Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
• • 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
  • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

Definitions

• the present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet manufactured using the same, an optical member, and a display device.
• the flat panel display includes a liquid crystal display (LCD), a plasma display panel (PDP), an organic electroluminescence display (OLED), and the like.
• a flat panel display device includes a display panel and an optical film.
• As the optical film a polarizing film, a retardation film, an anti-glare film, a wide viewing angle compensation film, a brightness improving film, and the like are used.
• OCA optically clear adhesive
• PSA pressure sensitive adhesive
• the optical pressure-sensitive adhesive requires high transmittance and low haze, and must satisfy physical properties such as adhesion to various substrates, durability such as heat resistance and moisture resistance. In addition, if a defect occurs on the surface of the display panel or optical film, reworkability is also required for smooth replacement.
• a touch screen panel (hereinafter, referred to as a 'touch panel'), which is an optical display element, is formed on the display surface side of the flat panel display, etc., and the display device and the coordinate axis are recognized immediately.
• a touch screen panel hereinafter, referred to as a 'touch panel'
• the display device and the coordinate axis are recognized immediately.
• the capacitive method composed of two conductive ITO (Indium Tin Oxide) layers detects signals through electromagnetic changes rather than physical contact between the upper and lower electrodes. For this reason, the capacitive method has been widely used in recent years.
• ITO Indium Tin Oxide
• the optical adhesive is provided between the touch panel and the optical member and may be used to bond the two devices.
• an indium tin oxide (ITO) layer for implementing a capacitive touch panel has a step difference due to patterning, and thus there is a problem of visibility due to a difference in refractive index.
• Korean Patent Application Laid-Open No. 10-2016-0045199 discloses an adhesive film having excellent adhesion between various substrates while containing nanoparticles of high refractive index in the adhesive film, which is higher than 1.48, the refractive index of a general adhesive, and have.
• the adhesive film contains nanoparticles, haze properties may be poor, and when nanoparticles of 100 nm or less are used, there is a problem in that the viscosity of the crude liquid increases. necessity is raised
• An object of the present invention is to provide a pressure-sensitive adhesive composition having an improved refractive index.
• Another object of the present invention is to provide a pressure-sensitive adhesive composition having improved step water absorption.
• an object of the present invention is to provide a pressure-sensitive adhesive composition having improved haze properties.
• Another object of the present invention is to provide a pressure-sensitive adhesive sheet prepared by using the pressure-sensitive adhesive composition.
• this invention makes it an object of invention to provide the optical member containing the adhesive layer formed from the said adhesive composition.
• Another object of the present invention is to provide a display device including the optical member.
• the present invention relates to a pressure-sensitive adhesive composition
• a pressure-sensitive adhesive composition comprising an acrylic copolymer having a refractive index of 1.55 to 1.70.
• the acrylic copolymer may include a repeating unit derived from a high refractive acrylic monomer having a refractive index of 1.58 or more of the homopolymer.
• the high refractive acrylic monomer having a refractive index of 1.58 or more of the homopolymer is pentabromophenyl (meth) acrylate, 2-(naphthalen-2-yloxy) ethyl (meth) acrylate , 2- (naphthalen-2-ylthio) ethyl (meth) acrylate, biphenylmethyl (meth) acrylate and 1-pyrene methyl (meth) acrylate containing one or more selected from the group consisting of can
• the high refractive acrylic monomer having a refractive index of 1.58 or more of the homopolymer may be included in an amount of 10 to 70% by weight based on the total weight of the acrylic copolymer.
• the acrylic copolymer is at least one of a repeating unit derived from an acrylic monomer having a hydrocarbon group having 1 to 20 carbon atoms and a repeating unit derived from a polymerizable monomer having a crosslinkable functional group. may further include
• the acrylic monomer having a hydrocarbon group having 1 to 20 carbon atoms is methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl ( meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) ) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isobornyl acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth)
• the polymerizable monomer having a crosslinkable functional group includes a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, a cyano group-containing monomer, a vinyl ester monomer, an aromatic vinyl monomer, a carboxyl group-containing monomer, and an acid anhydride. It may include at least one selected from the group consisting of a group-containing monomer, a hydroxyl group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, an imide group-containing monomer, an epoxy group-containing monomer, and an ether group-containing monomer.
• the pressure-sensitive adhesive composition may further include at least one or more of a photoinitiator, a thermal curing agent, and nanoparticles.
• the thermal curing agent may include an isocyanate-based crosslinking agent.
• the nanoparticles are titanium oxide, zinc oxide, zirconium oxide, magnesium oxide, zirconium titanate, zirconium silicate, strontium titanate, aluminum titanate, silicon ferrite, nickel ferrite. , cobalt ferrite, barium carbonate, silicon carbide, yttrium carbide, magnesium silicate, zinc sulfate, and may include one or more selected from the group consisting of barium sulfate.
• the glass transition temperature (Tg) of the pressure-sensitive adhesive composition may be -10 °C or less.
• the refractive index of the pressure-sensitive adhesive layer prepared by the pressure-sensitive adhesive composition may be 1.58 or more.
• the haze of the pressure-sensitive adhesive layer prepared by the pressure-sensitive adhesive composition may be less than 2%.
• this invention relates to the adhesive sheet manufactured using the said adhesive composition.
• the refractive index of the pressure-sensitive adhesive sheet may be 1.58 or more.
• this invention relates to the optical member containing the adhesive layer formed from the said adhesive composition.
• this invention relates to the display apparatus containing the said optical member.
• the refractive index is improved compared to the conventional pressure-sensitive adhesive composition, and the visibility may be improved without including a separate high refractive index pattern layer.
• the step absorbency is improved compared to the conventional pressure-sensitive adhesive composition, and may exhibit excellent reliability even in a wide temperature range.
• haze (Haze) characteristics are improved compared to the conventional pressure-sensitive adhesive composition, it may be particularly suitable for use as an optical pressure-sensitive adhesive.
• the pressure-sensitive adhesive composition according to the present invention it is possible to prevent an increase in the viscosity of the crude liquid compared to the conventional pressure-sensitive adhesive composition, and thus processability may be further improved.
• the present invention provides a pressure-sensitive adhesive composition
• a pressure-sensitive adhesive composition comprising an acrylic copolymer having a refractive index of 1.55 to 1.70, and a pressure-sensitive adhesive sheet, an optical member, and a display device manufactured using the same.
• the pressure-sensitive adhesive composition of the present invention by including the acrylic copolymer having a refractive index of 1.55 to 1.70, it is possible to improve the refractive index, haze (Haze) characteristics and reliability of the pressure-sensitive adhesive layer.
• (meth)acrylate described in the present invention is defined as a concept including both acrylates and methacrylates.
• the pressure-sensitive adhesive composition of the present invention may include an acrylic copolymer and, if necessary, further include at least one or more of a photoinitiator, a thermal curing agent, and nanoparticles.
• the adhesive composition of this invention has a glass transition temperature (Tg) of -10 degrees C or less.
• Tg glass transition temperature
• the pressure-sensitive adhesive layer formed by the pressure-sensitive adhesive composition may exhibit good adhesive properties.
• the pressure-sensitive adhesive layer prepared by the pressure-sensitive adhesive composition of the present invention may have a refractive index of 1.58 or more, more preferably 1.58 to 1.70, and most preferably, 1.60 to 1.70. In this case, visibility may be improved without including a separate high refractive index pattern layer in the display device including the touch panel.
• the pressure-sensitive adhesive layer prepared by the pressure-sensitive adhesive composition of the present invention can exhibit a high refractive index without including an excessive amount of nanoparticles, there is an advantage in terms of optical properties.
• haze may be less than 2%.
• the light transmittance is improved, and it may be particularly suitable for use as an optical adhesive for a display device or the like.
• the pressure-sensitive adhesive composition according to the present invention includes an acrylic copolymer for adhesion properties and durability.
• the acrylic copolymer preferably has a refractive index of 1.55 to 1.70.
• the refractive index of the acrylic copolymer is 1.55 to 1.70, it is close to the target refractive index of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive sheet. Therefore, it is possible to implement a high refractive index of the pressure-sensitive adhesive layer even without including separate nanoparticles, there may be advantages in terms of fairness and light transmittance, and the elastic modulus may be improved to prevent deterioration of durability.
• by further including nanoparticles of high refractive index if necessary it is possible to exhibit a more improved refractive index compared to the conventional pressure-sensitive adhesive composition.
• the structure thereof is not particularly limited, but preferably includes a repeating unit derived from a high refractive acrylic monomer having a refractive index of 1.58 or more of a homopolymer.
• the high refractive acrylic monomer having a refractive index of 1.58 or more of the homopolymer is, for example, pentabromophenyl (meth)acrylate, 2-(naphthalen-2-yloxy)ethyl (meth) Acrylate (2-(Naphthalen-2-yloxy)ethyl (meth)acrylate), 2-(Naphthalen-2-ylthio)ethyl (meth)acrylate ), biphenyl methyl (meth) acrylate, and 1-pyrene methyl (meth) acrylate (1-Pyrene methyl (meth) acrylate) containing at least one selected from the group consisting of may be, but is not limited thereto as described above.
• the high refractive acrylic monomer having a refractive index of 1.58 or more of the homopolymer is not particularly limited as long as it can improve the refractive index and elastic modulus of the matrix, but it is included in an amount of 10 to 70% by weight based on the total weight of the acrylic copolymer. Preferably, it may be 15 to 60% by weight, more preferably.
• the content of the high refractive acrylic monomer having a refractive index of 1.58 or more of the homopolymer is less than 10% by weight, the effect of improving the refractive index and elastic modulus is insignificant, and when it exceeds 70% by weight, the adhesive properties and durability of the pressure-sensitive adhesive composition itself are reduced can be
• the acrylic copolymer further comprises at least one of a repeating unit derived from an acrylic monomer having a hydrocarbon group having 1 to 20 carbon atoms and a repeating unit derived from a polymerizable monomer having a crosslinkable functional group. may include.
• the acrylic monomer having a hydrocarbon group having 1 to 20 carbon atoms is preferably a (meth)acrylate-based monomer, but is not limited thereto.
• the hydrocarbon group may include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
• a hydrogen atom included in the hydrocarbon group may be substituted with an alkyl group, a halogen atom, an alkoxy group, a phenoxy group, or the like, and -CH 2 - included in the hydrocarbon group is a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Or -(CH 2 CH 2 O)m- may be substituted. In this case, m may be 1 to 4.
• the acrylic monomer having a hydrocarbon group having 1 to 20 carbon atoms is not particularly limited as long as it imparts adhesive properties or cohesive force to the pressure-sensitive adhesive composition.
• the acrylic monomer having a hydrocarbon group having 1 to 20 carbon atoms is methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) Acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylic Rate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isobornyl acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate , n-decyl (meth) acrylate,
• the acrylic copolymer has a repeating unit derived from an acrylic monomer having a hydrocarbon group having 1 to 20 carbon atoms
• the acrylic monomer having a hydrocarbon group having 1 to 20 carbon atoms is used in an amount of 30 to 90% by weight based on the total weight of the acrylic copolymer. It is preferably included, and more preferably 30 to 60% by weight.
• the content of the acrylic monomer having a hydrocarbon group having 1 to 20 carbon atoms is less than 30% by weight, the adhesive force may be slightly lowered, and if it exceeds 90% by weight, the cohesive force may be somewhat reduced.
• the polymerizable monomer having the crosslinkable functional group is not particularly limited as long as it reacts with the crosslinking agent to impart cohesive force or adhesive strength by chemical bonding so that the cohesive force breakage of the pressure-sensitive adhesive does not occur under high temperature or humidity conditions.
• the polymerizable monomer having a crosslinkable functional group is a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, a cyano group-containing monomer, a vinyl ester monomer, an aromatic vinyl monomer, a carboxyl group-containing monomer, an acid anhydride group-containing monomer It may include at least one selected from the group consisting of a monomer, a hydroxyl group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, an imide group-containing monomer, an epoxy group-containing monomer, and an ether group-containing monomer.
• the sulfonic acid group-containing monomer is, for example, styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl (meth)acrylate , (meth)acryloyloxynaphthalenesulfonic acid, sodium vinylsulfonate, and the like.
• Examples of the phosphoric acid group-containing monomer include 2-hydroxyethyl acryloyl phosphate, and the cyano group-containing monomer includes, for example, (meth)acrylonitrile.
• the vinyl ester monomer includes, for example, vinyl acetate, vinyl propionate, vinyl laurate, and the like, and the aromatic vinyl monomer is, for example, styrene, chlorostyrene, chloromethylstyrene, ⁇ -methylstyrene, and other substituted styrenes.
• the carboxyl group-containing monomer for example, monoacids such as (meth)acrylic acid, crotonic acid, isocrotonic acid, carboxyethyl (meth)acrylate, and carboxypentyl (meth)acrylate; diacids such as maleic acid, itaconic acid and fumaric acid and monoalkyl esters thereof; Ring-opening adduct of succinic acid anhydride of 2-hydroxyalkyl (meth)acrylate having 2 to 3 carbon atoms in the alkyl group, and ring-opening adduct of succinic anhydride in hydroxyalkylene glycol (meth)acrylate having 2 to 4 carbon atoms in the alkylene group , a compound obtained by ring-opening addition of succinic anhydride to the caprolactone adduct of 2-hydroxyalkyl (meth)acrylate having 2 to 3 carbon atoms in the alkyl group, among which (meth)acrylic acid is preferable.
• the acid anhydride-containing monomer includes, for example, maleic anhydride, itaconic anhydride, and acid anhydrides thereof
• the hydroxyl group-containing monomer is, for example, 2-hydroxyethyl (meth)acrylate , 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl acrylate, N-methylol (meth)acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxy hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, etc. are mentioned.
• the amide group-containing monomer is, for example, (meth) acrylamide, N-isopropyl acrylamide, N-tert-butyl acrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (meth) ) Acrylamide, 6-hydroxyhexyl (meth)acrylamide, 8-hydroxyoctyl (meth)acrylamide, 2-hydroxyethylhexyl (meth)acrylamide, etc. are mentioned.
• the amino group-containing monomer is, for example, N,N- (dimethylamino) ethyl (meth) acrylate, N, N- (diethylamino) ethyl (meth) acrylate, N, N- (dimethylamino) propyl (meth)acrylate etc. are mentioned, As for the said imide group containing monomer, cyclohexyl maleimide, isopropyl maleimide, etc. are mentioned, for example.
• the epoxy group-containing monomer includes, for example, (meth) glycidyl acrylate, methyl glycidyl (meth) acrylate, and the like, and the ether group-containing monomer is, for example, 3-methoxybutyl (meth) ) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2-methoxybutyl (meth) acrylate and oxypolyethylene glycol acrylate, ethoxy-diethylene glycol (meth) acrylate, and ethyl carbitol (meth) acrylate.
• the ether group-containing monomer is, for example, 3-methoxybutyl (meth) ) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2-methoxybutyl (meth) acrylate and oxypolyethylene glyco
• the polymerizable monomer having a crosslinkable functional group is preferably included in an amount of 0.05 to 10% by weight based on the total weight of the acrylic copolymer. and more preferably 1 to 10% by weight.
• the content of the polymerizable monomer having a crosslinkable functional group is less than 0.05% by weight, the durability may decrease as the cohesive force of the pressure-sensitive adhesive composition decreases, and if it exceeds 10% by weight, the adhesive strength and durability may be somewhat reduced.
• the acrylic copolymer may further include other monomers commonly used in the art to which the present invention pertains within a range that does not reduce adhesive strength in addition to the above monomers, for example, to the total weight of the acrylic copolymer It may be further included in an amount of 10% by weight or less.
• the acrylic copolymer may have a weight average molecular weight (in terms of polystyrene; Mw) measured by Gel Permeation Chromatography (GPC) of 500,000 to 2 million, more preferably 700,000 to 1.7 million .
• Mw weight average molecular weight measured by Gel Permeation Chromatography
• GPC Gel Permeation Chromatography
• Degradation may occur, and if it exceeds 2 million, the viscosity of the adhesive resin composition is too high when manufacturing the adhesive film, so a large amount of monomer is required to dilute to meet the appropriate viscosity required for manufacturing, and accordingly, high energy during UV polymerization and curing may be required or unreacted monomers may remain.
• the manufacturing method of the said acrylic copolymer is not specifically limited.
• methods such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, UV polymerization, which are commonly used in the art to which the present invention pertains, may be used, and preferably, solution polymerization or UV polymerization may be used. have.
• the pressure-sensitive adhesive composition of the present invention may further include a photoinitiator in order to efficiently induce a photocuring reaction even in light of a UV band, for example, a wavelength of 400 nm or less.
• the photoinitiator is not particularly limited as long as it is a component capable of initiating a photocuring reaction due to irradiation with actinic light, and a conventionally developed photoinitiator may be used.
• the photoinitiator of the present invention in one or more embodiments, is selected from the group consisting of acetophenone-based, benzophenone-based, triazine-based, thioxanthone-based, oxime-based, benzoin-based, and biimidazole-based compounds It may include one or more.
• acetophenone-based compound examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy-1-[4-( 2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl[4-(1-methylvinyl)phenyl]propane-1 -On oligomers, etc. are mentioned.
• benzophenone-based compound examples include benzophenone, 2,2'-hydroxy-4,4'-dimethoxybenzophenone, methyl o-benzoylbenzoate, 4-phenylzophenone, and 4-benzoyl-4.
• benzophenone 2,2'-hydroxy-4,4'-dimethoxybenzophenone, methyl o-benzoylbenzoate, 4-phenylzophenone, and 4-benzoyl-4.
• '-methyldiphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.
• triazine-based compound examples include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl). )-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5- Triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloro methyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino) -2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichlor
• thioxanthone-based compound examples include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Chloro-4-propoxythioxanthone etc. are mentioned.
• Examples of the oxime compound include 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2-(O-benzoyloxime), 1-[4-(phenylthio)phenyl] -octane-1,2-dione 2-(O-benzoyloxime), 1-[4-(benzoyl)phenyl]-octane-1,2-dione 2-(O-benzoyloxime), 1-[9-ethyl -6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethanone 1-(O-acetyloxime), 1-[9-ethyl-6-(3-methylbenzoyl)-9H-carb bazol-3-yl]-ethanone 1-(O-acetyloxime), 1-(9-ethyl-6-benzoyl-9H-carbazol-3-yl)-ethanone 1-(O-acetyloxime), Ethanone-1-[9-
• benzoin type compound benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzo isobutyl ether, etc. are mentioned, for example.
• biimidazole compound examples include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1; 2'-biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimi Dazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl) )-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5 '-Tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,
• the photoinitiator may be included in an amount of 0.3 to 3 wt%, more preferably, 0.5 to 2 wt%, based on the total weight of the acrylic copolymer.
• the polymerization or crosslinking reaction of the monomer may be effectively initiated during treatment with magnetic rays of a specific wavelength region, illuminance, and amount of light of the pressure-sensitive adhesive composition, and durability may be exhibited and variability may be excellent.
• the pressure-sensitive adhesive composition of the present invention may further include a heat curing agent in order to strengthen the cohesive force of the pressure-sensitive adhesive.
• thermosetting agent is not particularly limited as long as it is a component capable of strengthening the cohesive force of the pressure-sensitive adhesive by appropriately crosslinking the acrylic copolymer, but is preferably an isocyanate-based crosslinking agent.
• the isocyanate-based crosslinking agent is, for example, tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, isophorone diisocyanate, Addition trimers, such as tetramethylxylene diisocyanate, naphthalene diisocyanate, and 2,4-toluene diisocyanate addition trimer, or an isocyanurate trimer, etc. are mentioned, but it is not limited to this.
• the thermal curing agent based on the total weight of the acrylic copolymer, preferably included in an amount of 0.1 to 1% by weight, more preferably, may be 0.1 to 0.5% by weight.
• the content of the thermal curing agent is less than 0.1% by weight, the adhesive strength or cohesive force of the pressure-sensitive adhesive composition may be somewhat reduced, and if it exceeds 1% by weight, the compatibility may be slightly lowered and surface migration may occur, and the crosslinking reaction may proceed too much As a result, the adhesive strength may be slightly lowered.
• the pressure-sensitive adhesive composition of the present invention by including the above-described acrylic copolymer, can improve the refractive index without including nanoparticles, but for the purpose of further improving the refractive index, it is not limited to further include nanoparticles as necessary does not
• the nanoparticles are not particularly limited as long as they can exhibit characteristics of high refractive index, and nanoparticles developed conventionally or later may be used.
• the nanoparticles of the present invention are titanium oxide, zinc oxide, zirconium oxide, magnesium oxide, zirconium titanate, zirconium silicate, strontium titanate, aluminum titanate, silicon ferrite, nickel ferrite. , cobalt ferrite, barium carbonate, silicon carbide, yttrium carbide, magnesium silicate, zinc sulfate, and may include one or more selected from the group consisting of barium sulfate.
• the average particle diameter of the nanoparticles is preferably 1 to 100 nm, more preferably, 50 to 100 nm, in order to realize the characteristic of high refractive index.
• the average particle diameter of the nanoparticles is less than 1 nm, dispersion in the pressure-sensitive adhesive composition may be difficult to inhibit the light transmittance, and if the average particle diameter exceeds 100 nm, the light transmittance of visible light may be inhibited due to the size of the particle size.
• the nanoparticles are preferably included in an amount of 0.1 to 30% by weight based on the total weight of the acrylic copolymer.
• the content of nanoparticles is less than 0.1% by weight, the refractive index is not improved because the refractive index change is insignificant.
• UV blocker ultraviolet (UV) blocker
• silane coupling agent antioxidant
• corrosion inhibitor corrosion inhibitor
• defoamer filler
• antistatic agent antistatic agent
• One embodiment of the present invention relates to a pressure-sensitive adhesive sheet comprising a cured product of the above-described pressure-sensitive adhesive composition.
• the pressure-sensitive adhesive sheet may include a base film and an adhesive layer laminated on at least one surface of the base film.
• the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to the present invention on the base film, or the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to the present invention between two base films may be interposed.
• the base film may be used without any particular limitation as long as it is a base material used in the art, and a film having excellent transparency, mechanical strength, thermal stability, moisture shielding property, isotropy, and the like is preferable.
• the said base film is polyester-type resin, such as a polyethylene terephthalate, a polyethylene isophthalate, a polyethylene naphthalate, and a polybutylene terephthalate; Cellulose resins, such as a diacetyl cellulose and a triacetyl cellulose; polycarbonate-based resin; acrylic resins such as polymethyl (meth)acrylate and polyethyl (meth)acrylate; styrenic resins such as polystyrene and acrylonitrile-styrene copolymer; polyolefin-based resins such as polyethylene, polypropylene, polyolefin having a cyclo-based or norbornene structure, and an ethylene-propy
• thermosetting resin or ultraviolet curable resin such as (meth)acrylic, urethane, acrylic urethane, epoxy, or silicone may be used.
• a polyimide-based resin may be used for easier application to an image display device.
• the pressure-sensitive adhesive sheet may have a pressure-sensitive adhesive layer laminated on one surface of the base film, and a hard coating layer may be formed on the other surface of the base film on which the pressure-sensitive adhesive layer is not laminated. If necessary, a separator may be formed on one surface of the pressure-sensitive adhesive layer.
• the method for producing the pressure-sensitive adhesive sheet is not particularly limited, but for example, the pressure-sensitive adhesive composition described above is applied to one or both surfaces of a base film at a temperature of around 40° C. to form a pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer is photo-applied It can be prepared by hardening through heating.
• the pressure-sensitive adhesive composition may be applied to the surface of a base film subjected to a surface release treatment with silicone, fluorine, or the like, and dried by heating to form a pressure-sensitive adhesive layer.
• corona discharge treatment plasma treatment, blast treatment, chemical etching treatment, primer treatment, etc. may be performed on the surface of the base film in order to improve the adhesion to the pressure-sensitive adhesive layer.
• the application may be generally performed by a knife coater, a roll coater, a calender coater, a comma coater, or the like. In addition, it may be carried out by a gravure coater, a rod coater, etc. depending on the coating thickness or the viscosity of the pressure-sensitive adhesive composition.
• the thickness of the pressure-sensitive adhesive layer may be, for example, 5 to 80 ⁇ m. When the thickness of the pressure-sensitive adhesive layer is within the above range, the adhesive strength is excellent, and there are advantages in terms of light transmittance, reliability and step absorption.
• the pressure-sensitive adhesive sheet may have a refractive index of 1.58 or more, more preferably 1.58 to 1.70, and most preferably, 1.60 to 1.70. In this case, visibility may be improved without including a separate high refractive index pattern layer in the display device including the touch panel. In particular, in the case of the pressure-sensitive adhesive sheet according to the present invention, it can exhibit a high refractive index without including an excessive amount of nanoparticles, there is an advantage in terms of optical properties.
• One embodiment of the present invention relates to an optical member including the above-described pressure-sensitive adhesive sheet or pressure-sensitive adhesive layer.
• the pressure-sensitive adhesive sheet or the pressure-sensitive adhesive layer may be an optical pressure-sensitive adhesive film (OCA).
• the optical member is, for example, a touch panel, a window, a polarizing plate, a color filter, a retardation film, an elliptically polarizing film, a reflective film, an anti-reflection film, a compensation film, a brightness enhancing film, an alignment film, a light diffusion film, a glass scattering prevention film, surface protection Transparent electrode such as film, plastic LCD substrate, indium tin oxide (ITO), fluorinated tin oxide (FTO), aluminum dopped zinc oxide (AZO), carbon nanotube (CNT), Ag nanowire, graphene, etc. A film etc. are mentioned.
• the method of manufacturing the optical member may be easily manufactured by a person skilled in the art to which the present invention pertains.
• the display device is not limited thereto, as long as it includes an optical member including the above-described pressure-sensitive adhesive sheet or pressure-sensitive adhesive layer, and for example, a liquid crystal display (LCD), an electroluminescent (EL) display device. , a plasma display panel (PDP), a field emission display (FED), an organic light emitting diode (OLED) display, and the like.
• LCD liquid crystal display
• EL electroluminescent
• PDP plasma display panel
• FED field emission display
• OLED organic light emitting diode
• the display device may include a configuration commonly known in the art, except for including the above-described optical member.
• a pressure-sensitive adhesive composition After uniformly stirring the monomer mixture, 0.07 parts by weight of azobisisobutyronitrile (AIBN) as a reaction initiator was added and reacted for 8 hours to prepare an acrylic copolymer having a weight average molecular weight of 1.53 million, and additionally an isocyanate-based crosslinking agent (AK75) was added in 0.5 parts by weight to prepare a pressure-sensitive adhesive composition.
• the pressure-sensitive adhesive composition was coated on a polyethylene terephthalate (PET) film having a thickness of 75 ⁇ m and subjected to a release treatment using a bar coater. Thereafter, after drying at 100° C. for 1 minute, and curing at room temperature for 7 days, a pressure-sensitive adhesive sheet having a thickness of the pressure-sensitive adhesive layer of 25 ⁇ m was prepared.
• a pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition of Example 2 was prepared in the same manner as in Example 1 with the components and contents shown in Table 1 below.
• a pressure-sensitive adhesive composition containing 0.5 parts by weight of oxycyclohexyl)phenylketone (Irgacure ® -184) was prepared, and the glass transition temperature of the pressure-sensitive adhesive composition was measured, and as a result, it was -13°C (measurement instrument: DSC8000, PerkinElmer Inc.).
• the pressure-sensitive adhesive composition was coated on a polyethylene terephthalate (PET) film having a thickness of 75 ⁇ m and subjected to a release treatment using a bar coater. Thereafter, by irradiating ultraviolet rays for 10 minutes using a UV lamp to cure, a pressure-sensitive adhesive sheet having a thickness of the pressure-sensitive adhesive layer of 25 ⁇ m was prepared.
• PET polyethylene terephthalate
• Adhesive sheets using the pressure-sensitive adhesive compositions of Examples 4 and 5 and Comparative Examples 1 to 4 were prepared in the same manner as in Example 3 with the components and contents shown in Table 1 below.
• Example comparative example One 2 3 4 5 One 2 3 4 Acrylic copolymer high refractive index monomer A1 40 40 A2 60 50 A3 40 A4 50 A5 40 A6 40 40 acryl monomer B1 15 55 47 55 55 55 B2 35 B3 40 47 57 polymeric monomer C1 5 5 5 5 C2 5 C3 3 3 3 3 nanoparticles D1 30 30 50 photoinitiator E1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 thermosetting agent F1 0.5 0.5 A1: pentabromophenyl acrylate (homopolymer refractive index: 1.67, Tg: 155°C Sigma-Aldrich) A2: 2-(naphthalen-2-ylthio)ethyl acrylate (homopolymer refractive index: 1.62, Tg: 77°C Daelim Chemical) A3: 2-(naphthalen-2-yloxy)ethyl acrylate (homopolymer refractive index: 1.589
• the pressure-sensitive adhesive layers according to the above examples and comparative examples were peeled off from the release film, bonded to a slide glass (manufactured by Matsunami Glass Kogyo, model number: S1111), and under an atmosphere of 25° C., Murakami Shiki Co., Ltd.
• the haze value (%) was measured according to JISK-7136 using the "Reflectance/Transmittance Meter HR-100 Type" manufactured by Jutsu Corporation.
• the value obtained by subtracting the haze value (0.2%) of the slide glass from the value was evaluated as the haze value of the pressure-sensitive adhesive layer, and the evaluation results are shown in Table 2 below.
• ⁇ refractive index 1.58 or more and less than 1.60
• the pressure-sensitive adhesive layer prepared by the pressure-sensitive adhesive composition of Examples 1 to 5 shows excellent transparency and a high refractive index of 1.58 or more.
• the pressure-sensitive adhesive layer prepared by the pressure-sensitive adhesive composition of Comparative Examples 1 to 3 has a poorer refractive index compared to the Example, and the pressure-sensitive adhesive layer prepared by the pressure-sensitive adhesive composition of Comparative Example 4 has poor transparency compared to the Example. have.
• the pressure-sensitive adhesive composition according to the present invention is particularly suitable for manufacturing a pressure-sensitive adhesive layer capable of improving visibility without including a separate high refractive index pattern layer in a display device including a touch panel while exhibiting excellent optical properties and reliability.
• the refractive index is improved compared to the conventional pressure-sensitive adhesive composition, and the visibility may be improved without including a separate high refractive index pattern layer.

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• 2021
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