably in the range of 50 to 99 mass %.
• the term "solid content of the composition for forming a hard coat layer” means the total amount of components excluding the solvent from the composition for forming a hard coat layer when the composition for forming a hard coat layer contains a solvent.
• the composition for forming the hard coat layer preferably further contains fine particles, and the fine particles are dispersed in the hard coat layer.
• the fine particles include metal oxide fine particles such as silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide; organic fine particles made of transparent polymers such as polymethyl methacrylate, polystyrene, polyurethane, acrylic-styrene copolymer, benzoguanamine, melamine, and polycarbonate; glass fine particles; and silicone fine particles.
• the lower limit of the average particle diameter of the microparticles is, for example, 0.001 ⁇ m or more.
• the upper limit of the average particle diameter of the microparticles is, for example, 10 ⁇ m or less, preferably 1 ⁇ m or less, and more preferably 0.5 ⁇ m or less.
• the average particle diameter of the microparticles can be measured using a call counter.
• microparticles used may be of one type alone or two or more types in combination.
• the content of the microparticles is, for example, in the range of 6 to 20 parts by mass per 100 parts by mass of the active energy ray-curable compound.
• the hard coat layer-forming composition may contain a solvent for the purpose of adjusting the viscosity and the like to provide coating suitability.
• the solvent include dibutyl ether, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole, phenetole, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, acetone, methyl ethyl ketone (MEK), diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate,
• solvent
• suitable alcohols include methyl alcohols such as ethyl propionate, 2-methoxyethanol, 2-propoxyethanol, 2-butoxyethanol, 1,2-diacetoxyacetone, acetylacetone, diacetone alcohol, methyl acetoacetate, and ethyl acetoacetate, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, cyclohexyl alcohol, isobutyl acetate, methyl isobutyl ketone (MiBK), 2-octanone, 2-pentanone, 2-hexanone, ethylene glycol ethyl ether, ethylene glycol isopropyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, ethyl carbitol, butyl carbitol, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethy
• the solvents used may be one type alone or two or more types in combination.
• the composition for forming a hard coat layer may optionally contain other additives such as a plasticizer, an infrared absorber, a colorant (pigment, dye, etc.), a fluorescent brightener, a dispersant, a heat stabilizer, a light stabilizer, an antistatic agent, an antioxidant, etc.
• additives such as a plasticizer, an infrared absorber, a colorant (pigment, dye, etc.), a fluorescent brightener, a dispersant, a heat stabilizer, a light stabilizer, an antistatic agent, an antioxidant, etc.
• the content of these other additives may be appropriately determined depending on the purpose and application.
• the method for producing the composition for forming the hard coat layer is not particularly limited, and it can be produced by a known method.
• the above-mentioned components may be mixed all at once, or the components may be mixed in portions and in stages.
• the composition for forming a hard coat layer of the present invention is applied to a substrate, and the resulting coating film is cured by irradiating it with active energy rays such as electron beams, ultraviolet rays, and visible light, thereby forming a hard coat layer (hereinafter sometimes referred to as the "hard coat layer of the present invention").
• active energy rays are ultraviolet rays
• the irradiation intensity of the ultraviolet rays may be, for example, in the range of 10 to 5,000 mW/cm 2
• the irradiation amount may be, for example, in the range of 10 to 10,000 mJ/cm 2 .
• the thickness of the hard coat layer is, for example, in the range of 1 ⁇ m to 30 ⁇ m, preferably in the range of 3 ⁇ m to 15 ⁇ m, and more preferably in the range of 5 ⁇ m to 12 ⁇ m.
• the substrate is not particularly limited, but examples include cellulose ester film, polycarbonate film, polyester films such as polyethylene terephthalate and polyethylene naphthalate, (meth)acrylic films such as polymethyl methacrylate, styrene copolymer films such as polystyrene and acrylonitrile-styrene copolymer, and cyclic polyolefin films.
• polarizers can be used, such as a film formed by dyeing a PVA-based resin film with a dichroic dye and uniaxially stretching it; or a film formed by applying a coating liquid containing a PVA-based resin to a substrate, dyeing the PVA-based resin layer of the laminate with a dichroic dye, and uniaxially stretching the laminate.
• the PVA-based resin may be modified, for example, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, etc., modified with aldehydes.
• the saponification degree of the PVA resin is preferably 85 mol % or more, more preferably 90 mol % or more, and even more preferably 99 mol % to 100 mol %.
• the degree of polymerization of the PVA-based resin is, for example, in the range of 1,000 to 10,000, and preferably in the range of 1,500 to 5,000.
• the polarizer preferably exhibits absorption dichroism at any wavelength between 380 nm and 780 nm.
• the single transmittance of the polarizer is, for example, 41.0% or more, preferably in the range of 43.0% to 46.0%, and more preferably in the range of 44.5% to 46.0%.
• the degree of polarization of the polarizer is preferably 97.0% or more, more preferably 99.0% or more, and even more preferably 99.9% or more.
• the thickness of the polarizer is, for example, in the range of 5 ⁇ m to 50 ⁇ m, preferably in the range of 5 ⁇ m to 40 ⁇ m, and more preferably in the range of 8 ⁇ m to 30 ⁇ m.
• the protective layer may be a known material, and examples thereof include transparent resin films such as cellulose-based resins such as triacetyl cellulose (TAC), polyester-based resins, polyvinyl alcohol-based resins, polycarbonate-based resins, polyamide-based resins, polyimide-based resins, polyethersulfone-based resins, polysulfone-based resins, polystyrene-based resins, polynorbornene-based resins, polyolefin-based resins, (meth)acrylic resins, and acetate-based resins.
• TAC triacetyl cellulose
• polyester-based resins such as triacetyl cellulose (TAC), polyester-based resins, polyvinyl alcohol-based resins, polycarbonate-based resins, polyamide-based resins, polyimide-based resins, polyethersulfone-based resins, polysulfone-based resins, polystyrene-based resins, polynorborn
• the thickness of the protective layer is, for example, in the range of 1 to 300 ⁇ m, preferably in the range of 5 ⁇ m to 200 ⁇ m, more preferably in the range of 10 ⁇ m to 100 ⁇ m, and even more preferably in the range of 10 ⁇ m to 60 ⁇ m.
• the adhesive constituting the adhesive layer may be an adhesive that is applicable to optical applications, and examples of such adhesives include water-based adhesives and photo-curable adhesives.
• a water-based adhesive containing a PVA-based resin (PVA-based adhesive) is preferably used.
• the average degree of polymerization of the PVA resin contained in the aqueous adhesive is, for example, in the range of 100 to 5,500, preferably in the range of 1,000 to 4,500, from the viewpoint of adhesiveness.
• the average degree of saponification of the PVA resin contained in the aqueous adhesive is, from the viewpoint of adhesiveness, for example, in the range of 85 mol % to 100 mol %, and preferably in the range of 90 mol % to 100 mol %.
• the PVA-based resin contained in the aqueous adhesive is preferably a PVA-based resin containing an acetoacetyl group, and the degree of acetoacetyl group modification of the acetoacetyl group-containing PVA-based resin is, for example, 0.1 mol % or more, and preferably in the range of 0.1 mol % to 20 mol %.
• the concentration of the PVA resin contained in the aqueous adhesive is, for example, in the range of 0.1% by mass to 15% by mass, and preferably in the range of 0.5% by mass to 10% by mass.
• the aqueous adhesive containing the PVA resin may further contain a crosslinking agent, such as a water-soluble epoxy compound, a dialdehyde, or an isocyanate.
• a crosslinking agent such as a water-soluble epoxy compound, a dialdehyde, or an isocyanate.
• the crosslinking agent is preferably one or more selected from glyoxal, glyoxylates, and methylolmelamine.
• the water-based adhesive may contain an organic solvent.
• the organic solvent is preferably an alcohol because it is miscible with water, and among alcohols, methanol and/or ethanol are preferred.
• the concentration of the alcohol is, for example, in the range of 10% by mass to 70% by mass, preferably in the range of 15% by mass to 60% by mass, and more preferably in the range of 20% by mass to 60% by mass.
• Photocurable adhesives are adhesives that harden when exposed to active energy rays, including ultraviolet rays.
• Examples include compositions containing photopolymerizable monomers such as photocurable epoxy monomers, photocurable acrylic monomers, and photocurable urethane monomers, as well as oligomers derived from these monomers, and substances that generate active species such as neutral radicals, anion radicals, and cation radicals when exposed to active energy rays.
• the thickness of the adhesive layer is, for example, in the range of 0.01 to 10 ⁇ m, preferably in the range of 0.01 to 5 ⁇ m, more preferably in the range of 0.01 to 2 ⁇ m, and even more preferably in the range of 0.01 to 1 ⁇ m.
• the optical function layer is a layer that adds an optical function to the polarizing plate, and an example of such a layer is a retardation layer.
• the retardation layer include a layer that imparts a retardation of ⁇ /2, a layer that imparts a retardation of ⁇ /4 (positive A plate), and a positive C plate.
• the polarizing plate can be a circular polarizing plate.
• retardation layers include birefringent films made from stretched films of light-transmitting thermoplastic resins, and liquid crystal layers formed on substrate films of cellulose ester resins such as triacetyl cellulose.
• optically functional layers include light-collecting plates, brightness-enhancing films, reflective layers (reflective films), semi-transparent reflective layers (semi-transparent reflective films), light-diffusing layers (light-diffusing films), and anti-reflection films.
• the polarizing plate of the present invention is suitable for use in image display devices, such as liquid crystal displays, electroluminescence (EL) displays, plasma displays (PDs), and field emission displays (FEDs).
• image display devices such as liquid crystal displays, electroluminescence (EL) displays, plasma displays (PDs), and field emission displays (FEDs).
• the weight average molecular weight (Mw) and number average molecular weight (Mn) are values calculated as polystyrene equivalents based on gel permeation chromatography (GPC) measurements.
• the GPC measurement conditions are as follows.
• Measurement equipment High-speed GPC equipment "HLC-8320GPC” manufactured by Tosoh Corporation Column: “TSKGUARDCOLUMN Super HZ-L” manufactured by Tosoh Corporation + “TSKgel Super HZM-N” manufactured by Tosoh Corporation + “TSKgel Super HZM-N” manufactured by Tosoh Corporation + “TSKgel Super HZM-N” manufactured by Tosoh Corporation + “TSKgel Super HZM-N” manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "EcoSEC Data Analysis Version 1.07" Column temperature: 40°C Developing solvent: tetrahydrofuran Flow rate: 0.35 mL/min Measurement sample: 7.5 mg of a sample was dissolved in 10 mL of tetrahydrofuran, and the resulting solution was filtered through a microfilter to prepare a measurement sample. Sample injection volume: 20 ⁇ L Standard sample
• a monomer polymerization initiator solution prepared by dissolving 33.0 g of 3-methacryloyloxypropyltris(trimethylsiloxy)silane (molecular weight 423), 67.0 g of polypropylene glycol monomethacrylate (average propylene glycol repeat number 4 to 6), and 7.5 g of the polymerization initiator t-butylperoxy-2-ethylhexanoate in 112.5 g of propylene glycol monomethyl ether acetate was placed in the dropping device, and added dropwise over 2 hours while maintaining the temperature inside the flask at 95°C.
• the mixture was allowed to react for 5 hours at 95°C under a nitrogen stream, and then the temperature was raised to 110°C and the mixture was allowed to react for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a silicone-containing random copolymer (1).
• a monomer polymerization initiator solution prepared by dissolving 44.0 g of 3-methacryloyloxypropyltris(trimethylsiloxy)silane (molecular weight 423), 56.0 g of polypropylene glycol monomethacrylate (average propylene glycol repeat number 4 to 6), and 7.5 g of the polymerization initiator t-butylperoxy-2-ethylhexanoate in 112.5 g of propylene glycol monomethyl ether acetate was placed in the dropping device, and added dropwise over 2 hours while maintaining the temperature inside the flask at 95°C.
• the molecular weight of the resulting silicone-containing random copolymer (1) was measured by GPC, and the weight average molecular weight (Mw) was found to be 10,000. Furthermore, based on the raw material charging ratio, the content of silicone-containing polymerizable monomer in copolymer (2) was found to be 44% by mass.
• the mixture was allowed to react for 5 hours at 90°C under a nitrogen stream, and then the temperature was raised to 110°C and the mixture was allowed to react for 1 hour. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a silicone-containing random copolymer (3).
• a silicone-containing polymerizable monomer weight average molecular weight 1,000
• the molecular weight of the resulting silicone-containing random copolymer (4) was measured by GPC, and the weight average molecular weight (Mw) was found to be 26,000. Furthermore, based on the raw material charging ratio, the content of silicone-containing polymerizable monomer in copolymer (4) was found to be 33% by mass.
• a coating composition for a hard coat layer was prepared by mixing and dissolving 5 parts by mass of an ultraviolet-curable urethane acrylate resin ("Luxidia 17-806" manufactured by DIC Corporation, a butyl acetate solution containing 80% by mass of ultraviolet-curable urethane acrylate resin), 0.2 parts by mass of Irgacure 184 (manufactured by Ciba Specialty Chemicals), 0.012 parts by mass of a copolymer shown in Table 1, 2 parts by mass of toluene, 1 part by mass of 2-propanol, 1 part by mass of ethyl acetate, and 1 part by mass of propylene glycol monomethyl ether.
• an ultraviolet-curable urethane acrylate resin ("Luxidia 17-806" manufactured by DIC Corporation, a butyl acetate solution containing 80% by mass of ultraviolet-curable urethane acrylate resin)
• Irgacure 184 manufactured by Ciba Specialty Chemical
• the smoothness of the hard coat layer of the prepared hard coat film was evaluated by the following method. The results are shown in Table 1. (Smoothness) The hard coat layer of the obtained hard coat film was visually observed, and the smoothness of the hard coat layer was evaluated according to the following criteria. ⁇ : Virtually no unevenness is observed on the surface of the hard coat layer. ⁇ : Unevenness is observed in some parts of the surface of the hard coat layer. x: Unevenness was observed on the entire surface of the hard coat layer.

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