WO2014208748A1 - Uv-curable hard-coating resin composition - Google Patents

Uv-curable hard-coating resin composition Download PDF

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Publication number
WO2014208748A1
WO2014208748A1 PCT/JP2014/067251 JP2014067251W WO2014208748A1 WO 2014208748 A1 WO2014208748 A1 WO 2014208748A1 JP 2014067251 W JP2014067251 W JP 2014067251W WO 2014208748 A1 WO2014208748 A1 WO 2014208748A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
meth
hard coat
ultraviolet curable
acrylate
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PCT/JP2014/067251
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French (fr)
Japanese (ja)
Inventor
康明 成田
彰雄 矢内
浩和 狩野
典明 望月
Original Assignee
日本化薬株式会社
株式会社ポラテクノ
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Priority to JP2015524142A priority Critical patent/JPWO2014208748A1/en
Publication of WO2014208748A1 publication Critical patent/WO2014208748A1/en

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Classifications

    • 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
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • 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
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • C08K5/3465—Six-membered rings condensed with carbocyclic rings
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers

Definitions

  • the present invention relates to an ultraviolet curable hard coat resin composition that imparts scratch resistance and blue light cut property to a plastic surface. More specifically, the present invention relates to a UV curable hard coat resin composition that is suitable for application to a plastic surface such as polyester, acrylic, triacetyl cellulose, polycarbonate, etc., and has excellent scratch resistance, chemical resistance, and blue light cut property. .
  • the film and sheet coated with this hard coat resin composition are particularly suitable for displays such as smartphones, tablet PCs, notebook computers, and liquid crystal monitors with LED backlights because of their excellent blue light cutting properties. ing.
  • the present invention provides a hard coat film capable of obtaining a molded product having the blue light cut characteristics without causing cracks in the curved surface portion of the molded product surface by selecting a flexible resin composition. give. It is particularly suitable for in-mold molding and film integral molding, and is also suitable for imparting a blue light cut function to sunglasses.
  • plastics are used in large quantities in various industries including the automobile industry, home appliance industry, and electrical and electronics industry.
  • the reason why such a large amount of plastic is used is that, in addition to its processability and transparency, it is lightweight, inexpensive and has excellent optical properties.
  • it has disadvantages such as being softer than glass and being easily scratched on the surface.
  • it is a common means to coat the surface with a hard coating agent.
  • the hard coat agent thermosetting hard coat agents such as silicone paints, acrylic paints, and melamine paints are used.
  • silicone hard coat agents are particularly frequently used because of their high hardness and excellent quality.
  • it has a long curing time, is expensive, and cannot be said to be suitable for a hard coat layer provided on a continuously processed film.
  • photosensitive acrylic hard coating agents have been developed and used (see Patent Document 1).
  • the photosensitive hard coat agent is cured immediately upon irradiation with radiation such as ultraviolet rays to form a hard film, so the processing speed is fast, and it has excellent performance in terms of hardness and scratch resistance. Now it has become the mainstream in the hard coat field because it is cheaper. It is particularly suitable for continuous processing of films such as polyester.
  • plastic films include polyester film, acrylic film, polycarbonate film, vinyl chloride film, triacetyl cellulose film, and polyethersulfone film. Polyester film and triacetyl cellulose film are widely used due to various excellent properties. ing.
  • This polyester film is a glass anti-scattering film, an automobile light-shielding film, a whiteboard surface film, a system kitchen surface antifouling film, and electronic materials such as CRT flat TVs, touch panels, liquid crystal displays, plasma displays, etc. Widely used as a functional film.
  • the triacetyl cellulose film is used as a protective film of a polarizing plate used for a liquid crystal display. All of these are coated with a hard coat so as not to scratch the surface.
  • polycarbonate and acrylic sheets and substrates with hard coatings are also used for liquid crystal related members around optical disks and backlights.
  • a fluorine material or silicone oil is mixed in the coating composition to improve the surface water / oil repellency, or similar to sebum components.
  • a method for improving fingerprint wiping as a fingerprint resistance for example, a fluorine material or silicone oil is mixed in the coating composition to improve the surface water / oil repellency, or similar to sebum components.
  • the component is used in the coating composition so that the attached fingerprint becomes familiar, difficult to see, and easy to wipe (see Patent Document 4).
  • Blue light refers to light with a short wavelength of 380 nm to 495 nm among visible light, and is said to be emitted from a liquid crystal monitor that uses LEDs as a backlight.
  • This blue light is a major cause of eye strain, and further, it is said that it disturbs the biological rhythm and becomes a sleep disorder, and blue light cut is attracting attention.
  • An object of the present invention is to provide an ultraviolet curable hard coat resin composition having high transparency, high hardness, and excellent blue light cut function by stably dissolving a dye having a specific structure.
  • an ultraviolet curable hard coat resin composition having a specific compound and composition can solve the above problems, and have reached the present invention.
  • the present invention “(1) Ultraviolet curable hard coat resin composition comprising an ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule and a dye having the structure of formula (1) object, (R 1 represents a halogen atom, R 2 represents an alkyl group having 1 to 3 carbon atoms or a sulfonamide group having a substituent, and n represents an integer of 1 to 4) (2) The ultraviolet curable hard coat resin composition according to (1), which contains a photopolymerization initiator, (3) The ultraviolet curable hard coat resin composition according to (1) or (2), comprising a diluent, (4) The ultraviolet curable hard coat resin composition according to any one of (1) to (3), which contains organic and / or inorganic particles, (5) A substrate having a cured layer made of the ultraviolet curable hard coat resin composition according to any one of (1) to (4), (6) The base material according to (5), which is a transparent polymer or a film thereof, (7) The
  • an ultraviolet curable hard coat resin composition having excellent blue light cut property, scratch resistance, high hardness and transparency can be provided.
  • Examples of the ultraviolet curable polyfunctional (meth) acrylate (A) having at least two (meth) acryloyl groups in the molecule used in the present invention include polyethylene glycol di (meth) acrylate, tripropylene glycol di ( Di (meth) acrylate of ⁇ -caprolactone adduct of (meth) acrylate, hydroxypivalate neopentyl glycol (for example, KAYARAD HX-220, HX-620 etc., manufactured by Nippon Kayaku Co., Ltd.), EO adduct of bisphenol A Di (meth) acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri ( Acrylate), epichlorohydrin (ECH) modified glycerol tri (me
  • Examples of the polyfunctional (meth) acrylate having active hydrogen include pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol tetra (meth).
  • Pentaerythritols such as acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, methylols such as trimethylolpropane di (meth) acrylate, epoxy acrylates such as bisphenol A diepoxy acrylate, etc. Can be mentioned. Of these, pentaerythritol triacrylate and dipentaerythritol pentaacrylate are preferable.
  • These polyfunctional (meth) acrylates having active hydrogen may be used alone or in admixture of two or
  • polyisocyanate polyisocyanates composed of chain saturated hydrocarbons, cyclic saturated hydrocarbons (alicyclic), and aromatic hydrocarbons can be used.
  • polyisocyanates include chain saturated hydrocarbon polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and methylenebis (4-cyclohexyl).
  • Isocyanate hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, etc., cyclic saturated hydrocarbon (alicyclic) polyisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene Diisocyanate, 3,3′-dimethyl-4,4′-diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate Aromatic polyisocyanates such as 1,5-naphthalene diisocyanate. Of these, isophorone diisocyanate and hexamethylene diisocyanate are preferable. These polyisocyanates may be used alone or in combination of two or more.
  • the polyfunctional urethane (meth) acrylate is obtained by reacting the polyfunctional (meth) acrylate having active hydrogen with a polyisocyanate.
  • polyisocyanate is usually in the range of 0.1 to 50 equivalent, preferably in the range of 0.1 to 10 equivalent as the isocyanate group equivalent. is there.
  • the reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C.
  • the end point of the reaction is the time when the polyisocyanate calculated by the method of reacting residual isocyanate with excess n-butylamine and back titrating with 1N hydrochloric acid is 0.5% by weight or less.
  • a catalyst may be added for the purpose of shortening the reaction time.
  • a basic catalyst or an acidic catalyst is used.
  • the basic catalyst include amines such as triethylamine, diethylamine, dibutylamine, and ammonia, phosphines such as tributylphosphine and triphenylphosphine, pyridine, pyrrole, and the like.
  • the acidic catalyst examples include metal salts such as copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, trititanium tetrabutoxide, zirconium tetrabutoxide, Lewis acids such as aluminum chloride, 2-ethylhexanetin, Examples thereof include tin compounds such as octyltin trilaurate, dibutyltin dilaurate, and octyltin diacetate. When these catalysts are used, the amount added is usually about 0.1 to 1 part by weight per 100 parts by weight of the polyisocyanate.
  • a polymerization inhibitor for example, methoquinone, hydroquinone, methylhydroquinone, phenothiazine, etc.
  • the amount used is 0.01 weight with respect to the reaction mixture. % To about 1% by weight, preferably about 0.05% to 0.5% by weight.
  • the reaction temperature is 60 to 150 ° C, preferably 80 to 120 ° C.
  • the amount of the ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule is 100% by weight based on the solid content of the resin composition of the present invention. In this case, it is usually 80 to 95% by weight, preferably 90 to 95% by weight.
  • a (meth) acrylate compound other than the ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule is optionally used as necessary.
  • Examples of (meth) acrylate compounds include (meth) acrylate monomers.
  • Examples of the (meth) acrylate monomer include tricyclodecane (meth) acrylate, dicyclopentadieneoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantane (meth) acrylate, benzyl ( (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholine (meth) acrylate, phenylglycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( And meth) acrylate and ethyl carbitol (meth) acrylate.
  • the present invention is characterized by further containing an ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule and a dye having the structure of formula (1),
  • the ultraviolet curable hard coat resin composition containing a pigment can provide an ultraviolet curable hard coat resin composition having high transparency, high hardness, and excellent blue light cut function.
  • a dye other than that described in Formula (1) is used, not only the blue light cut function is lowered, but also transparency is lowered, hardness is lowered, and the ultraviolet curable resin is not yet treated after the polymerization reaction. Problems such as an increase in reactive residual monomers occur.
  • R 1 represents a halogen atom
  • R 2 represents an alkyl group having 1 to 3 carbon atoms or a sulfonamide group having a substituent
  • n represents an integer of 1 to 4
  • the average light transmittance of 440 nm to 480 nm is reduced by 1% or more with respect to the total light transmittance, although the total light transmittance is 90% or more, preferably 3 % Or more, more preferably 6% or more, and further, a film or a substrate having an absolute value of the difference in each transmittance of 440 nm to 480 nm within 1% can be obtained.
  • a film or substrate obtained by a composition of a dye represented by formula (1) and an ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule The transmittance of 440 nm to 480 nm has a characteristic of almost constant transmittance, and a stable blue light cut can be realized in the range of 440 nm to 480 nm.
  • photopolymerization initiator used in the present invention examples include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1, 1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane Acetophenones such as 1-one; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; 2,4-diethylthio Thioxanthones such as xanthone, 2-iso
  • Irgacure 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure 907 (2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl)-produced by BASF Corporation 1-propanone), lucillin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) and the like are easily available. Moreover, you may use these individually or in mixture of 2 or more types.
  • the amount used when the photopolymerization initiator component is used is 0.5 to 10% by weight when the solid content of the resin composition of the present invention is 100% by weight. It is preferably 1 to 7% by weight.
  • the above photopolymerization initiator can be used in combination with a curing accelerator.
  • the curing accelerator that can be used in combination include triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethylbenzoate, dimethylaminoacetophenone, p-dimethylaminobenzoic acid isoamino ester, amines such as EPA, 2- And hydrogen donors such as mercaptobenzothiazole.
  • the amount of these curing accelerators used is 0 to 5% by weight when the solid content of the resin composition of the present invention is 100% by weight.
  • Examples of the diluent that can be used in the present invention include lactones such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -heptalactone, ⁇ -acetyl- ⁇ -butyrolactone, and ⁇ -caprolactone; 2-dimethoxymethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, etc.
  • lactones such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -heptalactone, ⁇ -acetyl- ⁇ -butyrolactone, and ⁇
  • Ethers carbonates such as ethylene carbonate and propylene carbonate; Ketones such as ruethylketone, methylisobutylketone, cyclopentanone, cyclohexanone, acetophenone; phenols such as phenol, cresol, xylenol; ethyl acetate, butyl acetate, ethyl lactate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butylcarbi Esters such as tall acetate and propylene glycol monomethyl ether acetate; Hydrocarbons such as toluene, xylene, diethylbenzene and cyclohexane; Halogenated hydrocarbons such as trichloroethane, tetrachloroethane and monochlorobenzene; Petroleum such as petroleum ether and petroleum naphtha Organic solvents such as organic solvents, flu
  • the amount used when the diluent component is used is in the range of 20 to 80% by weight, preferably 30 to 70% by weight, based on the total amount of the resin composition of the present invention. It is.
  • organic and / or inorganic particles can be added to impart an antiglare property and an antireflection function.
  • the organic particles include plastic beads, melamine beads, acrylic beads, acrylic-styrene beads, polycarbonate beads, polyethylene beads, and polystyrene beads.
  • the inorganic particles include amorphous particles of silicon dioxide as silica, true spherical particles, and metal oxides such as tin oxide, zinc oxide, titanium oxide, and alumina. The particle size and addition amount of these particles can be adjusted according to the target haze and other characteristics.
  • a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor and the like are added to the photosensitive resin composition of the present invention as necessary.
  • antioxidants include phenolic compounds
  • polymerization inhibitors include methoquinone, methylhydroquinone, hydroquinone, and the like.
  • the resin composition of the present invention comprises the above-mentioned ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups, a dye exemplified by formula (1), a photopolymerization initiator, and a diluent. It can be obtained by mixing and mixing other components as required.
  • the resin composition of the present invention thus obtained is stable over time.
  • the UV curable hard coat resin composition of the present invention is applied onto a substrate so that the film thickness after drying of the resin composition is usually 0.1 to 20 ⁇ m, preferably 1 to 10 ⁇ m, and dried. It can obtain as a hard coat film by irradiating back ultraviolet rays and forming a cured film.
  • examples of the substrate film include polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, triacetylcellulose, polyethersulfone, and cycloolefin polymer.
  • the film may be a thick sheet.
  • the film to be used may be one provided with a handle or an easy-adhesion layer, or one subjected to surface treatment such as corona treatment.
  • Examples of the coating method of the resin composition include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, micro gravure coating, micro reverse gravure coater, and die coater. Examples thereof include coating, dip coating, spin coating coating, and spray coating.
  • ultraviolet rays are irradiated for curing
  • an electron beam or the like can also be used.
  • an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp or the like is used as a light source, and the light amount, the arrangement of the light source, etc. are adjusted as necessary.
  • a high-pressure mercury lamp it is preferable to cure at 100 to 1000 mJ / cm 2 at a conveyance speed of 5 to 60 m / min with respect to one lamp having energy of 80 to 160 W / cm 2 .
  • an electron beam accelerator having an energy of 100 to 500 eV.
  • a transparent polymer or a film thereof is preferable.
  • the transparent polymer or film to be formed is preferably a transparent polymer or film having high mechanical strength and good thermal stability.
  • a substance used as a transparent protective layer for example, cellulose acetate resin such as triacetyl cellulose or diacetyl cellulose or film thereof, acrylic resin or film thereof, polyvinyl chloride resin or film thereof, nylon resin or film thereof, polyester resin or film thereof Film, polyarylate resin or film thereof, cyclic polyolefin resin or film thereof using cyclic olefin such as norbornene as a monomer, polyethylene, polypropylene, polyolefin having cyclo or norbornene skeleton or copolymer thereof, main chain or side chain Examples include imide and / or amide resins or polymers or films thereof.
  • the obtained substrate can be bonded to a polarizing element made of, for example, a polyvinyl alcohol resin film, or a polarizing plate laminated with triacetyl cellulose or the like via an adhesive or the like.
  • the film thus obtained becomes a hard coat film or substrate suitable for fields requiring hardness, transparency, scratch resistance and blue light cut in addition to the polarizing function when provided in a liquid crystal cell.
  • the resin composition of the present invention can be used for resin molding of films, lenses and the like, the resin composition of the present invention can be used even when such molded parts or molded bodies are produced.
  • Formulation Example 1 In 500 mL Kolben, 60 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name: KAYARAD PET-30, manufactured by Nippon Kayaku Co., Ltd.), polyfunctional urethane acrylate (trade name: KAYARAD UX-5000, Japan) 40 parts of Kayaku Co., Ltd.), 5 parts of 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by BASF Corporation) and 66.7 parts of toluene are mixed and dissolved at room temperature, and the solid content is 60%. A master liquid 1 was prepared.
  • Formulation Example 2 The compound shown in Formula (4) and the compound shown in Formula (5) were added to orthodichlorobenzene, and the temperature was raised while stirring to obtain a solution containing the compound shown in Compound Example 1. The obtained solution was filtered, and the residue was dried to obtain a pigment of Compound Example 1 having a maximum absorption wavelength at 450 nm. 0.1 part of the obtained pigment and 19.9 parts of toluene were mixed and dissolved to prepare a master liquid 2.
  • Comparative Example 1 The master liquid 1 was applied onto an 80 ⁇ m triacetylcellulose film with a bar coater, dried for 2 minutes in an 80 ° C. dryer, and then cured with an ultraviolet light irradiation apparatus equipped with a 160 W high-pressure mercury lamp at an integrated light amount of 250 mJ / cm 2 A hard coat film having a thickness of 4 to 5 ⁇ m was obtained.
  • Examples 1 to 3 The resin composition containing the materials shown in Table 1 below was coated on an 80 ⁇ m triacetylcellulose film with a bar coater, dried in an 80 ° C. dryer for 2 minutes, and then integrated with a UV irradiation device equipped with a 160 W high-pressure mercury lamp. Curing was performed at 250 mJ / cm 2 to obtain a blue light-cut hard coat film having a thickness of 4 to 5 ⁇ m. In Table 1, the unit indicates “part”.
  • Comparative Examples 2 to 4 The same procedure was performed except that the dye used in Examples 1 to 3 was changed to Yellow Dye Flavine FG manufactured by Nippon Kayaku Co., Ltd. having a maximum absorption wavelength at 420 nm, and Comparative Examples 2 to 4 were obtained.
  • Table 4 shows the transmittance of 440 nm to 480 nm obtained by measuring the transmittance
  • Table 5 shows the wavelength transmittances of 440 nm to 480 nm.
  • the pencil hardness of the coated film having the above composition was measured using a pencil scratch tester. Specifically, on the polyester film having the cured film to be measured, the pencil is applied with a load of 750 g from the top at a 45 degree angle, and is scratched for about 5 mm. expressed.
  • Total light transmittance Measurement was performed using HM-150 manufactured by Murakami Color Research Laboratory.
  • Example 1 to 3 it was possible to cut the transmittance at 440 nm, which is the blue light cut region, while maintaining the total light transmittance at 90% or more. Moreover, it was confirmed by the comparison with a comparative example that the characteristic as a hard coat film is maintained. That is, the blue light cut function could be imparted without causing deterioration of the pigment while maintaining the characteristics of the conventional hard coat film. In addition, it can be seen that a film or a substrate having a substantially uniform transmittance from 440 nm to 480 nm is obtained.
  • the hard coat film obtained with the resin composition of the present invention has excellent blue light cutability, high transparency, and good hardness, especially a smartphone equipped with a touch panel, a tablet PC, a notebook PC, a plastic optical component, etc. It is a hard coat film suitable for fields requiring hardness, transparency, scratch resistance and blue light cut.

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Abstract

[Problem] To provide a hard-coating film or base material that is suitable for use in fields that require hardness, optical transparency, resistance to abrasion scratches, and blue-light reduction. [Solution] A film or base material using a UV-curable hard-coating resin composition that contains the following: a UV-curable polyfunctional (meth)acrylate that has at least two (meth)acryloyl groups per molecule; and a pigment that has a structure that can be represented by formula (1).

Description

紫外線硬化型ハードコート樹脂組成物UV curable hard coat resin composition
　本発明は、プラスチック表面の耐擦傷性、ブルーライトカット性を付与する紫外線硬化型ハードコート樹脂組成物に関する。更に詳しくはポリエステル、アクリル、トリアセチルセルロース、ポリカーボネート等のプラスチック表面に塗布するのに適した、透明で耐擦傷性、耐薬品性及びブルーライトカット性に優れた紫外線硬化型ハードコート樹脂組成物に関する。特にブルーライトカット性に優れていることから、本ハードコート樹脂組成物をコーティングしたフィルムやシートは、ＬＥＤをバックライトとするスマートフォン、タブレット型ＰＣ、ノートパソコン、液晶モニターなどのディスプレイ類などに適している。 The present invention relates to an ultraviolet curable hard coat resin composition that imparts scratch resistance and blue light cut property to a plastic surface. More specifically, the present invention relates to a UV curable hard coat resin composition that is suitable for application to a plastic surface such as polyester, acrylic, triacetyl cellulose, polycarbonate, etc., and has excellent scratch resistance, chemical resistance, and blue light cut property. . The film and sheet coated with this hard coat resin composition are particularly suitable for displays such as smartphones, tablet PCs, notebook computers, and liquid crystal monitors with LED backlights because of their excellent blue light cutting properties. ing.
　更に、本発明は柔軟性のある樹脂組成物を選択することにより成形品表面部分の曲面部においてもクラックを発生させずに前記ブルーライトカット特性を有する成形品を得ることのできるハードコートフィルムを与える。特にインモールド成形、フィルム一体成形に適し、サングラスへのブルーライトカット機能の付与等にも適する。 Furthermore, the present invention provides a hard coat film capable of obtaining a molded product having the blue light cut characteristics without causing cracks in the curved surface portion of the molded product surface by selecting a flexible resin composition. give. It is particularly suitable for in-mold molding and film integral molding, and is also suitable for imparting a blue light cut function to sunglasses.
　現在、プラスチックは自動車業界、家電業界、電気電子業界を初めとして種々の産業界で大量に使われている。このようにプラスチックが大量に使われている理由は、その加工性、透明性に加えて軽量、安価、光学特性が優れているなどの理由による。しかしながら、ガラスなどに比べて柔らかく、表面に傷が付きやすいなどの欠点を有している。これらの欠点を改良するために、表面にハードコート剤をコーティングする事が一般的な手段として行われている。このハードコート剤には、シリコーン系塗料、アクリル系塗料、メラミン系塗料などの熱硬化型のハードコート剤が用いられている。この中でも特に、シリコーン系ハードコート剤は、ハードネスが高く、品質が優れているため多く用いられている。しかしながら、硬化時間が長く、高価であり、連続的に加工するフィルムに設けられるハードコート層には適しているとは言えない。 Currently, plastics are used in large quantities in various industries including the automobile industry, home appliance industry, and electrical and electronics industry. The reason why such a large amount of plastic is used is that, in addition to its processability and transparency, it is lightweight, inexpensive and has excellent optical properties. However, it has disadvantages such as being softer than glass and being easily scratched on the surface. In order to improve these drawbacks, it is a common means to coat the surface with a hard coating agent. As the hard coat agent, thermosetting hard coat agents such as silicone paints, acrylic paints, and melamine paints are used. Of these, silicone hard coat agents are particularly frequently used because of their high hardness and excellent quality. However, it has a long curing time, is expensive, and cannot be said to be suitable for a hard coat layer provided on a continuously processed film.
　近年、感光性のアクリル系ハードコート剤が開発され、利用されるようになった（特許文献１参照）。感光性ハードコート剤は、紫外線などの放射線を照射することにより、直ちに硬化して硬い皮膜を形成するため、加工処理スピードが速く、またハードネス、耐擦傷性などに優れた性能を持ち、トータルコスト的に安価になるため、今やハードコート分野の主流になっている。特に、ポリエステルなどのフィルムの連続加工には適している。プラスチックのフィルムとしては、ポリエステルフィルム、アクリルフィルム、ポリカーボネートフィルム、塩化ビニルフィルム、トリアセチルセルロースフィルム、ポリエーテルスルホンフィルムなどがあるが、ポリエステルフィルム、トリアセチルセルロースフィルムが種々の優れた特性から広く使用されている。このポリエステルフィルムは、ガラスの飛散防止フィルム、あるいは、自動車の遮光フィルム、ホワイトボード用表面フィルム、システムキッチン表面防汚フィルム、電子材料的には、ＣＲＴフラットテレビ、タッチパネル、液晶ディスプレイ、プラズマディスプレイなどの機能性フィルムとして広く用いられている。また、トリアセチルセルロースフィルムは、液晶ディスプレイに使用される偏光板の保護フィルムとして用いられている。これらはいずれもその表面に傷が付かないようにするためにハードコートを塗工している。 In recent years, photosensitive acrylic hard coating agents have been developed and used (see Patent Document 1). The photosensitive hard coat agent is cured immediately upon irradiation with radiation such as ultraviolet rays to form a hard film, so the processing speed is fast, and it has excellent performance in terms of hardness and scratch resistance. Now it has become the mainstream in the hard coat field because it is cheaper. It is particularly suitable for continuous processing of films such as polyester. Examples of plastic films include polyester film, acrylic film, polycarbonate film, vinyl chloride film, triacetyl cellulose film, and polyethersulfone film. Polyester film and triacetyl cellulose film are widely used due to various excellent properties. ing. This polyester film is a glass anti-scattering film, an automobile light-shielding film, a whiteboard surface film, a system kitchen surface antifouling film, and electronic materials such as CRT flat TVs, touch panels, liquid crystal displays, plasma displays, etc. Widely used as a functional film. Moreover, the triacetyl cellulose film is used as a protective film of a polarizing plate used for a liquid crystal display. All of these are coated with a hard coat so as not to scratch the surface.
　また、プラスチックのフィルム以外ではポリカーボネートやアクリル等のシートや基板についてハードコートをされたものが、光ディスクやバックライト周辺の液晶関連部材にも使用されている。 In addition to plastic films, polycarbonate and acrylic sheets and substrates with hard coatings are also used for liquid crystal related members around optical disks and backlights.
　更に近年におけるハードコート剤をコーティングした基材については、耐擦傷性というハードコートとしての性能以外の機能性を求められてきている。例えば、フィルムを設けたＬＣＤ、ＰＤＰなどの表示体では、反射により表示体画面が見難くなり、目が疲れやすいと言う問題が生ずるため、用途によっては、表面反射防止能のあるハードコート処理が必要となっている。表面反射防止の方法としては、感光性樹脂中に無機フィラーや有機フィラーを分散させたものをフィルム上にコーティングし、表面に凹凸をつけて反射防止する方法（ＡＧ処理）、フィルム上に高屈折率層、低屈折率層の順に多層構造を設け、屈折率の差による光の干渉を利用し映り込み、反射を防止する方法（ＡＲ処理）、または上記２つの方法を合わせたＡＧ／ＡＲ処理の方法などがある（特許文献２参照）。 Furthermore, for a substrate coated with a hard coating agent in recent years, functionality other than the performance as a hard coat called scratch resistance has been demanded. For example, in a display body such as LCD or PDP provided with a film, the display body screen is difficult to see due to reflection, and the eyes are likely to get tired. It is necessary. As a method for preventing surface reflection, a film in which inorganic filler or organic filler is dispersed in a photosensitive resin is coated on the film, and the surface is made uneven to prevent reflection (AG treatment). High refraction on the film A method of preventing reflection by providing a multilayer structure in the order of a refractive index layer and a low refractive index layer and using light interference due to a difference in refractive index (AR processing), or AG / AR processing combining the above two methods (See Patent Document 2).
　また、帯電防止機能を付与したハードコートも開発されており、界面活性剤や導電性の金属酸化物を使用する方法がある（特許文献３参照）。 Also, a hard coat having an antistatic function has been developed, and there is a method using a surfactant or a conductive metal oxide (see Patent Document 3).
　更に、近年スマートフォンやタブレットＰＣの普及でディスプレイに直接指で触れるタッチパネルが急速に立ち上がっている。そのため、ディスプレイの表面に指紋が付着しない、付着しにくい、付着しても見えにくい、拭き取りやすいといった所謂、耐指紋性の付与が求められている。 Furthermore, in recent years, with the spread of smartphones and tablet PCs, touch panels that directly touch the display with a finger are rapidly emerging. Therefore, there is a demand for imparting so-called fingerprint resistance that fingerprints do not adhere to the surface of the display, are difficult to adhere, difficult to see even if attached, and easy to wipe off.
　耐指紋性としての指紋拭き取り性向上の方法として、例えば、フッ素系材料やシリコーンオイル等をコーティング組成物中に混合して、表面の撥水・撥油性を向上させる方法や、皮脂成分に似通った成分をコーティング組成物に使用することにより、付着した指紋を馴染ませ、見えにくく、拭き取りやすくするといった方法もある（特許文献４参照）。 As a method for improving fingerprint wiping as a fingerprint resistance, for example, a fluorine material or silicone oil is mixed in the coating composition to improve the surface water / oil repellency, or similar to sebum components. There is also a method in which the component is used in the coating composition so that the attached fingerprint becomes familiar, difficult to see, and easy to wipe (see Patent Document 4).
　近年、液晶ディスプレイのバックライトがＣＣＦＬからＬＥＤに置き換わり、ブルーライトの問題が議論されている。ブルーライトとは、可視光線の中でも波長が短い、３８０ナノメートルから４９５ナノメートル前後の光を指し、バックライトにＬＥＤを使用する液晶モニターから多く発せられると言われている。このブルーライトは眼精疲労の大きな原因となり、更には生体リズムを狂わし、睡眠障害になるとも言われおり、ブルーライトカットが注目されている。 In recent years, the backlight of liquid crystal displays has been replaced by LEDs from CCFL, and the problem of blue light has been discussed. Blue light refers to light with a short wavelength of 380 nm to 495 nm among visible light, and is said to be emitted from a liquid crystal monitor that uses LEDs as a backlight. This blue light is a major cause of eye strain, and further, it is said that it disturbs the biological rhythm and becomes a sleep disorder, and blue light cut is attracting attention.
　現在、ブルーライトカット機能を付与したフィルムは市場に出回っているが、紫外線硬化型ハードコート樹脂組成物については知られていない。特にブルーライトカット機能を持った機能性色素と紫外線硬化型樹脂であるアクリレート化合物を混合すると色素が分解し、ブルーライトカットの機能を発現しないという問題があった。 Currently, films with a blue light cut function are on the market, but no UV curable hard coat resin composition is known. In particular, when a functional dye having a blue light cut function and an acrylate compound which is an ultraviolet curable resin are mixed, there is a problem that the dye is decomposed and the blue light cut function is not exhibited.
特開平９－４８９３４号公報Japanese Patent Laid-Open No. 9-48934 特開平９－１４５９０３号公報Japanese Patent Laid-Open No. 9-145903 特開平１０－２３１４４４号公報Japanese Patent Laid-Open No. 10-231444 特開２００８－２５５３０１号公報JP 2008-255301 A
本発明は、特定の構造を有する色素を安定に溶解することにより、透明性が高く、高い硬度を有し、ブルーライトカット機能に優れた紫外線硬化型ハードコート樹脂組成物を提供することを目的とする。 An object of the present invention is to provide an ultraviolet curable hard coat resin composition having high transparency, high hardness, and excellent blue light cut function by stably dissolving a dye having a specific structure. And
本発明者らは前記課題を解決するため、鋭意検討を行った結果、特定の化合物及び組成を有する紫外線硬化型ハードコート樹脂組成物が前記課題を解決することを見いだし、本発明に到達した。 As a result of intensive studies to solve the above problems, the present inventors have found that an ultraviolet curable hard coat resin composition having a specific compound and composition can solve the above problems, and have reached the present invention.
即ち、本発明は、
「（１）分子中に少なくとも２個以上の（メタ）アクリロイル基を有する紫外線硬化型多官能（メタ）アクリレート、及び、式（１）の構造を有する色素を含有する紫外線硬化型ハードコート樹脂組成物、
Figure JPOXMLDOC01-appb-C000002
 （Ｒ１はハロゲン原子を示し、Ｒ２は炭素数が１乃至３のアルキル基、もしくは、置換基を有するスルホンアミド基を示し、ｎは１乃至４の整数を示す。）
（２）光重合開始剤を含有することを特徴とする（１）に記載の紫外線硬化型ハードコート樹脂組成物、
（３）希釈剤を含有することを特徴とする（１）または（２）に記載の紫外線硬化型ハードコート樹脂組成物、
（４）有機及び／又は無機粒子を含有することを特徴とする（１）乃至（３）のいずれか一項に記載の紫外線硬化型ハードコート樹脂組成物、
（５）（１）乃至（４）のいずれか一項に記載の紫外線硬化型ハードコート樹脂組成物よりなる硬化層を有する基材、
（６）透明ポリマーまたはそのフィルムである、（５）に記載の基材、
（７）全光線透過率が９０％以上であって、かつ、４４０ｎｍ乃至４８０ｎｍの平均透過率が全光線透過率に対して１％以上低下し、さらに、４４０ｎｍ乃至４８０ｎｍの各透過率における差の絶対値が１％以内であることを特徴とする（５）または（６）に記載の基材、
（８）請求項１乃至４のいずれか一項に記載の紫外線硬化型ハードコート樹脂組成物の硬化層を含む偏光板、
（９）（１）乃至（４）のいずれか一項に記載の紫外線硬化型ハードコート樹脂組成物の硬化層を含む液晶表示装置、
（１０）（１）乃至（４）のいずれか一項に記載の紫外線硬化型ハードコート樹脂組成物の硬化層を有する成型物。」、に関する。 That is, the present invention
“(1) Ultraviolet curable hard coat resin composition comprising an ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule and a dye having the structure of formula (1) object,
Figure JPOXMLDOC01-appb-C000002
 (R 1 represents a halogen atom, R 2 represents an alkyl group having 1 to 3 carbon atoms or a sulfonamide group having a substituent, and n represents an integer of 1 to 4)
(2) The ultraviolet curable hard coat resin composition according to (1), which contains a photopolymerization initiator,
(3) The ultraviolet curable hard coat resin composition according to (1) or (2), comprising a diluent,
(4) The ultraviolet curable hard coat resin composition according to any one of (1) to (3), which contains organic and / or inorganic particles,
(5) A substrate having a cured layer made of the ultraviolet curable hard coat resin composition according to any one of (1) to (4),
(6) The base material according to (5), which is a transparent polymer or a film thereof,
(7) The total light transmittance is 90% or more, the average transmittance from 440 nm to 480 nm is decreased by 1% or more with respect to the total light transmittance, and the difference in each transmittance from 440 nm to 480 nm The base material according to (5) or (6), wherein the absolute value is within 1%,
(8) A polarizing plate comprising a cured layer of the ultraviolet curable hard coat resin composition according to any one of claims 1 to 4,
(9) A liquid crystal display device comprising a cured layer of the ultraviolet curable hard coat resin composition according to any one of (1) to (4),
(10) A molded article having a cured layer of the ultraviolet curable hard coat resin composition according to any one of (1) to (4). ".
　本発明により、優れたブルーライトカット性、耐擦傷性、高硬度、透明性を有する紫外線硬化型ハードコート樹脂組成物を提供することができる。 According to the present invention, an ultraviolet curable hard coat resin composition having excellent blue light cut property, scratch resistance, high hardness and transparency can be provided.
　以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
　本発明において使用する、分子中に少なくとも２個以上の（メタ）アクリロイル基を有する紫外線硬化型多官能（メタ）アクリレート（Ａ）としては、例えばポリエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ヒドロキシピバリン酸ネオペンチルグリコールのε－カプロラクトン付加物のジ（メタ）アクリレート（例えば、日本化薬（株）製、ＫＡＹＡＲＡＤ　ＨＸ－２２０、ＨＸ－６２０など）、ビスフェノールＡのＥＯ付加物のジ（メタ）アクリレート、１，４－ブタンジオールジアクリレート、１，６－ヘキサンジオールジアクリレート、１，９－ノナンジオールジアクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンポリエトキシトリ（メタ）アクリレート、エピクロルヒドリン（ＥＣＨ）変性グリセロールトリ（メタ）アクリレート、エチレンオキシド（ＥＯ）変性グリセロールトリ（メタ）アクリレート、プロピレンオキシド（ＰＯ）変性グリセロールトリ（メタ）アクリレート、ＥＯ変性リン酸トリ（メタ）アクリレート、カプロラクトン変性トリメチロールプロパントリ（メタ）アクリレート、ＥＯ変性トリメチロールプロパントリ（メタ）アクリレート、ＰＯ変性トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、トリペンタエリスリトールオクタ（メタ）アクリレート、トリス（アクリロキシエチル）イソシアヌレート、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレート、ペンタエリスチトールエトキシテトラ（メタ）アクリレート、シリコーンヘキサ（メタ）アクリレート、ポリグリシジル化合物（ビスフェノールＡ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、トリスフェノールメタン型エポキシ樹脂、ポリエチレングリコールジグリシジルエーテル、グリセリンポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテルなど）と（メタ）アクリル酸の反応物であるエポキシ（メタ）アクリレート、ジオールとポリイソシアネートと水酸基を有する（メタ）アクリレートとの反応物であるウレタンアクリレート、活性水素（水酸基、アミン等）を有する多官能（メタ）アクリレートとポリイソシアネート化合物の反応物である多官能ウレタン（メタ）アクリレートなどが挙げられる。これらは、単独または２種以上を混合して使用しても良い。好ましいものは、３官能以上の多官能（メタ）アクリレートである。 Examples of the ultraviolet curable polyfunctional (meth) acrylate (A) having at least two (meth) acryloyl groups in the molecule used in the present invention include polyethylene glycol di (meth) acrylate, tripropylene glycol di ( Di (meth) acrylate of ε-caprolactone adduct of (meth) acrylate, hydroxypivalate neopentyl glycol (for example, KAYARAD HX-220, HX-620 etc., manufactured by Nippon Kayaku Co., Ltd.), EO adduct of bisphenol A Di (meth) acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri ( Acrylate), epichlorohydrin (ECH) modified glycerol tri (meth) acrylate, ethylene oxide (EO) modified glycerol tri (meth) acrylate, propylene oxide (PO) modified glycerol tri (meth) acrylate, EO modified phosphoric acid tri (meth) acrylate , Caprolactone-modified trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol oct (Meth) acrylate, tris (acryloxyethyl) isocyanurate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, silicone hexa (meth) acrylate, polyglycidyl compound (bisphenol A) Type epoxy resin, phenol novolac type epoxy resin, trisphenol methane type epoxy resin, polyethylene glycol diglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, etc.) and epoxy (meta) that is a reaction product of (meth) acrylic acid ) Urethane acrylate, active hydrogen (water) which is a reaction product of acrylate, diol, polyisocyanate and (meth) acrylate having hydroxyl group Group, such as a polyfunctional (meth) acrylate and a polyfunctional urethane (meth) acrylate which is a reaction product of a polyisocyanate compound having an amine and the like). You may use these individually or in mixture of 2 or more types. Preferred is a trifunctional or higher polyfunctional (meth) acrylate.
　前記の活性水素を有する多官能（メタ）アクリレートとしては、例えば、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールジ（メタ）アクリレート等のペンタエリスリトール類、トリメチロールプロパンジ（メタ）アクリレート等のメチロール類、ビスフェノールＡジエポキシアクリレート等のエポキシアクリレート類等が挙げられる。中でも、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレートが好ましい。これらの活性水素を有する多官能（メタ）アクリレートは単独で用いても２種以上混合して用いてもよい。 Examples of the polyfunctional (meth) acrylate having active hydrogen include pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol tetra (meth). Pentaerythritols such as acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, methylols such as trimethylolpropane di (meth) acrylate, epoxy acrylates such as bisphenol A diepoxy acrylate, etc. Can be mentioned. Of these, pentaerythritol triacrylate and dipentaerythritol pentaacrylate are preferable. These polyfunctional (meth) acrylates having active hydrogen may be used alone or in admixture of two or more.
　前記のポリイソシアネートとしては、鎖状飽和炭化水素、環状飽和炭化水素（脂環式）、芳香族炭化水素で構成されるポリイソシアネートを用いることができる。このようなポリイソシアネートとしては、例えば、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート等の鎖状飽和炭化水素ポリイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、メチレンビス（４－シクロヘキシルイソシアネート）、水添ジフェニルメタンジイソシアネート、水添キシレンジイソシアネート、水添トルエンジイソシアネート等の環状飽和炭化水素（脂環式）ポリイソシアネート、２，４－トリレンジイソシアネート、１，３－キシリレンジイソシアネート、ｐ－フェニレンジイソシアネート、３，３’－ジメチル－４，４’－ジイソシアネート、６－イソプロピル－１，３－フェニルジイソシアネート、１，５－ナフタレンジイソシアネート等の芳香族ポリイソシアネートが挙げられる。中でも、イソホロンジイソシアネート、ヘキサメチレンジイソシアネートが好ましい。これらポリイソシアネートは単独で用いても２種以上混合して用いてもよい。 As the polyisocyanate, polyisocyanates composed of chain saturated hydrocarbons, cyclic saturated hydrocarbons (alicyclic), and aromatic hydrocarbons can be used. Examples of such polyisocyanates include chain saturated hydrocarbon polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and methylenebis (4-cyclohexyl). Isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, etc., cyclic saturated hydrocarbon (alicyclic) polyisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene Diisocyanate, 3,3′-dimethyl-4,4′-diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate Aromatic polyisocyanates such as 1,5-naphthalene diisocyanate. Of these, isophorone diisocyanate and hexamethylene diisocyanate are preferable. These polyisocyanates may be used alone or in combination of two or more.
　前記の多官能ウレタン（メタ）アクリレートは、前記の活性水素を有する多官能（メタ）アクリレートとポリイソシアネートとを反応させて得られる。活性水素を有する多官能（メタ）アクリレート中の活性水素基１当量に対し、ポリイソシアネートは、そのイソシアネート基当量として通常０．１～５０当量の範囲、好ましくは０．１～１０当量の範囲である。反応温度は通常３０～１５０℃、好ましくは５０～１００℃の範囲である。反応の終点は残存イソシアネートを過剰のｎ－ブチルアミンで反応させ、１Ｎ塩酸にて逆滴定する方法により算出したポリイソシアネートが０．５重量％以下となった時点とする。 The polyfunctional urethane (meth) acrylate is obtained by reacting the polyfunctional (meth) acrylate having active hydrogen with a polyisocyanate. With respect to 1 equivalent of active hydrogen group in the polyfunctional (meth) acrylate having active hydrogen, polyisocyanate is usually in the range of 0.1 to 50 equivalent, preferably in the range of 0.1 to 10 equivalent as the isocyanate group equivalent. is there. The reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C. The end point of the reaction is the time when the polyisocyanate calculated by the method of reacting residual isocyanate with excess n-butylamine and back titrating with 1N hydrochloric acid is 0.5% by weight or less.
　反応時間の短縮を目的として触媒を添加してもよい。該触媒としては塩基性触媒又は酸性触媒のいずれかが用いられる。該塩基性触媒としては、例えば、トリエチルアミン、ジエチルアミン、ジブチルアミン、アンモニア等のアミン類、トリブチルホスフィン、トリフェニルホスフィン等のホスフィン類、ピリジン、ピロール等が挙げられる。該酸性触媒としては、例えば、ナフテン酸銅、ナフテン酸コバルト、ナフテン酸亜鉛、トリブトキシアルミニウム、トリチタニウムテトラブトキシド、ジルコニウムテトラブトキシド等の金属塩類、塩化アルミニウム等のルイス酸類、２－エチルヘキサンスズ、オクチルスズトリラウリレート、ジブチルスズジラウリレート、オクチルスズジアセテート等のスズ化合物が挙げられる。これらの触媒を使用する場合、その添加量はポリイソシアネート１００重量部に対して通常０．１重量部～１重量部程度である。 A catalyst may be added for the purpose of shortening the reaction time. As the catalyst, either a basic catalyst or an acidic catalyst is used. Examples of the basic catalyst include amines such as triethylamine, diethylamine, dibutylamine, and ammonia, phosphines such as tributylphosphine and triphenylphosphine, pyridine, pyrrole, and the like. Examples of the acidic catalyst include metal salts such as copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, trititanium tetrabutoxide, zirconium tetrabutoxide, Lewis acids such as aluminum chloride, 2-ethylhexanetin, Examples thereof include tin compounds such as octyltin trilaurate, dibutyltin dilaurate, and octyltin diacetate. When these catalysts are used, the amount added is usually about 0.1 to 1 part by weight per 100 parts by weight of the polyisocyanate.
　更に、反応に際しては反応中の重合を防止するために重合禁止剤（例えば、メトキノン、ハイドロキノン、メチルハイドロキノン、フェノチアジン等）を使用することが好ましく、その使用量は反応混合物に対して０．０１重量％～１重量％程度、好ましくは０．０５重量％～０．５重量％程度である。反応温度は６０～１５０℃、好ましくは８０～１２０℃である。 Further, in the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, phenothiazine, etc.) in order to prevent polymerization during the reaction, and the amount used is 0.01 weight with respect to the reaction mixture. % To about 1% by weight, preferably about 0.05% to 0.5% by weight. The reaction temperature is 60 to 150 ° C, preferably 80 to 120 ° C.
　本発明の樹脂組成物において、分子中に少なくとも２個以上の（メタ）アクリロイル基を有する紫外線硬化型多官能（メタ）アクリレートの使用量は、本発明の樹脂組成物の固形分を１００重量％とし場合、通常８０～９５重量％であり、好ましくは９０～９５重量％である。 In the resin composition of the present invention, the amount of the ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule is 100% by weight based on the solid content of the resin composition of the present invention. In this case, it is usually 80 to 95% by weight, preferably 90 to 95% by weight.
　本発明の樹脂組成物には必要に応じて、分子中に少なくとも２個以上の（メタ）アクリロイル基を有する紫外線硬化型多官能（メタ）アクリレート以外の（メタ）アクリレート化合物を任意に使用することができる。（メタ）アクリレート化合物としては、（メタ）アクリレートモノマーを挙げることができる。 In the resin composition of the present invention, a (meth) acrylate compound other than the ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule is optionally used as necessary. Can do. Examples of (meth) acrylate compounds include (meth) acrylate monomers.
　（メタ）アクリレートモノマーとしては、例えばトリシクロデカン（メタ）アクリレート、ジシクロペンタジエンオキシエチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、イソボニル（メタ）アクリレート、アダマンタン（メタ）アクリレート、ベンジル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、モルフォリン（メタ）アクリレート、フェニルグリシジル（メタ）アクリレート、２－ヒドリキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、エチルカルビトール（メタ）アクリレート等が挙げられる。 Examples of the (meth) acrylate monomer include tricyclodecane (meth) acrylate, dicyclopentadieneoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantane (meth) acrylate, benzyl ( (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholine (meth) acrylate, phenylglycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( And meth) acrylate and ethyl carbitol (meth) acrylate.
　本発明では、さらに分子中に少なくとも２個以上の（メタ）アクリロイル基を有する紫外線硬化型多官能（メタ）アクリレートと、式（１）の構造を有する色素を含有することが特徴であり、該色素を含有した紫外線硬化型ハードコート樹脂組成物によって、透明性が高く、高い硬度を有し、ブルーライトカット機能に優れた紫外線硬化型ハードコート樹脂組成物を提供できる。式（１）に記載された以外の色素を用いると、ブルーライトカット機能が低下するだけでなく、透明性が低下したり、硬度が低下したり、紫外線硬化型樹脂が重合反応後において、未反応な残留モノマーが増加するなど問題が発生する。 The present invention is characterized by further containing an ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule and a dye having the structure of formula (1), The ultraviolet curable hard coat resin composition containing a pigment can provide an ultraviolet curable hard coat resin composition having high transparency, high hardness, and excellent blue light cut function. When a dye other than that described in Formula (1) is used, not only the blue light cut function is lowered, but also transparency is lowered, hardness is lowered, and the ultraviolet curable resin is not yet treated after the polymerization reaction. Problems such as an increase in reactive residual monomers occur.
Figure JPOXMLDOC01-appb-C000003
 （Ｒ１はハロゲン原子を示し、Ｒ２は炭素数が１乃至３のアルキル基、もしくは、置換基を有するスルホンアミド基を示し、ｎは１乃至４の整数を示す。）
Figure JPOXMLDOC01-appb-C000003
 (R 1 represents a halogen atom, R 2 represents an alkyl group having 1 to 3 carbon atoms or a sulfonamide group having a substituent, and n represents an integer of 1 to 4)
　式（１）に示される色素を用いることによって、全光線透過率が９０％以上でありながらも、４４０ｎｍ乃至４８０ｎｍの平均透過率が全光線透過率に対して１％以上低下し、好ましくは３％以上低下し、さらに好ましくは６％以上低下し、さらに、４４０ｎｍ乃至４８０ｎｍの各透過率における差の絶対値が１％以内であるフィルムまたは基材を得ることができる。つまり、式（１）で示される色素と、さらに分子中に少なくとも２個以上の（メタ）アクリロイル基を有する紫外線硬化型多官能（メタ）アクリレートとの組成物によって得られるフィルム、または基材において、４４０ｎｍ乃至４８０ｎｍの透過率が、ほぼ一定の透過率を有する特徴を持ち、４４０ｎｍ乃至４８０ｎｍの範囲で安定したブルーライトカットを実現できる。 By using the dye represented by the formula (1), the average light transmittance of 440 nm to 480 nm is reduced by 1% or more with respect to the total light transmittance, although the total light transmittance is 90% or more, preferably 3 % Or more, more preferably 6% or more, and further, a film or a substrate having an absolute value of the difference in each transmittance of 440 nm to 480 nm within 1% can be obtained. That is, in a film or substrate obtained by a composition of a dye represented by formula (1) and an ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule The transmittance of 440 nm to 480 nm has a characteristic of almost constant transmittance, and a stable blue light cut can be realized in the range of 440 nm to 480 nm.
　こういった色素の合成方法としては、例えば、オルソジクロロベンゼンを溶媒にして、式（２）に例示される置換基を有する無水フタル酸と、式（３）に例示される置換基を有する１，８‐ナフチレンジアミンの脱水縮合によって得られるが、これに限定されるものではない。なお、式（２）、式（３）のＲ１、Ｒ２、ｎは、同じものを示す。 As a method for synthesizing such a dye, for example, using orthodichlorobenzene as a solvent, phthalic anhydride having a substituent exemplified in Formula (2) and 1,1 having a substituent exemplified in Formula (3) Although obtained by dehydration condensation of 8-naphthylenediamine, it is not limited to this. In addition, R < 1 >, R < 2 >, n of Formula (2) and Formula (3) shows the same thing.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　次に、式（１）で表される色素を、より具体的な例を、下記に示す。 Next, more specific examples of the dye represented by the formula (1) are shown below.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　本発明において使用する光重合開始剤としては、例えばベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、ベンゾインイソブチルエーテルなどのベンゾイン類；アセトフェノン、２，２－ジエトキシ－２－フェニルアセトフェノン、１，１－ジクロロアセトフェノン、２－ヒドロキシ－２－メチル－フェニルプロパン－１－オン、ジエトキシアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、２－メチル－１－〔４－（メチルチオ）フェニル〕－２－モルホリノプロパン－１－オンなどのアセトフェノン類；２－エチルアントラキノン、２－ｔ－ブチルアントラキノン、２－クロロアントラキノン、２－アミルアントラキノンなどのアントラキノン類；２，４－ジエチルチオキサントン、２－イソプロピルチオキサントン、２－クロロチオキサントンなどのチオキサントン類；アセトフェノンジメチルケタール、ベンジルジメチルケタールなどのケタール類；ベンゾフェノン、４－ベンゾイル－４’－メチルジフェニルサルファイド、４，４’－ビスメチルアミノベンゾフェノンなどのベンゾフェノン類；２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイドなどのホスフィンオキサイド類等が挙げられる。また、具体的には、市場より、ＢＡＳＦ社製イルガキュア１８４（１－ヒドロキシシクロヘキシルフェニルケトン）、イルガキュア９０７（２－メチル－１－（４－（メチルチオ）フェニル）－２－（４－モルフォリニル）－１－プロパノン）、ルシリンＴＰＯ（２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド）等を容易に入手出来る。また、これらは、単独又は２種以上を混合して使用しても良い。 Examples of the photopolymerization initiator used in the present invention include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1, 1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane Acetophenones such as 1-one; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-amylanthraquinone; 2,4-diethylthio Thioxanthones such as xanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone Benzophenones such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. Specifically, from the market, Irgacure 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure 907 (2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl)-produced by BASF Corporation 1-propanone), lucillin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) and the like are easily available. Moreover, you may use these individually or in mixture of 2 or more types.
　本発明の樹脂組成物において、上記、光重合開始剤成分を使用する場合の使用量は、本発明の樹脂組成物の固形分を１００重量％とした場合、０．５～１０重量％であり、好ましくは１～７重量％である。 In the resin composition of the present invention, the amount used when the photopolymerization initiator component is used is 0.5 to 10% by weight when the solid content of the resin composition of the present invention is 100% by weight. It is preferably 1 to 7% by weight.
　また、上記の光重合開始剤は硬化促進剤と併用することもできる。併用しうる硬化促進剤としては、例えばトリエタノールアミン、ジエタノールアミン、Ｎ－メチルジエタノールアミン、２－メチルアミノエチルベンゾエート、ジメチルアミノアセトフェノン、ｐ－ジメチルアミノ安息香酸イソアミノエステル、ＥＰＡなどのアミン類、２－メルカプトベンゾチアゾールなどの水素供与体が挙げられる。これらの硬化促進剤の使用量は、本発明の樹脂組成物の固形分を１００重量％とした場合、０～５重量％である。 Also, the above photopolymerization initiator can be used in combination with a curing accelerator. Examples of the curing accelerator that can be used in combination include triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethylbenzoate, dimethylaminoacetophenone, p-dimethylaminobenzoic acid isoamino ester, amines such as EPA, 2- And hydrogen donors such as mercaptobenzothiazole. The amount of these curing accelerators used is 0 to 5% by weight when the solid content of the resin composition of the present invention is 100% by weight.
　本発明において使用しうる希釈剤としては、例えばγ－ブチロラクトン、γ－バレロラクトン、γ－カプロラクトン、γ－ヘプタラクトン、α－アセチル－γ－ブチロラクトン、ε－カプロラクトン等のラクトン類；ジオキサン、１,２－ジメトキシメタン、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、トリエチレングリコールジメチルエーテル、トリエチレングリコールジエチルエーテル、テトラエチレングリコールジメチルエーテル、テトラエチレングリコールジエチルエーテル等のエーテル類；エチレンカーボネート、プロピレンカーボネート等のカーボネート類；メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン、アセトフェノン等のケトン類；フェノール、クレゾール、キシレノール等のフェノール類；酢酸エチル、酢酸ブチル、乳酸エチル、エチルセロソルブアセテート、ブチルセロソルブアセテート、カルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテルアセテート等のエステル類；トルエン、キシレン、ジエチルベンゼン、シクロヘキサン等の炭化水素類；トリクロロエタン、テトラクロロエタン、モノクロロベンゼン等のハロゲン化炭化水素類等、石油エーテル、石油ナフサ等の石油系溶剤等の有機溶剤類、２Ｈ，３Ｈ－テトラフルオロプロパノール等のフッ素系アルコール類、パーフルオロブチルメチルエーテル、パーフルオロブチルエチルエーテル等のハイドロフルオロエーテル類；メチルアルコール、エチルアルコール、イソプロピルアルコール、ｎ－プロピルアルコール等のアルコール類；ケトンとアルコールの両方の性能を兼ね備えたダイアセトンアルコールなどが挙げられる。これらは、単独又は２種以上を混合して使用しても良い。 Examples of the diluent that can be used in the present invention include lactones such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, and ε-caprolactone; 2-dimethoxymethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, etc. Ethers; carbonates such as ethylene carbonate and propylene carbonate; Ketones such as ruethylketone, methylisobutylketone, cyclopentanone, cyclohexanone, acetophenone; phenols such as phenol, cresol, xylenol; ethyl acetate, butyl acetate, ethyl lactate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butylcarbi Esters such as tall acetate and propylene glycol monomethyl ether acetate; Hydrocarbons such as toluene, xylene, diethylbenzene and cyclohexane; Halogenated hydrocarbons such as trichloroethane, tetrachloroethane and monochlorobenzene; Petroleum such as petroleum ether and petroleum naphtha Organic solvents such as organic solvents, fluorinated alcohols such as 2H, 3H-tetrafluoropropanol, and perfluorobutylmethyl ether Ether, hydrofluoroethers such as perfluorobutyl ethyl ether; methyl alcohol, ethyl alcohol, isopropyl alcohol, and n- propyl alcohol; and diacetone alcohol combines ketone and both alcohol performance thereof. You may use these individually or in mixture of 2 or more types.
　本発明の樹脂組成物において、上記、希釈剤成分を使用する場合の使用量は、本発明の樹脂組成物全体量に対し、２０～８０重量％の範囲であり、好ましくは３０～７０重量％である。 In the resin composition of the present invention, the amount used when the diluent component is used is in the range of 20 to 80% by weight, preferably 30 to 70% by weight, based on the total amount of the resin composition of the present invention. It is.
　更に、本発明の樹脂組成物において、有機及び／又は無機粒子を添加し、防眩性、反射防止機能を付与することが可能である。有機粒子としては、例えば、プラスチックビーズのメラミンビーズ、アクリルビーズ、アクリル－スチレンビーズ、ポリカーボネートビーズ、ポリエチレンビーズ、ポリスチレンビーズ等が挙げられる。無機粒子としては、例えば、シリカとして二酸化ケイ素の無定形粒子、真球粒子、金属酸化物として、酸化錫、酸化亜鉛、酸化チタン、アルミナ等が挙げられる。これら粒子の粒径や添加量は、目標とするヘイズやその他特性により調整することが出来る。 Furthermore, in the resin composition of the present invention, organic and / or inorganic particles can be added to impart an antiglare property and an antireflection function. Examples of the organic particles include plastic beads, melamine beads, acrylic beads, acrylic-styrene beads, polycarbonate beads, polyethylene beads, and polystyrene beads. Examples of the inorganic particles include amorphous particles of silicon dioxide as silica, true spherical particles, and metal oxides such as tin oxide, zinc oxide, titanium oxide, and alumina. The particle size and addition amount of these particles can be adjusted according to the target haze and other characteristics.
　更に、本発明の樹脂組成物には、必要に応じてレベリング剤、消泡剤、紫外線吸収剤、光安定化剤、酸化防止剤、重合禁止剤などを本発明の感光性樹脂組成物に添加し、それぞれ目的とする機能性を付与することも可能である。レベリング剤としてはフッ素系化合物、シリコーン系化合物、アクリル系化合物等が、紫外線吸収剤としては、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物、トリアジン系化合物等、光安定化剤としてはヒンダードアミン系化合物、ベンゾエート系化合物等、酸化防止剤としてはフェノール系化合物等、重合禁止剤としては、メトキノン、メチルハイドロキノン、ハイドロキノン等が挙げられる。 Furthermore, a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor and the like are added to the photosensitive resin composition of the present invention as necessary. However, it is also possible to provide each intended functionality. Fluorine compounds, silicone compounds, acrylic compounds, etc. as leveling agents, benzotriazole compounds, benzophenone compounds, triazine compounds, etc. as UV absorbers, hindered amine compounds, benzoate compounds as light stabilizers Compounds, etc., antioxidants include phenolic compounds, and polymerization inhibitors include methoquinone, methylhydroquinone, hydroquinone, and the like.
　本発明の樹脂組成物は、上記、少なくとも２個以上の（メタ）アクリロイル基を有する紫外線硬化型多官能（メタ）アクリレート、式（１）に例示される色素、光重合開始剤、希釈剤を含有し、必要に応じて、その他の成分を混合することにより得ることができる。 The resin composition of the present invention comprises the above-mentioned ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups, a dye exemplified by formula (1), a photopolymerization initiator, and a diluent. It can be obtained by mixing and mixing other components as required.
　こうして得られた本発明の樹脂組成物は、経時的に安定である。 The resin composition of the present invention thus obtained is stable over time.
　本発明の上記の紫外線硬化型ハードコート樹脂組成物を基材上に、該樹脂組成物の乾燥後の膜厚が通常０．１～２０μｍ、好ましくは１～１０μｍになるように塗布し、乾燥後紫外線を照射して硬化膜を形成させることにより、ハードコートフィルムとして得ることができる。 The UV curable hard coat resin composition of the present invention is applied onto a substrate so that the film thickness after drying of the resin composition is usually 0.1 to 20 μm, preferably 1 to 10 μm, and dried. It can obtain as a hard coat film by irradiating back ultraviolet rays and forming a cured film.
　基材にフィルムを使用する場合、基材フィルムとしては、例えば、ポリエステル、ポリプロピレン、ポリエチレン、ポリアクリレート、ポリカーボネート、トリアセチルセルロース、ポリエーテルスルホン、シクロオレフィン系ポリマーなどが挙げられる。フィルムはある程度厚いシート状のものであっても良い。使用するフィルムは、柄や易接着層を設けたもの、コロナ処理等の表面処理をしたものであっても良い。 When using a film for the substrate, examples of the substrate film include polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, triacetylcellulose, polyethersulfone, and cycloolefin polymer. The film may be a thick sheet. The film to be used may be one provided with a handle or an easy-adhesion layer, or one subjected to surface treatment such as corona treatment.
　上記の樹脂組成物の塗布方法としては、例えば、バーコーター塗工、メイヤーバー塗工、エアナイフ塗工、グラビア塗工、リバースグラビア塗工、マイクログラビア塗工、マイクロリバースグラビアコーター塗工、ダイコーター塗工、ディップ塗工、スピンコート塗工、スプレー塗工などが挙げられる。 Examples of the coating method of the resin composition include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, micro gravure coating, micro reverse gravure coater, and die coater. Examples thereof include coating, dip coating, spin coating coating, and spray coating.
　硬化のために紫外線を照射するが、電子線などを使用することもできる。紫外線により硬化させる場合、光源としては、キセノンランプ、高圧水銀灯、メタルハライドランプなどを有する紫外線照射装置が使用され、必要に応じて光量、光源の配置などが調整される。高圧水銀灯を使用する場合、８０～１６０Ｗ／ｃｍ2のエネルギーを有するランプ１灯に対して搬送速度５～６０ｍ／分で１００～１０００ｍＪ／ｃｍ２で硬化させるのが好ましい。一方、電子線により硬化させる場合は、光重合開始剤は添加しなくても良く、１００～５００ｅＶのエネルギーを有する電子線加速装置を使用するのが好ましい。 Although ultraviolet rays are irradiated for curing, an electron beam or the like can also be used. In the case of curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp or the like is used as a light source, and the light amount, the arrangement of the light source, etc. are adjusted as necessary. When a high-pressure mercury lamp is used, it is preferable to cure at 100 to 1000 mJ / cm 2 at a conveyance speed of 5 to 60 m / min with respect to one lamp having energy of 80 to 160 W / cm 2 . On the other hand, when curing with an electron beam, it is not necessary to add a photopolymerization initiator, and it is preferable to use an electron beam accelerator having an energy of 100 to 500 eV.
　以上によって得られた基材としては、透明ポリマーまたは、そのフィルムが好ましい。形成する透明ポリマー又はフィルムとしては、機械的強度が高く、熱安定性が良好な透明ポリマー又はフィルムが好ましい。透明保護層として用いる物質として、例えば、トリアセチルセルロースやジアセチルセルロースのようなセルロースアセテート樹脂又はそのフィルム、アクリル樹脂又はそのフィルム、ポリ塩化ビニル樹脂又はそのフィルム、ナイロン樹脂またはそのフィルム、ポリエステル樹脂又はそのフィルム、ポリアリレート樹脂又はそのフィルム、ノルボルネンのような環状オレフィンをモノマーとする環状ポリオレフィン樹脂又はそのフィルム、ポリエチレン、ポリプロピレン、シクロ系ないしはノルボルネン骨格を有するポリオレフィン又はその共重合体、主鎖又は側鎖がイミド及び／又はアミドの樹脂又はポリマー又はそのフィルムが例示される。 As the substrate obtained as described above, a transparent polymer or a film thereof is preferable. The transparent polymer or film to be formed is preferably a transparent polymer or film having high mechanical strength and good thermal stability. As a substance used as a transparent protective layer, for example, cellulose acetate resin such as triacetyl cellulose or diacetyl cellulose or film thereof, acrylic resin or film thereof, polyvinyl chloride resin or film thereof, nylon resin or film thereof, polyester resin or film thereof Film, polyarylate resin or film thereof, cyclic polyolefin resin or film thereof using cyclic olefin such as norbornene as a monomer, polyethylene, polypropylene, polyolefin having cyclo or norbornene skeleton or copolymer thereof, main chain or side chain Examples include imide and / or amide resins or polymers or films thereof.
　得られた基材は、例えば、ポリビニルアルコール系樹脂フィルムよりなる偏光素子、または、その偏光素子をトリアセチルセルロース等でラミネートされた偏光板へ接着剤等を介して貼合することもできる。こうして得られるフィルムは、液晶セルに設ける場合に偏光機能に加えて、硬度、透明性、耐擦傷性、ブルーライトカットを必要とする分野に好適なハードコートフィルム、または、基材になる。 The obtained substrate can be bonded to a polarizing element made of, for example, a polyvinyl alcohol resin film, or a polarizing plate laminated with triacetyl cellulose or the like via an adhesive or the like. The film thus obtained becomes a hard coat film or substrate suitable for fields requiring hardness, transparency, scratch resistance and blue light cut in addition to the polarizing function when provided in a liquid crystal cell.
　また、本発明の樹脂組成物を用いて、フィルム、レンズなども樹脂成型できるため、そういった成型部品、または成型体を作製するにしても、本発明樹脂組成物は用いることが出来る。 Also, since the resin composition of the present invention can be used for resin molding of films, lenses and the like, the resin composition of the present invention can be used even when such molded parts or molded bodies are produced.
　以下、本発明を実施例により更に詳細に説明するが、本発明はこれら実施例によって限定されるものではない。また、実施例中、特に断りがない限り、部は重量％を示す。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Moreover, unless otherwise indicated in an Example, a part shows weight%.
　調合例１
５００ｍＬコルベンに、ペンタエリスリトールトリアクリレートとペンタエリスリトールテトラアクリレートの混合物（商品名：ＫＡＹＡＲＡＤ　ＰＥＴ－３０、日本化薬（株）製）を６０部、多官能ウレタンアクリレート（商品名：ＫＡＹＡＲＡＤ　ＵＸ－５０００、日本化薬（株）製）を４０部、１－ヒドロキシシクロヘキシルフェニルケトン（商品名：イルガキュア１８４、ＢＡＳＦ（株）製）を５部、トルエン６６．７部を室温で混合溶解し、固形分６０％のマスター液１を作製した。 Formulation Example 1
In 500 mL Kolben, 60 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name: KAYARAD PET-30, manufactured by Nippon Kayaku Co., Ltd.), polyfunctional urethane acrylate (trade name: KAYARAD UX-5000, Japan) 40 parts of Kayaku Co., Ltd.), 5 parts of 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by BASF Corporation) and 66.7 parts of toluene are mixed and dissolved at room temperature, and the solid content is 60%. A master liquid 1 was prepared.
　調合例２
式（４）に示す化合物と、式（５）に示す化合物をオルソジクロロベンゼンに添加し、撹拌しながら昇温させて、化合物例１に示す化合物を含む溶液を得た。得られた溶液を、ろ過し、残留分を乾燥させて、４５０ｎｍに極大吸収波長を有する化合物例１の色素を得た。得られた色素を０．１部と、トルエン１９．９部を混合溶解し、マスター液２を作製した。 Formulation Example 2
The compound shown in Formula (4) and the compound shown in Formula (5) were added to orthodichlorobenzene, and the temperature was raised while stirring to obtain a solution containing the compound shown in Compound Example 1. The obtained solution was filtered, and the residue was dried to obtain a pigment of Compound Example 1 having a maximum absorption wavelength at 450 nm. 0.1 part of the obtained pigment and 19.9 parts of toluene were mixed and dissolved to prepare a master liquid 2.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　比較例１
　マスター液１を８０μｍトリアセチルセルロースフィルム上にバーコーターにて塗布し、８０℃乾燥機中で２分乾燥後、１６０Ｗ高圧水銀灯を設置した紫外線照射装置により積算光量２５０ｍＪ／ｃｍ２にて硬化させ、膜厚４～５μｍのハードコートフィルムを得た。 Comparative Example 1
The master liquid 1 was applied onto an 80 μm triacetylcellulose film with a bar coater, dried for 2 minutes in an 80 ° C. dryer, and then cured with an ultraviolet light irradiation apparatus equipped with a 160 W high-pressure mercury lamp at an integrated light amount of 250 mJ / cm 2 A hard coat film having a thickness of 4 to 5 μm was obtained.
　実施例１乃至３
　下表１に示す材料を配合した樹脂組成物を８０μｍトリアセチルセルロースフィルム上にバーコーターにて塗布し、８０℃乾燥機中で２分乾燥後、１６０Ｗ高圧水銀灯を設置した紫外線照射装置により積算光量２５０ｍＪ／ｃｍ２にて硬化させ、膜厚４～５μｍのブルーライトカット性ハードコートフィルムを得た。尚、表１において単位は「部」を示す。 Examples 1 to 3
The resin composition containing the materials shown in Table 1 below was coated on an 80 μm triacetylcellulose film with a bar coater, dried in an 80 ° C. dryer for 2 minutes, and then integrated with a UV irradiation device equipped with a 160 W high-pressure mercury lamp. Curing was performed at 250 mJ / cm 2 to obtain a blue light-cut hard coat film having a thickness of 4 to 5 μm. In Table 1, the unit indicates “part”.
Figure JPOXMLDOC01-appb-I000015
Figure JPOXMLDOC01-appb-I000015
比較例２乃至４
実施例１乃至３において使用した色素を、４２０ｎｍに極大吸収波長を有する日本化薬社製のＹｅｌｌｏｗ色素　Ｆｌａｖｉｎｅ　ＦＧに変えた以外は同様に実施し、比較例２乃至４とした。 Comparative Examples 2 to 4
The same procedure was performed except that the dye used in Examples 1 to 3 was changed to Yellow Dye Flavine FG manufactured by Nippon Kayaku Co., Ltd. having a maximum absorption wavelength at 420 nm, and Comparative Examples 2 to 4 were obtained.
　実施例１乃至３、比較例で得られたブルーライトカット性ハードコートフィルムにつき、下記項目を評価しその結果を表２、表３に示した。表４には、透過率を測定してえられた４４０ｎｍ乃至４８０ｎｍの透過率、表５には４４０ｎｍ乃至４８０ｎｍの各波長透過率を示す。 The following items were evaluated for the blue light cut hard coat films obtained in Examples 1 to 3 and Comparative Example, and the results are shown in Tables 2 and 3. Table 4 shows the transmittance of 440 nm to 480 nm obtained by measuring the transmittance, and Table 5 shows the wavelength transmittances of 440 nm to 480 nm.
（鉛筆硬度）
　ＪＩＳ　Ｋ　５４００に従い、鉛筆引っかき試験機を用いて、上記組成の塗工フィルムの鉛筆硬度を測定した。詳しくは、測定する硬化皮膜を有するポリエステルフィルム上に、鉛筆を４５度の角度で、上から７５０ｇの荷重を掛け５ｍｍ程度引っかき、５回中、４回以上傷の付かなかった鉛筆の硬さで表した。 (Pencil hardness)
According to JIS K 5400, the pencil hardness of the coated film having the above composition was measured using a pencil scratch tester. Specifically, on the polyester film having the cured film to be measured, the pencil is applied with a load of 750 g from the top at a 45 degree angle, and is scratched for about 5 mm. expressed.
（全光線透過率）
(株)村上色彩技術研究所製、ＨＭ－１５０を使用し測定した。 (Total light transmittance)
Measurement was performed using HM-150 manufactured by Murakami Color Research Laboratory.
（ヘイズ）
(株)村上色彩技術研究所製、ＨＭ－１５０を使用し測定した。 (Haze)
Measurement was performed using HM-150 manufactured by Murakami Color Research Laboratory.
（色度）
(株)日立製作所製、Ｕ－４１００を使用し、ハロゲンランプでのＬ＊、ａ＊、ｂ＊を測定した。 (Chromaticity)
Using U-4100 manufactured by Hitachi, Ltd., L *, a *, and b * were measured with a halogen lamp.
（耐擦傷性）
　スチールウール＃００００を使用し、２５０ｇ／ｃｍ２の荷重にて１往復／にて、１０往復摩耗した後、摩耗面を観察し、下記の評価を実施した。
　評価・・・○：傷無し、×：傷発生 (Abrasion resistance)
Steel wool # 0000 was used, and after 10 reciprocating wears at 1 reciprocation / load at 250 g / cm 2 , the wear surface was observed and the following evaluation was performed.
Evaluation: ○: No scratch, ×: Scratch occurrence
（密着性）
　実施例のハードコート層に１ｍｍ間隔で１００個のマス目をカッターで作製し、セロテープをしっかり密着させた後、９０度方向に一気に剥がし、下記の評価を実施した。
　評価・・・○：１００／１００密着良好、×：剥れ発生 (Adhesion)
100 squares were produced on the hard coat layer of the example at intervals of 1 mm with a cutter, and after the cellophane was firmly adhered, it was peeled off at a 90 degree direction, and the following evaluation was performed.
Evaluation: ○: 100/100 good adhesion, x: peeling occurred
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019
　実施例１乃至３では、全光線透過率を９０％以上に維持しながらも、ブルーライトカット領域である４４０ｎｍでの透過率をカットすることが可能であった。また、ハードコートフィルムとしての特性は維持していることが、比較例との比較で確認された。すなわち、従来のハードコートフィルムの特性を保ったまま、ブルーライトカット機能を色素の劣化を起こすことなく付与することが出来た。また、４４０ｎｍ乃至４８０ｎｍの透過率がほぼ均一なフィルム、または、基材が得られていることが分かる。 In Examples 1 to 3, it was possible to cut the transmittance at 440 nm, which is the blue light cut region, while maintaining the total light transmittance at 90% or more. Moreover, it was confirmed by the comparison with a comparative example that the characteristic as a hard coat film is maintained. That is, the blue light cut function could be imparted without causing deterioration of the pigment while maintaining the characteristics of the conventional hard coat film. In addition, it can be seen that a film or a substrate having a substantially uniform transmittance from 440 nm to 480 nm is obtained.
　本発明の樹脂組成物で得られたハードコートフィルムは、ブルーライトカット性に優れ、透明性が高く、硬度も良好であり、特にタッチパネルを搭載したスマートフォン、タブレットＰＣ、ノートＰＣ、プラスチック光学部品など、硬度、透明性、耐擦傷性、ブルーライトカットを必要とする分野に好適なハードコートフィルムである。 The hard coat film obtained with the resin composition of the present invention has excellent blue light cutability, high transparency, and good hardness, especially a smartphone equipped with a touch panel, a tablet PC, a notebook PC, a plastic optical component, etc. It is a hard coat film suitable for fields requiring hardness, transparency, scratch resistance and blue light cut.

Claims (10)

  1. 分子中に少なくとも２個以上の（メタ）アクリロイル基を有する紫外線硬化型多官能（メタ）アクリレート、及び、式（１）の構造を有する色素を含有する紫外線硬化型ハードコート樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     （Ｒ１はハロゲン原子を示し、Ｒ２は炭素数が１乃至３のアルキル基、もしくは、置換基を有するスルホンアミド基を示し、ｎは１乃至４の整数を示す。）     An ultraviolet curable hard coat resin composition comprising an ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in a molecule and a dye having a structure of the formula (1).
    Figure JPOXMLDOC01-appb-C000001
     (R 1 represents a halogen atom, R 2 represents an alkyl group having 1 to 3 carbon atoms or a sulfonamide group having a substituent, and n represents an integer of 1 to 4)
  2. 光重合開始剤を含有することを特徴とする請求項１に記載の紫外線硬化型ハードコート樹脂組成物。 The ultraviolet curable hard coat resin composition according to claim 1, further comprising a photopolymerization initiator.
  3. 希釈剤を含有することを特徴とする請求項１または２に記載の紫外線硬化型ハードコート樹脂組成物。 The ultraviolet curable hard coat resin composition according to claim 1 or 2, further comprising a diluent.
  4. 有機及び／又は無機粒子を含有することを特徴とする請求項１乃至請求項３のいずれか一項に記載の紫外線硬化型ハードコート樹脂組成物。 The ultraviolet curable hard coat resin composition according to any one of claims 1 to 3, comprising organic and / or inorganic particles.
  5. 請求項１乃至４のいずれか一項に記載の紫外線硬化型ハードコート樹脂組成物よりなる硬化層を有する基材。 The base material which has a hardened layer which consists of an ultraviolet curable hard coat resin composition as described in any one of Claims 1 thru | or 4.
  6. 透明ポリマーまたはそのフィルムである、請求項５に記載の基材。 The substrate according to claim 5, which is a transparent polymer or a film thereof.
  7. 全光線透過率が９０％以上であって、かつ、４４０ｎｍ乃至４８０ｎｍの平均透過率が全光線透過率に対して１％以上低下し、さらに、４４０ｎｍ乃至４８０ｎｍの各透過率における差の絶対値が１％以内であることを特徴とする請求項５または６に記載の基材。 The total light transmittance is 90% or more, the average transmittance from 440 nm to 480 nm is reduced by 1% or more with respect to the total light transmittance, and the absolute value of the difference in each transmittance from 440 nm to 480 nm is The substrate according to claim 5 or 6, wherein the content is within 1%.
  8. 請求項１乃至４のいずれか一項に記載の紫外線硬化型ハードコート樹脂組成物の硬化層を含む偏光板。 A polarizing plate comprising a cured layer of the ultraviolet curable hard coat resin composition according to any one of claims 1 to 4.
  9. 請求項１乃至４のいずれか一項に記載の紫外線硬化型ハードコート樹脂組成物の硬化層を含む液晶表示装置。 A liquid crystal display device comprising a cured layer of the ultraviolet curable hard coat resin composition according to claim 1.
  10. 請求項１乃至４のいずれか一項に記載の紫外線硬化型ハードコート樹脂組成物の硬化層を有する成型物。 The molding which has a hardened layer of the ultraviolet curable hard coat resin composition as described in any one of Claims 1 thru | or 4.
PCT/JP2014/067251 2013-06-28 2014-06-27 Uv-curable hard-coating resin composition WO2014208748A1 (en)

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JP2015194553A (en) * 2014-03-31 2015-11-05 大日本印刷株式会社 Blue light cut film, display device, and blue light cut film resin composition
JP2016143026A (en) * 2015-02-05 2016-08-08 住友化学株式会社 Composite polarizing plate and liquid crystal display device
US11073638B2 (en) 2016-09-07 2021-07-27 Largan Precision Co., Ltd. Optical image lens assembly and plastic material thereof, image capturing apparatus and electronic device
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JP2015194553A (en) * 2014-03-31 2015-11-05 大日本印刷株式会社 Blue light cut film, display device, and blue light cut film resin composition
JP2016143026A (en) * 2015-02-05 2016-08-08 住友化学株式会社 Composite polarizing plate and liquid crystal display device
US11073638B2 (en) 2016-09-07 2021-07-27 Largan Precision Co., Ltd. Optical image lens assembly and plastic material thereof, image capturing apparatus and electronic device
EP3418782B1 (en) * 2016-12-26 2023-05-03 LG Chem, Ltd. Polarizer protection film, polarizing plate comprising the same, liquid crystal display comprising the polarizing plate, and coating composition for polarizer protecting film

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