WO2018052178A1 - Optically clear adhesive composition, optically clear adhesive film comprising same, and flat display device - Google Patents

Optically clear adhesive composition, optically clear adhesive film comprising same, and flat display device Download PDF

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Publication number
WO2018052178A1
WO2018052178A1 PCT/KR2017/005951 KR2017005951W WO2018052178A1 WO 2018052178 A1 WO2018052178 A1 WO 2018052178A1 KR 2017005951 W KR2017005951 W KR 2017005951W WO 2018052178 A1 WO2018052178 A1 WO 2018052178A1
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Prior art keywords
meth
adhesive composition
acrylate
optically transparent
weight
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PCT/KR2017/005951
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French (fr)
Korean (ko)
Inventor
최한영
정경문
박일성
유병묵
Original Assignee
동우 화인켐 주식회사
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Publication of WO2018052178A1 publication Critical patent/WO2018052178A1/en

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    • 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
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-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
    • 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]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • 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

Definitions

  • the present invention relates to an optically transparent adhesive composition, an optically transparent adhesive film and a flat panel display device including the same.
  • the flat panel display includes a liquid crystal display (LCD), a plasma display panel (PDP), an organic electroluminescent display (OLED), and the like.
  • LCD liquid crystal display
  • PDP plasma display panel
  • OLED organic electroluminescent display
  • Such a flat panel display includes a display panel and an optical film.
  • a polarizing film, a retardation film, an anti-glare film, a wide viewing angle compensation film, a brightness improving film, etc. are used.
  • an optically clear adhesive (OCA) is used. Therefore, optically clear adhesive (OCA) should basically have excellent moisture resistance, heat resistance and adhesion with optical properties.
  • OCAs optically transparent adhesives
  • an optically clear adhesive (OCA) used in a flexible display device should have excellent folding properties to enable flexible folding of the device.
  • OCA optically clear adhesive
  • the folding characteristics at low temperature should be excellent.
  • an optically transparent adhesive (OCA) used in a flexible display device requires more enhanced heat and moisture resistance. Because the flexible display device repeats the folding and unfolding process during use, the likelihood of penetration of moisture through the folded and unfolded portion increases.
  • OCAs optically transparent adhesives
  • the present invention has been made to solve the above problems of the prior art,
  • An object of the present invention is to provide an optically transparent pressure-sensitive adhesive (OCA) composition that can sufficiently satisfy the folding properties, moist heat resistance, heat resistance, and adhesion required in a flexible display device.
  • OCA optically transparent pressure-sensitive adhesive
  • Another object of the present invention is to provide an optically transparent adhesive film and a flat panel display device including the optically transparent adhesive (OCA) composition.
  • the present invention is an optically transparent pressure-sensitive adhesive composition
  • a photocurable (meth) acrylate copolymer and a photopolymerization initiator
  • the hydroxy group-containing acrylic copolymer includes an ethylene oxide group-containing (meth) acrylate monomer having a glass transition temperature (Tg) of -75 to -55 ° C and a hydroxy group-containing alkyl acrylate monomer,
  • It provides an optically transparent adhesive composition which has a weight average molecular weight of 200,000 to 1 million.
  • the present invention provides an optically transparent adhesive film, which is prepared by coating the optical transparent adhesive composition of the present invention on a transfer film.
  • the present invention provides a flat panel display comprising a pressure-sensitive adhesive layer formed of the optically transparent pressure-sensitive adhesive composition of the present invention.
  • optically clear adhesive (OCA) composition and the optically clear adhesive film of the present invention provide sufficient folding properties, heat-and-moisture resistance, heat resistance, and adhesion to be used in a flat panel display as well as a flexible display device, thereby providing excellent durability. to provide.
  • the flat panel display device of the present invention is manufactured using the above-described pressure-sensitive adhesive composition, it is possible to provide excellent folding characteristics, heat and humidity resistance, heat resistance, adhesiveness, and excellent durability.
  • the present invention is an optically transparent pressure-sensitive adhesive composition
  • a photocurable (meth) acrylate copolymer and a photopolymerization initiator
  • the hydroxy group-containing acrylic copolymer includes an ethylene oxide group-containing (meth) acrylate monomer having a glass transition temperature (Tg) of -75 to -55 ° C and a hydroxy group-containing alkyl acrylate monomer,
  • a weight average molecular weight is 200,000-1 million, and it is related with the optically transparent adhesive composition characterized by the above-mentioned.
  • Optical transparent pressure-sensitive adhesive composition of the present invention can improve the folding properties by including an ethylene oxide group-containing (meth) acrylate monomer having a low glass transition temperature (Tg), and by including a hydroxy group-containing alkyl acrylate monomer moist heat resistance and adhesion It is possible to improve, and to increase the crosslinking density through the urethane bond of the hydroxy group and the isocyanate group can provide an optically transparent adhesive composition excellent in heat resistance and durability.
  • Tg glass transition temperature
  • the "(meth) acrylate” means "acrylate” or "methacrylate”.
  • the photocurable acrylate copolymer copolymerizes an ethylene oxide group-containing (meth) acrylate monomer and a hydroxy group-containing alkyl acrylate monomer having a glass transition temperature (Tg) of -75 to -55 ° C, and is thermosetting at a branched chain or terminal.
  • Tg glass transition temperature
  • transduced was prepared, and then the isocyanate group containing (meth) acrylate type monomer was made to react with a main chain on suitable conditions, and the thermosetting functional group (OH group) of a main chain It can be prepared by substituting at least a portion with an isocyanate group-containing (meth) acrylate.
  • the main chain is prepared by conventional polymerization methods such as, for example, solution polymerization, photo polymerization, bulk polymerization, suspension polymerization or emulsion polymerization. Can be.
  • An ethylene oxide group-containing (meth) acrylate monomer having a glass transition temperature (Tg) of -75 to -55 ° C included in a polymerized form in the hydroxy group-containing acrylic copolymer may be represented by the following Formula 1.
  • R 1 is hydrogen or a methyl group
  • R 2 is a linear alkyl group having 1 to 4 carbon atoms
  • A is a natural number of 1 to 15.
  • Formula 1 specifically includes one or more selected from the group consisting of the following Formulas 2 to 4.
  • the glass transition temperature (Tg) of the ethylene oxide group-containing (meth) acrylate monomer is less than -75 ° C, it is difficult to use due to economical efficiency, and the durability of the optically transparent adhesive composition may be deteriorated. There arises a problem that the folding characteristic at low temperature is reduced.
  • the hydroxy group-containing alkyl acrylate monomer included in the polymerized form in the hydroxy group-containing acrylic copolymer is specifically, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, 8-hydroxyoctyl acrylate, 2-hydroxyethylene glycol acrylate, 2-hydroxypropylene glycol acrylate, and the like.
  • monomers such as 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate can be preferably used, and more preferably 4-hydroxybutyl acrylate can be used.
  • monomers such as 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate can be preferably used, and more preferably 4-hydroxybutyl acrylate can be used.
  • 4-hydroxybutyl acrylate such as 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate
  • 4-hydroxybutyl acrylate can be used.
  • the structure of the photocurable acrylate copolymer of the present invention may be represented by the following formula (5).
  • R 3 is a linear alkyl group having 1 to 4 carbon atoms containing 1 to 15 ethylene oxide groups
  • R 4 is hydrogen or a methyl group
  • R 5 is hydrogen or a methyl group
  • R 6 is a straight or C4-10 branched alkylene group having 1 to 10 carbon atoms
  • R 7 is hydrogen or a methyl group
  • O is a natural number of 2 to 6
  • the l, m and n each have a value formed according to the range of usage of the monomers described above.
  • hydroxy group-containing acrylic copolymer 50 to 95% by weight of the ethylene oxide group-containing (meth) acrylate monomer having a glass transition temperature (Tg) of -75 to -55 ° C based on the total weight of monomers included in the copolymer. It is included as, hydroxy group-containing alkyl acrylate monomer is preferably included in 5 to 50% by weight.
  • the hydroxy group-containing alkyl acrylate monomer when included in less than 5% by weight, the hydroxy group due to hydrophilicity is insufficient in the pressure-sensitive adhesive to prevent moisture from the pressure-sensitive adhesive layer, the moisture is discharged to the interface, resulting in a problem that the moisture resistance (adhesiveness) is lowered And, when included in excess of 50% by weight, the pressure-sensitive adhesive absorbs excessive moisture, the volume expands, and the cohesive force is lowered, causing a problem of interfacial peeling and bubbles.
  • the hydroxy group-containing acrylic copolymer may further include other copolymerizable monomers known in the art in a polymerized form.
  • the kind of the other copolymerizable monomer is not particularly limited, and examples thereof include (meth) acrylonitrile, (meth) acrylamide, N-methyl (meth) acrylamide or N-butoxy methyl (meth) acrylamide.
  • Such nitrogen-containing monomers Styrene-based monomers such as styrene or methyl styrene; Glycidyl (meth) acrylate; Or vinyl esters of carboxylic acids such as vinyl acetate, but are not limited thereto.
  • the content thereof is preferably adjusted to 20 parts by weight or less based on 100 parts by weight of the total monomers described above.
  • the weight average molecular weight means a conversion value with respect to standard polystyrene measured by gel permeation chromatograph (GPC).
  • the weight average molecular weight of the hydroxy group-containing acrylic copolymer is 200,000 to 1 million.
  • Isocyanate C 1 to C 10 alkyl acrylate monomers may be used as the isocyanate group-containing (meth) acrylate monomer included in the photocurable (meth) acrylate copolymer, and specifically, isocyanato C 1 to C 10 straight or C 4 to C 10 branched alkyl acrylates may be used.
  • the C 1 to C 10 straight or C 4 to C 10 branched alkyl group may be methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decanyl and the like can be cited, and among these, ethyl, propyl and the like can be preferably used.
  • the isocyanate group-containing (meth) acrylate-based monomer may be included in an amount of 0.1 wt% to 5 wt% based on the total weight of the structural units included in the photocurable (meth) acrylate copolymer.
  • the isocyanate group-containing (meth) acrylate-based monomer is included in less than 0.1% by weight, the cohesive force and heat resistance of the pressure-sensitive adhesive composition may be lowered, and when it exceeds 5% by weight, the cohesive force of the pressure-sensitive adhesive becomes too strong This can be degraded.
  • the optically transparent adhesive composition of this invention contains a photoinitiator in order to induce reaction of a radically polymerizable group efficiently.
  • the photopolymerization initiator may be used in the polymerization of the hydroxyl group-containing acrylic copolymer, and finally included in the optically transparent adhesive composition together with the photocurable (meth) acrylate copolymer.
  • the photopolymerization initiator is not particularly limited and photopolymerization initiators known in the art may be used. Specifically, general initiators such as benzoin initiators, hydroxyketone initiators, amino ketone initiators or phosphine oxide initiators can be used to generate radicals by irradiation with ultraviolet rays to initiate photopolymerization.
  • the effect of the addition may be insignificant, and when too large, it may adversely affect physical properties such as durability and transparency, so that an appropriate content range may be selected in consideration of this point. .
  • the photopolymerization initiator may be included in an amount of 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the photocurable (meth) acrylate copolymer.
  • the optically transparent adhesive composition of this invention may further contain a polyfunctional crosslinking agent.
  • a polyfunctional crosslinking agent is not particularly limited, and those known in the art may be used. Specifically, a thermosetting polyfunctional isocyanate crosslinking agent, a polyfunctional (meth) acrylate crosslinking agent, etc. are mentioned.
  • the multifunctional crosslinking agent may be further included in an amount of 0.02 to 5 parts by weight based on 100 parts by weight of the photocurable (meth) acrylate copolymer.
  • the optically transparent adhesive composition of this invention can contain a silane coupling agent further.
  • the kind of coupling agent is not particularly limited, and a coupling agent commonly known in the art of adhesive production can be used.
  • a silane coupling agent gamma-glycidoxypropyl triethoxy silane, gamma-glycidoxypropyl trimethoxy silane, gamma-glycidoxypropyl methyldiethoxy silane, gamma-glycidoxypropyl triethoxy Silane, 3-mercaptopropyl trimethoxy silane, vinyltrimethoxysilane, vinyltriethoxy silane, gamma-methacryloxypropyl trimethoxy silane, gamma-methacryloxy propyl triethoxy silane, gamma-aminopropyl Trimethoxy silane, gamma-aminopropyl triethoxy silane, 3-isocyanatopropyl trieth
  • the silane coupling agent may be included in an amount of 0.01 to 5 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the photocurable (meth) acrylate copolymer.
  • the optically transparent adhesive composition of this invention may further contain a tackifier for control of adhesive performance.
  • additives selected from the group consisting of epoxy resins, curing agents, ultraviolet stabilizers, antioxidants, colorants, reinforcing agents, fillers, antifoaming agents, surfactants and plasticizers.
  • the optically transparent adhesive composition of this invention may further contain a solvent.
  • a solvent any solvent known in the art may be used without limitation as long as it can dissolve monomers and copolymers used in the optically transparent adhesive composition.
  • solvent examples include ethyl acetate, methyl ethyl ketone, toluene, acetonitrile and the like.
  • the solvent may be included in an amount of 40 to 85 parts by weight based on 100 parts by weight of the photocurable (meth) acrylate copolymer.
  • the viscosity of the optically transparent adhesive composition of the present invention may preferably be used in the range of 23 to 500 cP to 2,500 Cp.
  • the optically transparent adhesive composition of the present invention secures folding properties by using monomers having a low glass transition temperature (Tg), while suitably combining a curing system by radical polymerization with a curing system by a crosslinking agent and a thermosetting functional group (-OH group). It has the characteristic to ensure durability.
  • Tg glass transition temperature
  • -OH group thermosetting functional group
  • the method of preparing the optically transparent adhesive composition of the present invention may be carried out by a method commonly used in this field except as described above. At this time, molecular weight regulators, catalysts and the like used in this field may also be used without limitation.
  • the method of applying the optically transparent adhesive composition of the present invention is not particularly limited, and examples thereof include bar coating, spin coating, comma coating, gravure coating, and the like. This can be done in a general purpose way.
  • the crosslinking agent forms a crosslinked structure in the curing and aging process after the coating operation, thereby improving the cohesion, adhesive properties, and cuttability of the pressure-sensitive adhesive.
  • the application process is preferably performed after sufficiently removing the bubble-inducing components such as volatile components or reaction residues inside the pressure-sensitive adhesive composition.
  • the crosslinking density or molecular weight of the pressure-sensitive adhesive is too low, the elastic modulus is lowered, and bubbles present between the glass plate and the pressure-sensitive adhesive layer in a high temperature state may be increased to prevent a phenomenon in which scattering bodies are formed inside.
  • the coating layer of the optically transparent adhesive composition After forming the coating layer of the optically transparent adhesive composition, it is cured through light irradiation.
  • the ultraviolet irradiation may be performed using a means such as a high pressure mercury lamp, an electrodeless lamp or a xenon lamp.
  • an appropriate aging process may be conducted to induce reaction of the functional group of the crosslinking agent in the composition with the thermosetting functional group of the polymer, and the conditions in the process are not particularly limited as long as an appropriate crosslinking reaction can occur. .
  • the pressure-sensitive adhesive composition for an optical film of the present invention for example, laminated optical films such as a polarizing film, a retardation film, an anti-glare film, a wide viewing angle compensation film or a brightness enhancement film, or displays the optical film or a laminate thereof. It can be used for the purpose of attaching to adherends such as panels.
  • the pressure-sensitive adhesive composition for an optical film of the present invention can be preferably used in a flexible display device.
  • optical transparent pressure-sensitive adhesive film which is prepared by coating the optical transparent pressure-sensitive adhesive composition on a transfer film.
  • the transfer film used in the optically transparent adhesive film a film known in the art may be used without limitation.
  • the method of manufacturing the optically transparent adhesive film can be used without limitation methods known in the art.
  • It provides a flat panel display device comprising an adhesive layer formed of the optically transparent adhesive composition of the present invention.
  • the flat panel display is more preferably a flexible display device.
  • Nitrogen gas is refluxed, 60 parts by weight of the compound of formula 2 and 40 weight of 4-hydroxybutyl acrylate (4-HBA) having a glass transition temperature of -60 °C in a 1L reactor equipped with a cooling device to facilitate temperature control Added wealth.
  • EAc ethyl acetate
  • AIBN azobisisobutyronitrile
  • a photocurable acrylate copolymer (A2) was prepared in the same manner as in Preparation Example 1 except that the compound of Formula 3 having a glass transition temperature of ⁇ 60 ° C. instead of the compound of Formula 2 was used (acrylic copolymer). Weight average molecular weight of 560,000).
  • a photocurable acrylate copolymer (A3) was prepared in the same manner as in Preparation Example 1 except that the compound of Formula 4 having a glass transition temperature of ⁇ 71 ° C. instead of the compound of Formula 2 was used (acrylic copolymer). Weight average molecular weight of 510,000).
  • a photocurable acrylate copolymer (A4) was prepared in the same manner as in Preparation Example 1, except that hexyl acrylate (HA) having a glass transition temperature of ⁇ 58 ° C. was used instead of the compound of Formula 2 (acrylic air). Weight average molecular weight of coalescing: 370,000).
  • the silonic acid sol and diglycidyl ether are mixed in a weight ratio of 100: 10, and 2 parts by weight of triarylsulfonium hexafluoroantimonate salt is mixed with 100 parts by weight of the mixture to prepare a hard coating composition. Prepared.
  • the hard coating composition was coated with a thickness of 50 ⁇ m on a 40 ⁇ m thick COP (cycloolefin polymer, ZF-16, Zeon) film treated by corona to prepare a film.
  • the film was exposed to a mercury UV (Ultra Violet) lamp (20 mW / cm 2 ) for 5 minutes to initiate the reaction with the triarylsulfonium hexafluoroantimonate salt and at 50 ° C. and 50% relative humidity. Moisture heat treatment was performed for 60 minutes under the conditions to form a hard coat film.
  • Example 1 except that the photocurable (meth) acrylate copolymer (A2) prepared in Preparation Example 2 was used instead of the photocurable (meth) acrylate copolymer (A1) prepared in Preparation Example 1
  • An optically transparent adhesive composition was prepared in the same manner as in Example 1.
  • Example 1 except that the photocurable (meth) acrylate copolymer (A3) prepared in Preparation Example 3 was used instead of the photocurable (meth) acrylate copolymer (A1) prepared in Preparation Example 1
  • An optically transparent adhesive composition was prepared in the same manner as in Example 1.
  • Example 1 except that the photocurable (meth) acrylate copolymer (A4) prepared in Preparation Example 4 was used instead of the photocurable (meth) acrylate copolymer (A1) prepared in Preparation Example 1
  • An optically transparent adhesive composition was prepared in the same manner as in Example 1.
  • Example 4-1 using the optically transparent adhesive composition of Example 1
  • Example 4-2 using the optically transparent adhesive composition of Example 2)
  • Example 4-3 using the optically transparent adhesive composition of Example 3
  • the optical transparent pressure-sensitive adhesive film of Comparative Example 2-1 using the optical transparent pressure-sensitive adhesive composition of Comparative Example 1).
  • Example 4-1 Using the optical transparent pressure-sensitive adhesive film prepared in Example 4-1, Example 4-2, Example 4-3 and Comparative Example 2-1, a pressure-sensitive adhesive layer was applied to a 100 ⁇ m-thick PET film (100 um PET manufactured by Mitsubishi Corporation). Laminating and irradiating the amount of light of 1000mJ / cm 2 using a UV lamp (fusion yarn) in the release film direction of Example 5-1, Example 5-2, Example 5-3 and Comparative Example 3-1 The laminated body in which the adhesive layer was formed was manufactured.
  • a UV lamp fusion yarn
  • Example 5-1, Example 5-2, Example 5-3 and Comparative Example 3-1 were cut to a size of 50 mm x 100 mm. Subsequently, the release PET film attached to the pressure-sensitive adhesive layer of the cut laminate is peeled off, and then adhered onto a hard coating film for evaluation of flexibility prepared in Preparation Example 5 having a size of 50 mm ⁇ 100 mm, and the autoclave 50, 5 atm) for about 20 minutes, and cured for 24 hours at constant temperature and humidity conditions (23, 50% relative humidity), respectively, Example 6-1, Example 6-2, Example 6-3, and Comparative Example The hard coat film / adhesive layer / PET (100 micrometers) laminated body for the flexibility evaluation of 4-1 was manufactured.
  • Example 6-1, Example 6-2, Example 6-3, and Comparative Example 4-1 hard coating film / adhesive layer / PET laminate prepared in Example 6 to the above evaluation method Therefore, the folding characteristics are shown in Table 1 below.
  • Example 6-1, Example 6-2, Example 6-3 and Comparative Example 4-1 prepared in Example 6 hard coating film / adhesive layer / PET laminate for evaluation of the temperature at a temperature of 80 After leaving for a time to observe the occurrence of bubbles or peeling to evaluate the heat resistance and the results are shown in Table 1 below.
  • Example 6-1, Example 6-2, Example 6-3 and Comparative Example 4-1 prepared in Example 6 to the hard coating film / adhesive layer / PET laminate for evaluation of the temperature and 60 After leaving for 1,000 hours under the condition of% RH, it was observed whether bubbles or peeling occurred. At this time, immediately after evaluating the state of the specimen left at room temperature for 24 hours and observed to evaluate the heat and humidity resistance and the results are shown in Table 1 below.
  • the specimens were prepared by cutting the pressure-sensitive adhesive forming laminates prepared in Example 5-1, Example 5-2, Example 5-3, and Comparative Example 3-1 to 25 mm ⁇ 100 mm. It was. Subsequently, the release PET film adhered to the adhesive layer was peeled off, and the lamination agent in which the adhesive layer was formed was attached to the alkali free glass using the roller of 2 kg according to the provision of JIS Z 0237. Samples were prepared by compressing the alkali free glass with the laminating agent in an autoclave (50, 5 atm) for about 20 minutes and storing for 24 hours at constant temperature and humidity conditions (23, 50% relative humidity).
  • the adhesion was measured while peeling the laminate from an alkali free glass at a peel rate of 300 mm / min and a peel angle of 180 degrees. 2 is shown.
  • the optically transparent adhesive compositions of Examples of the present invention were confirmed to be excellent in all folding properties, moist heat resistance, heat resistance and adhesion.
  • the folding properties were found to be remarkably superior compared to the optically transparent adhesive compositions of the comparative example.
  • the optically transparent pressure-sensitive adhesive composition of the comparative example does not include a (meth) acrylate monomer having a glass transition temperature (Tg) of -75 to -55 ° C, resulting in very poor folding properties.

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Abstract

The present invention relates to: an optically clear adhesive composition comprising a radiation curable (meth)acrylate copolymer and a photopolymerization initiator, wherein the radiation curable (meth)acrylate copolymer comprises, on the basis of the total weight of the constituent elements contained in the copolymer, 95-99.9 wt% of an acrylic copolymer containing a hydroxyl group and 0.1-5 wt% of a (meth)acrylate-based monomer containing an isocyanate group, the acrylic copolymer containing a hydroxyl group and the (meth)acrylate-based monomer containing an isocyanate group form a urethane bond, and the acrylic copolymer containing a hydroxyl group comprises an ethylene oxide group-containing (meth)acrylate monomer having a glass transition temperature (Tg) of -75°C to -55°C and a hydroxyl group-containing alkyl acrylate monomer and has a weight average molecular weight of 200,000-1,000,000; an optically clear adhesive film comprising the same; and a flat display device.

Description

광학 투명 점착제 조성물, 그를 포함하는 광학 투명 점착 필름 및 평판표시장치Optical transparent adhesive composition, Optical transparent adhesive film and flat panel display device containing same
본 발명은 광학 투명 점착제 조성물, 그를 포함하는 광학 투명 점착 필름 및 평판표시장치에 관한 것이다.The present invention relates to an optically transparent adhesive composition, an optically transparent adhesive film and a flat panel display device including the same.
평판표시장치에는 액정 표시 장치(Liquid Crystal Display; LCD), 플라즈마 디스플레이 패널(Plasma Display Panel; PDP), 유기 발광 표시 장치(Organic Electro Luminescence Display; OLED) 등이 있다. The flat panel display includes a liquid crystal display (LCD), a plasma display panel (PDP), an organic electroluminescent display (OLED), and the like.
이러한 평판표시장치는 디스플레이 패널과 광학 필름을 포함한다. 상기 광학 필름으로는, 편광 필름, 위상차 필름, 눈부심 방지 필름, 광시야각 보상 필름, 휘도 향상 필름 등이 사용되고 있다. 이러한 광학 필름들을 서로 적층하거나 광학 필름을 디스플레이 패널에 부착하는 경우, 광학 투명 점착제(Optically Clear Adhesive, OCA)가 사용된다. 그러므로 광학 투명 점착제(OCA)는 기본적으로 광학적 특성과 함께 우수한 내습열성, 내열성, 밀착력을 갖추어야 한다. Such a flat panel display includes a display panel and an optical film. As said optical film, a polarizing film, a retardation film, an anti-glare film, a wide viewing angle compensation film, a brightness improving film, etc. are used. When laminating such optical films to each other or attaching the optical film to the display panel, an optically clear adhesive (OCA) is used. Therefore, optically clear adhesive (OCA) should basically have excellent moisture resistance, heat resistance and adhesion with optical properties.
특히, 최근에는 플렉서블 디스플레이 장치가 경쟁적으로 개발되고 있다. 플렉서블 디스플레이 장치는 장치 자체가 굽혀지거나(bending), 말아지거나(rolling), 접히게(folding) 되므로, 장치 내에 포함된 디스플레이 패널 및 광학필름들도 굽힘 응력을 받게 된다. 따라서 플렉서블 디스플레이에 사용되는 광학 투명 점착제(OCA)에는 더 강화되고 다양화된 물성이 요구된다. In particular, recently, flexible display devices have been competitively developed. Since the flexible display apparatus is bent, rolled, or folded, the display panel and the optical films included in the apparatus are also subjected to bending stress. Therefore, optically transparent adhesives (OCAs) used in flexible displays require more enhanced and diversified physical properties.
예를 들어, 플렉서블 디스플레이 장치에 사용되는 광학 투명 점착제(OCA)는 장치의 유연한 폴딩을 가능하게 하는 폴딩(folding) 특성이 우수해야 한다. 특히, 저온상태인 외부에서 플렉서블 디스플레이 장치를 장시간 사용하는 경우를 고려할 때, 저온에서의 폴딩 특성이 우수해야 한다. For example, an optically clear adhesive (OCA) used in a flexible display device should have excellent folding properties to enable flexible folding of the device. In particular, when considering the case of using the flexible display device for a long time in the low temperature state, the folding characteristics at low temperature should be excellent.
또한, 플렉서블 디스플레이 장치에 사용되는 광학 투명 점착제(OCA)에는 더욱 강화된 내습열성이 요구된다. 왜냐하면 플렉서블 디스플레이 장치는 사용하는 동안 접었다 펴는 과정을 무수히 반복하게 되므로 접혔다 펴지는 부분을 통하여 습기가 침투할 가능성도 그 만큼 커지기 때문이다.In addition, an optically transparent adhesive (OCA) used in a flexible display device requires more enhanced heat and moisture resistance. Because the flexible display device repeats the folding and unfolding process during use, the likelihood of penetration of moisture through the folded and unfolded portion increases.
또한, 플렉서블 디스플레이 장치가 굽혀지거나(bending), 말아지거나(rolling), 접히면서(folding) 장치 내에 포함된 디스플레이 패널 및 광학필름들도 굽힘 응력을 받게 된다. 따라서 적층된 디스플레이 패널 및 광학필름들 사이가 분리되기 쉬우므로 더 우수한 밀착성이 요구되며, 더 우수한 내구성도 요구된다. In addition, as the flexible display device is bent, rolled, or folded, display panels and optical films included in the device are also subjected to bending stress. Therefore, it is easy to be separated between the stacked display panel and the optical film is required for better adhesion, more excellent durability is also required.
그러나 현재까지 알려진 광학 투명 점착제(OCA)들은 플렉서블 디스플레이 장치에서 요구하는 상기와 같은 물성들을 충분히 제공하지 못하고 있는 실정이다.However, the optically transparent adhesives (OCAs) known to date do not sufficiently provide the above properties required by the flexible display device.
본 발명은 종래기술의 상기와 같은 문제를 해결하기 위하여 안출된 것으로서,The present invention has been made to solve the above problems of the prior art,
본 발명은 플렉서블 디스플레이 장치에서 요구되는 폴딩 특성, 내습열성, 내열성 및 밀착성을 충분히 충족시킬 수 있는 광학 투명 점착제(OCA) 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide an optically transparent pressure-sensitive adhesive (OCA) composition that can sufficiently satisfy the folding properties, moist heat resistance, heat resistance, and adhesion required in a flexible display device.
또한, 본 발명은 상기 광학 투명 점착제(OCA) 조성물을 포함하는 광학 투명 점착 필름 및 평판표시장치를 제공하는 것을 목적으로 한다.Another object of the present invention is to provide an optically transparent adhesive film and a flat panel display device including the optically transparent adhesive (OCA) composition.
상기 목적을 달성하기 위하여,In order to achieve the above object,
본 발명은 광경화성 (메타)아크릴레이트 공중합체 및 광중합 개시제를 포함하는 광학 투명 점착제 조성물로서,The present invention is an optically transparent pressure-sensitive adhesive composition comprising a photocurable (meth) acrylate copolymer and a photopolymerization initiator,
상기 광경화성 (메타)아크릴레이트 공중합체는,The photocurable (meth) acrylate copolymer,
공중합체에 포함되는 구성단위 총 중량에 대하여 히드록시기 함유 아크릴계 공중합체 95 내지 99.9 중량% 및 이소시아네이트기 함유 (메타)아크릴레이트계 단량체 0.1 내지 5 중량%를 포함하며,95 to 99.9 wt% of a hydroxy group-containing acrylic copolymer and 0.1 to 5 wt% of an isocyanate group-containing (meth) acrylate monomer based on the total weight of structural units included in the copolymer,
상기 히드록시기 함유 아크릴계 공중합체와 이소시아네이트기 함유 (메타)아크릴레이트계 단량체가 우레탄 결합을 형성한 것이며,The said hydroxyl group containing acrylic copolymer and the isocyanate group containing (meth) acrylate type monomer formed the urethane bond,
상기 히드록시기 함유 아크릴계 공중합체는 유리전이온도(Tg)가 -75 내지 -55℃인 에틸렌옥사이드기 함유 (메타)아크릴레이트 단량체 및 히드록시기 함유 알킬 아크릴레이트 단량체를 포함하며, The hydroxy group-containing acrylic copolymer includes an ethylene oxide group-containing (meth) acrylate monomer having a glass transition temperature (Tg) of -75 to -55 ° C and a hydroxy group-containing alkyl acrylate monomer,
중량평균 분자량이 20만 내지 100만인 것을 특징으로 하는 광학 투명 점착제 조성물을 제공한다.It provides an optically transparent adhesive composition which has a weight average molecular weight of 200,000 to 1 million.
또한, 본 발명은 상기 본 발명의 광학 투명 점착제 조성물을 전사필름에 코팅하여 제조되는 것을 특징으로 하는 광학 투명 점착제 필름을 제공한다.In addition, the present invention provides an optically transparent adhesive film, which is prepared by coating the optical transparent adhesive composition of the present invention on a transfer film.
또한, 본 발명은 상기 본 발명의 광학 투명 점착제 조성물로 형성된 점착층을 포함하는 것을 특징으로 하는 평판표시장치를 제공한다.In addition, the present invention provides a flat panel display comprising a pressure-sensitive adhesive layer formed of the optically transparent pressure-sensitive adhesive composition of the present invention.
본 발명의 광학 투명 점착제(OCA) 조성물 및 광학 투명 점착 필름은 평판 표시장치는 물론, 플렉서블 디스플레이 장치에서 사용할 수 있을 만큼 충분한 폴딩 특성, 내습열성, 내열성, 및 밀착성을 제공하며, 그에 따라 뛰어난 내구성도 제공한다. The optically clear adhesive (OCA) composition and the optically clear adhesive film of the present invention provide sufficient folding properties, heat-and-moisture resistance, heat resistance, and adhesion to be used in a flat panel display as well as a flexible display device, thereby providing excellent durability. to provide.
본 발명의 평판표시장치는 상기와 같은 점착제 조성물을 사용하여 제조되므로 우수한 폴딩 특성, 내습열성, 내열성, 점착성, 및 뛰어난 내구성을 제공할 수 있다.Since the flat panel display device of the present invention is manufactured using the above-described pressure-sensitive adhesive composition, it is possible to provide excellent folding characteristics, heat and humidity resistance, heat resistance, adhesiveness, and excellent durability.
이하, 본 발명을 보다 자세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 광경화성 (메타)아크릴레이트 공중합체 및 광중합 개시제를 포함하는 광학 투명 점착제 조성물로서,The present invention is an optically transparent pressure-sensitive adhesive composition comprising a photocurable (meth) acrylate copolymer and a photopolymerization initiator,
상기 광경화성 (메타)아크릴레이트 공중합체는,The photocurable (meth) acrylate copolymer,
공중합체에 포함되는 구성단위 총 중량에 대하여 히드록시기 함유 아크릴계 공중합체 95 내지 99.9 중량% 및 이소시아네이트기 함유 (메타)아크릴레이트계 단량체 0.1 내지 5 중량%를 포함하며,95 to 99.9 wt% of a hydroxy group-containing acrylic copolymer and 0.1 to 5 wt% of an isocyanate group-containing (meth) acrylate monomer based on the total weight of structural units included in the copolymer,
상기 히드록시기 함유 아크릴계 공중합체와 이소시아네이트기 함유 (메타)아크릴레이트계 단량체가 우레탄 결합을 형성한 것이며,The said hydroxyl group containing acrylic copolymer and the isocyanate group containing (meth) acrylate type monomer formed the urethane bond,
상기 히드록시기 함유 아크릴계 공중합체는 유리전이온도(Tg)가 -75 내지 -55℃인 에틸렌옥사이드기 함유 (메타)아크릴레이트 단량체 및 히드록시기 함유 알킬 아크릴레이트 단량체를 포함하며, The hydroxy group-containing acrylic copolymer includes an ethylene oxide group-containing (meth) acrylate monomer having a glass transition temperature (Tg) of -75 to -55 ° C and a hydroxy group-containing alkyl acrylate monomer,
중량평균 분자량이 20만 내지 100만인 것을 특징으로 하는 광학 투명 점착제 조성물에 관한 것이다.A weight average molecular weight is 200,000-1 million, and it is related with the optically transparent adhesive composition characterized by the above-mentioned.
본 발명의 광학 투명 점착제 조성물은 유리전이온도(Tg)가 낮은 에틸렌 옥사이드기 함유 (메타)아크릴레이트 단량체를 포함함으로써 폴딩 특성을 향상시킬 수 있으며, 히드록시기 함유 알킬 아크릴레이트 단량체를 포함함으로써 내습열성 및 밀착성을 향상시킬 수 있으며, 상기 히드록시기 및 이소시아네이트기의 우레탄 결합을 통하여 가교밀도를 높임으로써 내열성 및 내구성이 우수한 광학 투명 점착제 조성물을 제공할 수 있다.Optical transparent pressure-sensitive adhesive composition of the present invention can improve the folding properties by including an ethylene oxide group-containing (meth) acrylate monomer having a low glass transition temperature (Tg), and by including a hydroxy group-containing alkyl acrylate monomer moist heat resistance and adhesion It is possible to improve, and to increase the crosslinking density through the urethane bond of the hydroxy group and the isocyanate group can provide an optically transparent adhesive composition excellent in heat resistance and durability.
본 발명에서 상기 "(메타)아크릴레이트"는 "아크릴레이트" 또는 "메타크릴레이트"를 의미한다.In the present invention, the "(meth) acrylate" means "acrylate" or "methacrylate".
상기 광경화성 아크릴레이트 공중합체는, 유리전이온도(Tg)가 -75 내지 -55℃인 에틸렌옥사이드기 함유 (메타)아크릴레이트 단량체 및 히드록시기 함유 알킬 아크릴레이트 단량체를 공중합시켜, 분지쇄 또는 말단에 열경화성 관능기인 히드록시기(OH기)가 도입된 아크릴계 공중합체 주사슬을 제조하고, 이어서 이소시아네이트기 함유 (메타)아크릴레이트계 단량체를 주사슬과 적절한 조건에서 반응시킴으로써, 주사슬의 열경화성 관능기(OH기)의 적어도 일부를 이소시아네이트기 함유 (메타)아크릴레이트로 치환시켜 제조될 수 있다.The photocurable acrylate copolymer copolymerizes an ethylene oxide group-containing (meth) acrylate monomer and a hydroxy group-containing alkyl acrylate monomer having a glass transition temperature (Tg) of -75 to -55 ° C, and is thermosetting at a branched chain or terminal. The acrylic copolymer main chain into which the hydroxyl group (OH group) which is a functional group was introduce | transduced was prepared, and then the isocyanate group containing (meth) acrylate type monomer was made to react with a main chain on suitable conditions, and the thermosetting functional group (OH group) of a main chain It can be prepared by substituting at least a portion with an isocyanate group-containing (meth) acrylate.
상기 주사슬은 예를 들면, 용액 중합(solution polymerization), 광중합(photo polymerization), 괴상중합(bulk polymerization), 현탁중합(suspension polymerization) 또는 유화중합(emulsion polymerization)과 같은 통상적인 중합 방법을 통하여 제조될 수 있다.The main chain is prepared by conventional polymerization methods such as, for example, solution polymerization, photo polymerization, bulk polymerization, suspension polymerization or emulsion polymerization. Can be.
상기 히드록시기 함유 아크릴계 공중합체에 중합된 형태로 포함되는 유리전이온도(Tg)가 -75 내지 -55℃인 에틸렌옥사이드기 함유 (메타)아크릴레이트 단량체는 하기 화학식 1로 나타낼 수 있다.An ethylene oxide group-containing (meth) acrylate monomer having a glass transition temperature (Tg) of -75 to -55 ° C included in a polymerized form in the hydroxy group-containing acrylic copolymer may be represented by the following Formula 1.
[화학식 1][Formula 1]
Figure PCTKR2017005951-appb-I000001
Figure PCTKR2017005951-appb-I000001
상기 R1은 수소 또는 메틸기이고,R 1 is hydrogen or a methyl group,
상기 R2는 탄소수 1 내지 4의 직쇄 알킬기이고,R 2 is a linear alkyl group having 1 to 4 carbon atoms,
상기 a는 1 내지 15의 자연수이다.A is a natural number of 1 to 15.
또한, 상기 화학식 1은 구체적으로 하기 화학식 2 내지 4로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것이 바람직하다.In addition, it is preferable that Formula 1 specifically includes one or more selected from the group consisting of the following Formulas 2 to 4.
[화학식 2][Formula 2]
Figure PCTKR2017005951-appb-I000002
Figure PCTKR2017005951-appb-I000002
유리전이온도(Tg) : -70℃Glass Transition Temperature (Tg): -70 ℃
[화학식 3][Formula 3]
Figure PCTKR2017005951-appb-I000003
Figure PCTKR2017005951-appb-I000003
유리전이온도(Tg) : -60℃Glass Transition Temperature (Tg): -60 ℃
[화학식 4][Formula 4]
Figure PCTKR2017005951-appb-I000004
Figure PCTKR2017005951-appb-I000004
유리전이온도(Tg) : -71℃Glass Transition Temperature (Tg): -71 ℃
상기 에틸렌옥사이드기 함유 (메타)아크릴레이트 단량체의 유리전이온도(Tg)가 -75℃ 미만이면 경제성 때문에 사용하기 어렵고, 광학 투명 점착제 조성물의 내구성이 저하되는 문제가 발생하며, -55℃를 초과하면 저온에서의 폴딩(folding) 특성이 저하되는 문제가 발생한다.If the glass transition temperature (Tg) of the ethylene oxide group-containing (meth) acrylate monomer is less than -75 ° C, it is difficult to use due to economical efficiency, and the durability of the optically transparent adhesive composition may be deteriorated. There arises a problem that the folding characteristic at low temperature is reduced.
상기 히드록시기 함유 아크릴계 공중합체에 중합된 형태로 포함되는 히드록시기 함유 알킬 아크릴레이트 단량체는 구체적으로 예를 들면, 2-히드록시에틸 아크릴레이트, 2-히드록시프로필 아크릴레이트, 4-히드록시부틸 아크릴레이트, 5-히드록시펜틸 아크릴레이트, 6-히드록시헥실 아크릴레이트, 8-히드록시옥틸 아크릴레이트, 2-히드록시에틸렌글리콜 아크릴레이트 및 2-히드록시프로필렌글리콜 아크릴레이트 등을 들 수 있다. The hydroxy group-containing alkyl acrylate monomer included in the polymerized form in the hydroxy group-containing acrylic copolymer is specifically, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, 8-hydroxyoctyl acrylate, 2-hydroxyethylene glycol acrylate, 2-hydroxypropylene glycol acrylate, and the like.
이들 중에서도 특히, 4-히드록시부틸 아크릴레이트, 5-히드록시펜틸 아크릴레이트 및 6-히드록시헥실 아크릴레이트 등의 단량체가 바람직하게 사용될 수 있으며, 보다 바람직하게는 4-히드록시부틸 아크릴레이트가 사용될 수 있다.Among these, monomers such as 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate can be preferably used, and more preferably 4-hydroxybutyl acrylate can be used. Can be.
상기에서 예시한 히드록시기 함유 알킬 아크릴레이트 단량체를 사용할 경우, 본 발명의 광경화성 아크릴레이트 공중합체의 구조는 하기 화학식 5로 표시할 수 있다.When using the hydroxy group-containing alkyl acrylate monomers exemplified above, the structure of the photocurable acrylate copolymer of the present invention may be represented by the following formula (5).
[화학식 5][Formula 5]
Figure PCTKR2017005951-appb-I000005
Figure PCTKR2017005951-appb-I000005
상기 R3는 에틸렌옥사이드기를 1 내지 15개 포함하는 탄소수 1 내지 4의 직쇄 알킬기이고,R 3 is a linear alkyl group having 1 to 4 carbon atoms containing 1 to 15 ethylene oxide groups,
상기 R4는 수소 또는 메틸기이고,R 4 is hydrogen or a methyl group,
상기 R5은 수소 또는 메틸기이고,R 5 is hydrogen or a methyl group,
상기 R6는 탄소수 1 내지 10의 직쇄 또는 탄소수 4 내지 10의 분지쇄 알킬렌기이고,R 6 is a straight or C4-10 branched alkylene group having 1 to 10 carbon atoms,
상기 R7은 수소 또는 메틸기이고,R 7 is hydrogen or a methyl group,
상기 O는 2 내지 6의 자연수이고,O is a natural number of 2 to 6,
상기 l, m 및 n은 각각 상기에서 기술한 단량체들의 사용량 범위에 따라 형성되는 값을 갖는다.The l, m and n each have a value formed according to the range of usage of the monomers described above.
상기 히드록시기 함유 아크릴계 공중합체에 있어서, 공중합체에 포함된단량체 총 중량에 있어서, 유리전이온도(Tg)가 -75 내지 -55℃인 에틸렌옥사이드기 함유 (메타)아크릴레이트 단량체는 50 내지 95 중량%로 포함되며, 히드록시기 함유 알킬 아크릴레이트 단량체는 5 내지 50 중량%로 포함되는 것이 바람직하다. In the hydroxy group-containing acrylic copolymer, 50 to 95% by weight of the ethylene oxide group-containing (meth) acrylate monomer having a glass transition temperature (Tg) of -75 to -55 ° C based on the total weight of monomers included in the copolymer. It is included as, hydroxy group-containing alkyl acrylate monomer is preferably included in 5 to 50% by weight.
또한, 상기 히드록시기 함유 알킬 아크릴레이트 단량체가 5 중량% 미만으로 포함되면 점착제에 친수성 기인 히드록시기가 부족해져서 점착제층에서 습기를 잡아주지 못하고 계면으로 습기가 배출되어 내습열성(밀착성)이 저하되는 문제가 발생하며, 50 중량%를 초과하여 포함되는 경우에는 점착제가 수분을 과량 흡수하여 부피가 팽창하며 응집력이 저하되어 계면박리 및 기포가 발생하는 문제가 발생한다.In addition, when the hydroxy group-containing alkyl acrylate monomer is included in less than 5% by weight, the hydroxy group due to hydrophilicity is insufficient in the pressure-sensitive adhesive to prevent moisture from the pressure-sensitive adhesive layer, the moisture is discharged to the interface, resulting in a problem that the moisture resistance (adhesiveness) is lowered And, when included in excess of 50% by weight, the pressure-sensitive adhesive absorbs excessive moisture, the volume expands, and the cohesive force is lowered, causing a problem of interfacial peeling and bubbles.
상기 히드록시기 함유 아크릴계 공중합체는 이 분야에서 공지되어 있는 다른 공중합성 단량체를 중합된 형태로 더 포함할 수 있다. 상기 다른 공중합성 단량체의 종류는 특별히 제한되지 않으며, 예를 들면, (메타)아크릴로니트릴, (메타)아크릴아미드, N-메틸 (메타)아크릴아미드 또는 N-부톡시 메틸 (메타)아크릴아미드와 같은 질소 함유 단량체; 스티렌 또는 메틸 스티렌과 같은 스티렌계 단량체; 글리시딜 (메타)아크릴레이트; 또는 비닐 아세테이트와 같은 카복살산의 비닐 에스테르 등을 들 수 있으나, 이에 한정되는 것은 아니다.The hydroxy group-containing acrylic copolymer may further include other copolymerizable monomers known in the art in a polymerized form. The kind of the other copolymerizable monomer is not particularly limited, and examples thereof include (meth) acrylonitrile, (meth) acrylamide, N-methyl (meth) acrylamide or N-butoxy methyl (meth) acrylamide. Such nitrogen-containing monomers; Styrene-based monomers such as styrene or methyl styrene; Glycidyl (meth) acrylate; Or vinyl esters of carboxylic acids such as vinyl acetate, but are not limited thereto.
상기 다른 공중합성 단량체가 포함되는 경우, 유연성이나 박리력 등을 고려하여, 그 함량은 상기에서 기술된 단량체 총합 100 중량부를 기준으로 20 중량부 이하로 조절하는 것이 바람직하다.When the other copolymerizable monomer is included, in consideration of flexibility and peeling force, etc., the content thereof is preferably adjusted to 20 parts by weight or less based on 100 parts by weight of the total monomers described above.
상기 아크릴계 공중합체에 있어서 중량평균분자량은, GPC(Gel permeation chromatograph)로 측정되는 표준 폴리스티렌에 대한 환산수치를 의미한다.In the acrylic copolymer, the weight average molecular weight means a conversion value with respect to standard polystyrene measured by gel permeation chromatograph (GPC).
상기 히드록시기 함유 아크릴계 공중합체의 중량 평균 분자량은 20만 내지 100만이다.The weight average molecular weight of the hydroxy group-containing acrylic copolymer is 200,000 to 1 million.
상기 광경화성 (메타)아크릴레이트 공중합체에 포함되는 이소시아네이트기 함유 (메타)아크릴레이트계 단량체로는 이소시아네이토 C1~C10 알킬 아크릴레이트 단량체가 사용될 수 있으며, 구체적으로 이소시아네이토 C1~C10직쇄 또는 C4~C10분지쇄 알킬 아크릴레이트가 사용될 수 있다. 상기에서 C1~C10직쇄 또는 C4~C10분지쇄 알킬기로는 메틸, 에틸, 프로필, 이소프로필, 부틸, iso-부틸, sec-부틸, tert-부틸, 펜틸, 헥실, 헵틸, 옥틸, 2-에틸헥실, 노닐, 데카닐 등을 들 수 있으며, 이들 중에서 에틸, 프로필 등이 바람직하게 사용될 수 있다.Isocyanate C 1 to C 10 alkyl acrylate monomers may be used as the isocyanate group-containing (meth) acrylate monomer included in the photocurable (meth) acrylate copolymer, and specifically, isocyanato C 1 to C 10 straight or C 4 to C 10 branched alkyl acrylates may be used. The C 1 to C 10 straight or C 4 to C 10 branched alkyl group may be methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decanyl and the like can be cited, and among these, ethyl, propyl and the like can be preferably used.
상기 이소시아네이트기 함유 (메타)아크릴레이트계 단량체는 광경화성 (메타)아크릴레이트 공중합체에 포함되는 구성단위 총 중량에 대하여 0.1 중량% 내지 5 중량%로 포함될 수 있다. 상기 이소시아네이트기 함유 (메타)아크릴레이트계 단량체가 0.1 중량% 미만으로 포함되는 경우, 점착제 조성물의 응집력 및 내열성이 저하될 수 있으며, 5 중량%를 초과하는 경우에는 점착제의 응집력이 너무 강해지므로 폴딩특성이 저하될 수 있다.The isocyanate group-containing (meth) acrylate-based monomer may be included in an amount of 0.1 wt% to 5 wt% based on the total weight of the structural units included in the photocurable (meth) acrylate copolymer. When the isocyanate group-containing (meth) acrylate-based monomer is included in less than 0.1% by weight, the cohesive force and heat resistance of the pressure-sensitive adhesive composition may be lowered, and when it exceeds 5% by weight, the cohesive force of the pressure-sensitive adhesive becomes too strong This can be degraded.
본 발명의 광학 투명 점착제 조성물은 라디칼 중합성기의 반응을 효율적으로 유도하기 위하여, 광중합 개시제를 포함한다. 상기 광중합 개시제는 히드록시기 함유 아크릴계 공중합체의 중합시에 사용될 수 있으며, 최종적으로 광학 투명 점착제 조성물에도 광경화성 (메타)아크릴레이트 공중합체와 함께 포함된다. The optically transparent adhesive composition of this invention contains a photoinitiator in order to induce reaction of a radically polymerizable group efficiently. The photopolymerization initiator may be used in the polymerization of the hydroxyl group-containing acrylic copolymer, and finally included in the optically transparent adhesive composition together with the photocurable (meth) acrylate copolymer.
상기 광중합 개시제는, 특별히 한정되지 않으며 이 분야에 공지된 광중합 개시제가 사용될 수 있다. 구체적으로는 벤조인계 개시제, 히드록시케톤계 개시제, 아미노케톤계 개시제 또는 포스핀옥시드계 개시제 등과 같이, 자외선 등의 조사에 의해 라디칼을 발생시켜 광중합을 개시시킬 수 있는 일반적인 개시제를 들 수 있다. The photopolymerization initiator is not particularly limited and photopolymerization initiators known in the art may be used. Specifically, general initiators such as benzoin initiators, hydroxyketone initiators, amino ketone initiators or phosphine oxide initiators can be used to generate radicals by irradiation with ultraviolet rays to initiate photopolymerization.
상기 광중합 개시제의 함량이 지나치게 적을 경우, 첨가로 인한 효과가 미미할 수 있고, 지나치게 많을 경우에는, 내구신뢰성이나 투명성 등의 물성에 악영향을 미칠 수 있으므로, 이러한 점을 고려하여 적절한 함량 범위를 선택할 수 있다. When the content of the photopolymerization initiator is too small, the effect of the addition may be insignificant, and when too large, it may adversely affect physical properties such as durability and transparency, so that an appropriate content range may be selected in consideration of this point. .
상기 광중합 개시제는 광경화성 (메타)아크릴레이트 공중합체 100 중량부에 대하여 0.1 내지 5 중량부, 더욱 바람직하게는 0.5 내지 2 중량부로 포함될 수 있다.The photopolymerization initiator may be included in an amount of 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the photocurable (meth) acrylate copolymer.
본 발명의 광학 투명 점착제 조성물은 다관능성 가교제를 더 포함할 수 있다. 이러한 다관능성 가교제는 특별히 한정되지 않으며, 이 분야에서 공지된 것들이 사용될 수 있다. 구체적으로 예로는 열경화성 다관능 이소시아네이트 가교제, 다관능 (메타)아크릴레이트 가교제 등을 들 수 있다.The optically transparent adhesive composition of this invention may further contain a polyfunctional crosslinking agent. Such a multifunctional crosslinking agent is not particularly limited, and those known in the art may be used. Specifically, a thermosetting polyfunctional isocyanate crosslinking agent, a polyfunctional (meth) acrylate crosslinking agent, etc. are mentioned.
상기 다관능성 가교제는 광경화성 (메타)아크릴레이트 공중합체 100 중량부를 기준으로 0.02 내지 5 중량부로 더 포함될 수 있다.The multifunctional crosslinking agent may be further included in an amount of 0.02 to 5 parts by weight based on 100 parts by weight of the photocurable (meth) acrylate copolymer.
본 발명의 광학 투명 점착제 조성물은, 실란 커플링제를 추가로 포함할 수 있다. 커플링제의 종류는 특별히 제한되지 않으며, 점착제 제조 분야에서 통상적으로 공지된 커플링제를 사용할 수 있다. 예를 들면, 실란 커플링제로서 감마-글리시독시프로필 트리에톡시 실란, 감마-글리시독시프로필 트리메톡시 실란, 감마-글리시독시프로필 메틸디에톡시 실란, 감마-글리시독시프로필 트리에톡시 실란, 3-머캅토프로필 트리메톡시 실란, 비닐트리메톡시실란, 비닐트리에톡시 실란, 감마-메타크릴록시프로필 트리메톡시 실란, 감마-메타크릴록시 프로필 트리에톡시 실란, 감마-아미노프로필 트리메톡시 실란, 감마-아미노프로필 트리에톡시 실란 또는 3-이소시아네이토프로필 트리에톡시 실란 등을 들 수 있다.The optically transparent adhesive composition of this invention can contain a silane coupling agent further. The kind of coupling agent is not particularly limited, and a coupling agent commonly known in the art of adhesive production can be used. For example, as a silane coupling agent, gamma-glycidoxypropyl triethoxy silane, gamma-glycidoxypropyl trimethoxy silane, gamma-glycidoxypropyl methyldiethoxy silane, gamma-glycidoxypropyl triethoxy Silane, 3-mercaptopropyl trimethoxy silane, vinyltrimethoxysilane, vinyltriethoxy silane, gamma-methacryloxypropyl trimethoxy silane, gamma-methacryloxy propyl triethoxy silane, gamma-aminopropyl Trimethoxy silane, gamma-aminopropyl triethoxy silane, 3-isocyanatopropyl triethoxy silane, etc. are mentioned.
상기 실란 커플링제는 광경화성 (메타)아크릴레이트 공중합체 100 중량부에 대하여 0.01 중량부 내지 5 중량부, 바람직하게는 0.01 중량부 내지 1 중량부로 포함될 수 있다. The silane coupling agent may be included in an amount of 0.01 to 5 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the photocurable (meth) acrylate copolymer.
본 발명의 광학 투명 점착제 조성물은 또한, 점착 성능의 조절을 위하여 점착성 부여제를 추가로 포함할 수 있다. The optically transparent adhesive composition of this invention may further contain a tackifier for control of adhesive performance.
또한, 에폭시 수지, 경화제, 자외선 안정제, 산화 방지제, 조색제, 보강제, 충진제, 소포제, 계면 활성제 및 가소제로 이루어진 군으로부터 선택되는 하나 이상의 첨가제를 추가로 포함할 수 있다.It may further comprise one or more additives selected from the group consisting of epoxy resins, curing agents, ultraviolet stabilizers, antioxidants, colorants, reinforcing agents, fillers, antifoaming agents, surfactants and plasticizers.
본 발명의 광학 투명 점착제 조성물에는 용매가 더 포함될 수 있다. 상기 용매로는 광학 투명 점착제 조성물에 사용되는 단량체, 공중합체들을 용해할 수 있는 것이라면 이 분야에 공지된 용매가 제한 없이 사용될 수 있다. The optically transparent adhesive composition of this invention may further contain a solvent. As the solvent, any solvent known in the art may be used without limitation as long as it can dissolve monomers and copolymers used in the optically transparent adhesive composition.
상기 용매의 대표적인 예로는 에틸 아세테이트, 메틸에틸케톤, 톨루엔, 아세토니트릴 등을 들 수 있다. Representative examples of the solvent include ethyl acetate, methyl ethyl ketone, toluene, acetonitrile and the like.
상기 용매는 광경화성 (메타)아크릴레이트 공중합체 100 중량부를 기준으로 40 내지 85 중량부로 포함될 수 있다.The solvent may be included in an amount of 40 to 85 parts by weight based on 100 parts by weight of the photocurable (meth) acrylate copolymer.
본 발명의 광학 투명 점착제 조성물의 점도는 23에서 500cP 내지 2,500Cp인 범위인 것이 바람직하게 사용될 수 있다.The viscosity of the optically transparent adhesive composition of the present invention may preferably be used in the range of 23 to 500 cP to 2,500 Cp.
본 발명의 광학 투명 점착제 조성물은 유리전이온도(Tg)가 낮은 단량체들을 사용하여 폴딩 특성을 확보하면서도, 라디칼 중합에 의한 경화 시스템과 가교제와 열경화성 관능기(-OH기)에 의한 경화 시스템을 적절하게 함께 채용하여, 내구성을 확보하는 특징을 갖는다.The optically transparent adhesive composition of the present invention secures folding properties by using monomers having a low glass transition temperature (Tg), while suitably combining a curing system by radical polymerization with a curing system by a crosslinking agent and a thermosetting functional group (-OH group). It has the characteristic to ensure durability.
본 발명의 광학 투명 점착제 조성물의 제조방법은 상기에서 설명된 것을 제외하고는 이 분야에서 통상적으로 사용되는 방법으로 실시될 수 있다. 이 때 이 분야에서 사용되는 분자량 조절제, 촉매 등도 제한 없이 사용될 수 있다.The method of preparing the optically transparent adhesive composition of the present invention may be carried out by a method commonly used in this field except as described above. At this time, molecular weight regulators, catalysts and the like used in this field may also be used without limitation.
본 발명의 광학 투명 점착제 조성물을 도포하는 방법은 특별히 제한되지 않으며, 예를 들면, 바 코팅(bar coating), 스핀 코팅(spin coating), 콤마 코팅(comma coating) 또는 그라비어 코팅(gravure coating) 등의 범용의 방식으로 수행할 수 있다. 도포 과정에서는 점착제 조성물에 포함되는 다관능성 가교제의 작용기의 가교 반응이 진행되지 않도록 제어하는 것이 균일한 코팅 공정의 수행의 관점에서 바람직하다. 이를 통해, 가교제가 코팅 작업 후의 경화 및 숙성 과정에서 가교 구조를 형성하여 점착제의 응집력, 점착 물성 및 절단성(cuttability) 등을 향상시킬 수 있다.The method of applying the optically transparent adhesive composition of the present invention is not particularly limited, and examples thereof include bar coating, spin coating, comma coating, gravure coating, and the like. This can be done in a general purpose way. In the coating process, it is preferable to control so that the crosslinking reaction of the functional group of the polyfunctional crosslinking agent contained in an adhesive composition may not progress, from a viewpoint of performing a uniform coating process. Through this, the crosslinking agent forms a crosslinked structure in the curing and aging process after the coating operation, thereby improving the cohesion, adhesive properties, and cuttability of the pressure-sensitive adhesive.
또한, 도포 과정은, 점착제 조성물 내부의 휘발 성분 또는 반응 잔류물과 같은 기포 유발 성분을 충분히 제거한 후, 수행되는 것이 바람직하다. 이에 따라 점착제의 가교 밀도 또는 분자량 등이 지나치게 낮아 탄성률이 떨어지고, 고온 상태에서 유리판 및 점착제층 사이에 존재하는 기포들이 커져 내부에서 산란체를 형성하는 현상 등을 방지할 수 있다.In addition, the application process is preferably performed after sufficiently removing the bubble-inducing components such as volatile components or reaction residues inside the pressure-sensitive adhesive composition. As a result, the crosslinking density or molecular weight of the pressure-sensitive adhesive is too low, the elastic modulus is lowered, and bubbles present between the glass plate and the pressure-sensitive adhesive layer in a high temperature state may be increased to prevent a phenomenon in which scattering bodies are formed inside.
광학 투명 점착제 조성물의 코팅층을 형성한 후, 이를 광조사를 통해 경화시킨다. 본 출원에서, 예를 들어, 자외선 조사 방식을 적용할 경우에, 상기 자외선 조사는, 고압 수은 램프, 무전극 램프 또는 크세논 램프(xenon lamp) 등의 수단을 사용하여 수행할 수 있다. After forming the coating layer of the optically transparent adhesive composition, it is cured through light irradiation. In the present application, for example, when applying an ultraviolet irradiation method, the ultraviolet irradiation may be performed using a means such as a high pressure mercury lamp, an electrodeless lamp or a xenon lamp.
또한, 광조사 공정의 전 또는 후에 조성물 내의 가교제의 작용기와 중합체의 열경화성 관능기의 반응을 유도하는 적절한 숙성 공정을 진행할 수도 있고, 그 과정에서의 조건은 적절한 가교 반응이 일어날 수 있다면, 특별히 제한되지 않는다.Further, before or after the light irradiation process, an appropriate aging process may be conducted to induce reaction of the functional group of the crosslinking agent in the composition with the thermosetting functional group of the polymer, and the conditions in the process are not particularly limited as long as an appropriate crosslinking reaction can occur. .
본 발명의 광학 필름용 점착제 조성물은, 예를 들면, 편광필름, 위상차 필름, 눈부심 방지 필름, 광시야각 보상 필름 또는 휘도 향상 필름 등의 광학 필름을 서로 적층하거나, 상기 광학 필름 또는 그 적층체를 디스플레이 패널 등과 같은 피착체에 부착하기 위한 용도로 사용될 수 있다.The pressure-sensitive adhesive composition for an optical film of the present invention, for example, laminated optical films such as a polarizing film, a retardation film, an anti-glare film, a wide viewing angle compensation film or a brightness enhancement film, or displays the optical film or a laminate thereof. It can be used for the purpose of attaching to adherends such as panels.
특히, 본 발명의 광학 필름용 점착제 조성물은 플렉서블 디스플레이 장치에 바람직하게 사용될 수 있다.In particular, the pressure-sensitive adhesive composition for an optical film of the present invention can be preferably used in a flexible display device.
또한, 본 발명은In addition, the present invention
상기 광학 투명 점착제 조성물을 전사필름에 코팅하여 제조되는 것을 특징으로 하는 광학 투명 점착제 필름을 제공한다. It provides an optical transparent pressure-sensitive adhesive film, which is prepared by coating the optical transparent pressure-sensitive adhesive composition on a transfer film.
상기 광학 투명 점착제 필름에 사용되는 전사필름으로는 이 분야에서 공지된 필름이 제한 없이 사용될 수 있다. 또한, 광학 투명 점착제 필름의 제조방법은 이 분야에 공지된 방법이 제한 없이 사용될 수 있다.As the transfer film used in the optically transparent adhesive film, a film known in the art may be used without limitation. In addition, the method of manufacturing the optically transparent adhesive film can be used without limitation methods known in the art.
또한, 본 발명은 In addition, the present invention
본 발명의 광학 투명 점착제 조성물로 형성된 점착층을 포함하는 것을 특징으로 하는 평판표시장치를 제공한다.It provides a flat panel display device comprising an adhesive layer formed of the optically transparent adhesive composition of the present invention.
상기에서 평판표시장치는 플렉서블 디스플레이 장치인 것이 더욱 바람직하다.The flat panel display is more preferably a flexible display device.
이하, 본 발명을 실시예 및 비교예를 이용하여 더욱 상세하게 설명한다. 그러나 하기 실시예는 본 발명을 예시하기 위한 것으로서 본 발명은 하기 실시예에 의해 한정되지 않고 다양하게 수정 및 변경될 수 있다.Hereinafter, the present invention will be described in more detail using examples and comparative examples. However, the following examples are provided to illustrate the present invention, and the present invention is not limited to the following examples and may be variously modified and changed.
제조예Production Example 1.  One. 광경화성Photocurable 아크릴레이트Acrylate 공중합체(A1)의 제조 Preparation of Copolymer (A1)
질소 가스가 환류되고, 온도 조절이 용이하도록 냉각 장치를 설치한 1L 반응기에 유리전이온도가 -60℃인 하기 화학식 2의 화합물 60 중량부 및 4-히드록시부틸 아크릴레이트(4-HBA) 40 중량부를 투입하였다. 용제로서 에틸 아세테이트(EAc; ethyl acetate) 120 중량부를 투입한 후에, 산소 제거를 위해 질소 가스를 60분 동안 퍼징(purging)하였다. 그 후, 온도를 70℃로 유지하고, 반응 개시제인 AIBN(azobisisobutyronitrile) 0.1 중량부를 투입하고, 12시간 동안 반응시켜 중량 평균 분자량이 45만인 아크릴계 공중합체를 제조하였다.Nitrogen gas is refluxed, 60 parts by weight of the compound of formula 2 and 40 weight of 4-hydroxybutyl acrylate (4-HBA) having a glass transition temperature of -60 ℃ in a 1L reactor equipped with a cooling device to facilitate temperature control Added wealth. After adding 120 parts by weight of ethyl acetate (EAc) as a solvent, nitrogen gas was purged for 60 minutes to remove oxygen. Thereafter, the temperature was maintained at 70 ° C, 0.1 parts by weight of AIBN (azobisisobutyronitrile) as a reaction initiator was added thereto, and reacted for 12 hours to prepare an acrylic copolymer having a weight average molecular weight of 450,000.
[화학식 2][Formula 2]
Figure PCTKR2017005951-appb-I000006
Figure PCTKR2017005951-appb-I000006
상기 아크릴계 공중합체 100 중량부, 중합금지제 (BHT) 0.5중량부, 2-이소시아네이토에틸 메타크릴레이트(2- isocyanatoethyl methacrylate) 1 중량부 및 DBTDL(dibutyl tindilaulate) 0.1 중량부를 질소 가스가 환류되고, 온도 조절이 용이하도록 냉각 장치를 설치한 1L 반응기에 투입하였다.100 parts by weight of the acrylic copolymer, 0.5 part by weight of a polymerization inhibitor (BHT), 1 part by weight of 2-isocyanatoethyl methacrylate (2-isocyanatoethyl methacrylate) and 0.1 part by weight of dibutyl tindilaulate (DBTDL) under nitrogen gas reflux It was put in a 1L reactor equipped with a cooling device for easy temperature control.
이어서, 40의 온도 및 상압에서 4 시간 이상 반응시켜, 광경화성 (메타)아크릴레이트 공중합체(A1)을 제조하였다.Subsequently, the mixture was reacted for 4 hours or more at a temperature of 40 and normal pressure to prepare a photocurable (meth) acrylate copolymer (A1).
제조예Production Example 2.  2. 광경화성Photocurable 아크릴레이트Acrylate 공중합체(A2)의 제조 Preparation of Copolymer (A2)
상기 화학식 2의 화합물 대신 유리전이온도가 -60℃인 하기 화학식 3의 화합물을 사용한 것을 제외하고는 상기 제조예 1과 동일하게 실시하여 광경화성 아크릴레이트 공중합체(A2)를 제조하였다(아크릴계 공중합체의 중량평균분자량 : 56만).A photocurable acrylate copolymer (A2) was prepared in the same manner as in Preparation Example 1 except that the compound of Formula 3 having a glass transition temperature of −60 ° C. instead of the compound of Formula 2 was used (acrylic copolymer). Weight average molecular weight of 560,000).
[화학식 3][Formula 3]
Figure PCTKR2017005951-appb-I000007
Figure PCTKR2017005951-appb-I000007
제조예Production Example 3.  3. 광경화성Photocurable 아크릴레이트Acrylate 공중합체(A3)의 제조 Preparation of Copolymer (A3)
상기 화학식 2의 화합물 대신 유리전이온도가 -71℃인 하기 화학식 4의 화합물을 사용한 것을 제외하고는 상기 제조예 1과 동일하게 실시하여 광경화성 아크릴레이트 공중합체(A3)를 제조하였다(아크릴계 공중합체의 중량평균분자량 : 51만).A photocurable acrylate copolymer (A3) was prepared in the same manner as in Preparation Example 1 except that the compound of Formula 4 having a glass transition temperature of −71 ° C. instead of the compound of Formula 2 was used (acrylic copolymer). Weight average molecular weight of 510,000).
[화학식 4][Formula 4]
Figure PCTKR2017005951-appb-I000008
Figure PCTKR2017005951-appb-I000008
제조예Production Example 4.  4. 광경화성Photocurable 아크릴레이트Acrylate 공중합체(A4)의 제조 Preparation of Copolymer (A4)
상기 화학식 2의 화합물 대신 유리전이온도가 -58℃인 헥실아크릴레이트(HA)를 사용한 것을 제외하고는 상기 제조예 1과 동일하게 실시하여 광경화성 아크릴레이트 공중합체(A4)를 제조하였다(아크릴계 공중합체의 중량평균분자량 : 37만).A photocurable acrylate copolymer (A4) was prepared in the same manner as in Preparation Example 1, except that hexyl acrylate (HA) having a glass transition temperature of −58 ° C. was used instead of the compound of Formula 2 (acrylic air). Weight average molecular weight of coalescing: 370,000).
제조예Production Example 5.  5. 굴곡성Flexibility 평가용  For evaluation 하드코팅Hard coating 필름의 제조 Manufacture of film
<에폭시 <Epoxy 실록산Siloxane 수지 제조> Resin Manufacturing>
3-글리시독시프로필트리메톡시실란(GPTS, Gelest社)과 물을 23.63 g : 2.70 g (0.1mol : 0.15 mol)의 비율로 혼합하여 100 mL 2 neck 플라스크에 넣었다. 그 후 상기 혼합물에 0.05 mL의 암모니아를 촉매로 첨가하고 60℃에서 6 시간 동안 교반하여 실론산 졸을 제조하였다.3-Glycidoxypropyltrimethoxysilane (GPTS, Gelest, Inc.) and water were mixed in a ratio of 23.63 g: 2.70 g (0.1 mol: 0.15 mol) and placed in a 100 mL 2 neck flask. Then 0.05 mL of ammonia was added to the mixture as a catalyst and stirred at 60 ° C. for 6 hours to prepare a silonic acid sol.
<< 하드코팅Hard coating 조성물 제조> Composition Preparation>
상기 실론산 졸과 디글리시딜 에테르를 100:10의 중량비로 혼합하고, 상기의 혼합물 100중량부에 대하여 2 중량부의 트리아릴설포니움 헥사플로로안티모네이트염을 혼합하여 하드코팅 조성물을 제조하였다.The silonic acid sol and diglycidyl ether are mixed in a weight ratio of 100: 10, and 2 parts by weight of triarylsulfonium hexafluoroantimonate salt is mixed with 100 parts by weight of the mixture to prepare a hard coating composition. Prepared.
<< 하드코팅Hard coating 필름 제조> Film manufacturing>
상기 하드코팅 조성물을 코로나에 의해 표면처리된 40 ㎛ 두께의 COP (사이클로 올레핀 폴리머, ZF-16, Zeon사) 필름 위에 50 ㎛ 의 두께로 코팅하여 필름을 제작하였다. 상기 필름을 수은 UV (Ultra Violet) 램프 (20 mW/cm2)에 5 분간 노출하여 상기 트리아릴설포니움 헥사플로로안티모네이트염에 의하여 반응을 개시시키고, 50℃ 및 50%의 상대습도 조건 하에서 60 분 동안 수분 열처리를 실시하여 하드코팅막을 형성하였다.The hard coating composition was coated with a thickness of 50 μm on a 40 μm thick COP (cycloolefin polymer, ZF-16, Zeon) film treated by corona to prepare a film. The film was exposed to a mercury UV (Ultra Violet) lamp (20 mW / cm 2 ) for 5 minutes to initiate the reaction with the triarylsulfonium hexafluoroantimonate salt and at 50 ° C. and 50% relative humidity. Moisture heat treatment was performed for 60 minutes under the conditions to form a hard coat film.
<광학 투명 점착제 조성물의 제조><Production of Optical Transparent Adhesive Composition>
실시예Example 1. One.
상기 제조예 1에서 제조된 광경화성 (메타)아크릴레이트 공중합체(A1) 100 중량부에 대하여, 다관능성 이소시아네이트 가교제(Coronate L, 일본 NPU제) 0.5 중량부, 광중합개시제(히드록시시클로헥실페닐 케톤, irgacure 184, 스위스 시바스폐셜티 케미컬(제)) 0.2 중량부를 혼합하여 실시예 1의 광학 투명 점착제 조성물을 제조하였다.To 100 parts by weight of the photocurable (meth) acrylate copolymer (A1) prepared in Preparation Example 1, 0.5 part by weight of a polyfunctional isocyanate crosslinking agent (Coronate L, manufactured by Japan NPU), a photopolymerization initiator (hydroxycyclohexylphenyl ketone , irgacure 184, Swiss Civas Specialty Chemical (manufactured) 0.2 parts by weight were mixed to prepare an optically transparent adhesive composition of Example 1.
실시예Example 2. 2.
상기 실시예 1에서, 제조예 1에서 제조된 광경화성 (메타)아크릴레이트 공중합체(A1) 대신 제조예 2에서 제조된 광경화성 (메타)아크릴레이트 공중합체(A2)를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 광학 투명 점착제 조성물을 제조하였다.In Example 1, except that the photocurable (meth) acrylate copolymer (A2) prepared in Preparation Example 2 was used instead of the photocurable (meth) acrylate copolymer (A1) prepared in Preparation Example 1 An optically transparent adhesive composition was prepared in the same manner as in Example 1.
실시예Example 3. 3.
상기 실시예 1에서, 제조예 1에서 제조된 광경화성 (메타)아크릴레이트 공중합체(A1) 대신 제조예 3에서 제조된 광경화성 (메타)아크릴레이트 공중합체(A3)를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 광학 투명 점착제 조성물을 제조하였다.In Example 1, except that the photocurable (meth) acrylate copolymer (A3) prepared in Preparation Example 3 was used instead of the photocurable (meth) acrylate copolymer (A1) prepared in Preparation Example 1 An optically transparent adhesive composition was prepared in the same manner as in Example 1.
비교예Comparative example 1. One.
상기 실시예 1에서, 제조예 1에서 제조된 광경화성 (메타)아크릴레이트 공중합체(A1) 대신 제조예 4에서 제조된 광경화성 (메타)아크릴레이트 공중합체(A4)를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 광학 투명 점착제 조성물을 제조하였다.In Example 1, except that the photocurable (meth) acrylate copolymer (A4) prepared in Preparation Example 4 was used instead of the photocurable (meth) acrylate copolymer (A1) prepared in Preparation Example 1 An optically transparent adhesive composition was prepared in the same manner as in Example 1.
실시예Example 4. 광학 투명 점착제 필름의 제조 4. Preparation of Optical Transparent Adhesive Film
상기 실시예 1 내지 3 및 비교예 1에서 제조된 광학 투명 점착제 조성물 각각을 실리콘 이형제가 코팅된 50 ㎛ 두께의 PET 필름 상에 경화 후의 두께가 100 ㎛가 되도록 도포하고, 100에서 5분 동안 건조시켜서 실시예 4-1(실시예 1의 광학 투명 점착제 조성물 사용), 실시예 4-2(실시예 2의 광학 투명 점착제 조성물 사용), 실시예 4-3(실시예 3의 광학 투명 점착제 조성물 사용) 및 비교예 2-1(비교예 1의 광학 투명 점착제 조성물 사용) 의 광학 투명 점착제 필름을 제조하였다.Each of the optically transparent adhesive compositions prepared in Examples 1 to 3 and Comparative Example 1 was applied on a 50 μm-thick PET film coated with a silicone release agent so that the thickness after curing was 100 μm, and dried at 100 to 5 minutes. Example 4-1 (using the optically transparent adhesive composition of Example 1), Example 4-2 (using the optically transparent adhesive composition of Example 2), Example 4-3 (using the optically transparent adhesive composition of Example 3) And the optical transparent pressure-sensitive adhesive film of Comparative Example 2-1 (using the optical transparent pressure-sensitive adhesive composition of Comparative Example 1).
실시예Example 5.  5. 점착제층이Adhesive layer 형성된  Formed 적층체의Laminate 제조 Produce
상기 실시예 4-1, 실시예 4-2, 실시예 4-3 및 비교예 2-1에서 제조된 광학 투명 점착제 필름을 사용하여 두께 100㎛의 PET 필름 (미쯔비시사제 100um PET)에 점착제층을 적층하고, 이형필름 방향에서 UV램프(퓨전사)를 이용하여 1000mJ/cm2의 광량을 조사하여 각각 실시예 5-1, 실시예 5-2, 실시예 5-3 및 비교예 3-1의 점착제층이 형성된 적층체를 제조하였다. Using the optical transparent pressure-sensitive adhesive film prepared in Example 4-1, Example 4-2, Example 4-3 and Comparative Example 2-1, a pressure-sensitive adhesive layer was applied to a 100 μm-thick PET film (100 um PET manufactured by Mitsubishi Corporation). Laminating and irradiating the amount of light of 1000mJ / cm 2 using a UV lamp (fusion yarn) in the release film direction of Example 5-1, Example 5-2, Example 5-3 and Comparative Example 3-1 The laminated body in which the adhesive layer was formed was manufactured.
실시예Example 6.  6. 굴곡성Flexibility 평가용  For evaluation 하드코팅Hard coating 필름/ film/ 점착층Adhesive layer /PET / PET 적층체의Laminate 제조 Produce
상기 실시예 5-1, 실시예 5-2, 실시예 5-3 및 비교예 3-1의 적층체를 50 mm × 100 mm의 크기로 재단하였다. 이어서, 상기 재단된 적층체의 점착제층에 부착된 이형 PET 필름을 박리하고, 50 mm × 100 mm 크기의 상기 제조예 5에서 제조된 굴곡성 평가용 하드코팅 필름 상에 부착시키고, 오토클레이브(50, 5 기압)에서 약 20분 동안 압착 처리하고, 항온 항습 조건(23, 50% 상대습도)에서 24 시간 동안 양생하여 각각 실시예 6-1, 실시예 6-2, 실시예 6-3 및 비교예 4-1의 굴곡성 평가용 하드코팅 필름/점착층/PET(100㎛) 적층체를 제조하였다.The laminates of Example 5-1, Example 5-2, Example 5-3 and Comparative Example 3-1 were cut to a size of 50 mm x 100 mm. Subsequently, the release PET film attached to the pressure-sensitive adhesive layer of the cut laminate is peeled off, and then adhered onto a hard coating film for evaluation of flexibility prepared in Preparation Example 5 having a size of 50 mm × 100 mm, and the autoclave 50, 5 atm) for about 20 minutes, and cured for 24 hours at constant temperature and humidity conditions (23, 50% relative humidity), respectively, Example 6-1, Example 6-2, Example 6-3, and Comparative Example The hard coat film / adhesive layer / PET (100 micrometers) laminated body for the flexibility evaluation of 4-1 was manufactured.
실험예Experimental Example 1. 광학 투명 점착제 조성물의 물성 측정 1. Measurement of physical properties of optically transparent adhesive composition
1. One. 폴딩Folding (folding) 특성 평가(folding) property evaluation
<평가 방법><Evaluation method>
평가 표준:　IEC 62715Evaluation standard: IEC 62715
평가 장비: 면상체 무부하 U자 접기시험기 (DLDMLH-FS)Evaluation equipment: planar no-load U-fold tester (DLDMLH-FS)
장비 maker: YUASA SYSTEM(일본) Equipment maker: YUASA SYSTEM (Japan)
평가 조건: -20℃ / 1만회(하드코팅측이 안쪽으로 접히도록 굴곡시킴)Evaluation condition: -20 ° C / 10,000 times (flexing the hard coating side to be folded inward)
상기 실시예 6에서 제조된 실시예 6-1, 실시예 6-2, 실시예 6-3 및 비교예 4-1의 굴곡성 평가용 하드코팅 필름/점착층/PET 적층체를 상기의 평가방법에 따라서 폴딩특성을 평가하여 하기 표 1에 나타내었다.Example 6-1, Example 6-2, Example 6-3, and Comparative Example 4-1 hard coating film / adhesive layer / PET laminate prepared in Example 6 to the above evaluation method Therefore, the folding characteristics are shown in Table 1 below.
<평가기준><Evaluation Criteria>
○: 적층체에 기포, 박리, 크랙등의 불량모드가 관찰되지 않음(Circle): No defect modes, such as bubble, peeling, and a crack, are observed in a laminated body.
△: 적층체에 미세한 불량모드가 육안으로 미미하게 시인됨.(Triangle | delta): Fine defect mode is visually visually recognized by a laminated body.
X: 적층체의 폴딩부분에 육안으로 확연한 불량모드가 시인됨.X: The defect mode which was visually recognized in the folding part of a laminated body is recognized.
2. 내구성 평가2. Durability Rating
2-1. 내열성 평가2-1. Heat resistance rating
상기 실시예 6에서 제조된 실시예 6-1, 실시예 6-2, 실시예 6-3 및 비교예 4-1의 굴곡성 평가용 하드코팅 필름/점착층/PET 적층체를 80의 온도에서 1,000시간 동안 방치한 후에 기포나 박리의 발생 여부를 관찰하여 내열성을 평가하고 그 결과를 하기 표 1에 나타내었다.Example 6-1, Example 6-2, Example 6-3 and Comparative Example 4-1 prepared in Example 6 hard coating film / adhesive layer / PET laminate for evaluation of the temperature at a temperature of 80 After leaving for a time to observe the occurrence of bubbles or peeling to evaluate the heat resistance and the results are shown in Table 1 below.
<평가 기준><Evaluation Criteria>
◎: 기포나 박리 없음◎: no bubbles or peeling
○: 기포나 박리 < 5개○: bubble or peeling <5 pieces
△: 5개 ≤ 기포나 박리 < 10개△: 5 ≤ air bubbles or exfoliation <10
X: 10개 ≤ 기포나 박리X: 10 ≤ air bubbles or peeling
2-2. 2-2. 내습열성Moisture and Heat Resistance 평가 evaluation
상기 실시예 6에서 제조된 실시예 6-1, 실시예 6-2, 실시예 6-3 및 비교예 4-1의 굴곡성 평가용 하드코팅 필름/점착층/PET 적층체를 60의 온도 및 90%RH의 조건 하에서 1,000시간 방치한 후에 기포나 박리의 발생 여부를 관찰하였다. 이때, 시편의 상태를 평가하기 직전에 상온에서 24시간 방치한 후 관찰하여 내습열성을 평가하고 그 결과를 하기 표 1에 나타내었다.Example 6-1, Example 6-2, Example 6-3 and Comparative Example 4-1 prepared in Example 6 to the hard coating film / adhesive layer / PET laminate for evaluation of the temperature and 60 After leaving for 1,000 hours under the condition of% RH, it was observed whether bubbles or peeling occurred. At this time, immediately after evaluating the state of the specimen left at room temperature for 24 hours and observed to evaluate the heat and humidity resistance and the results are shown in Table 1 below.
<평가 기준><Evaluation Criteria>
◎: 기포나 박리 없음◎: no bubbles or peeling
○: 기포나 박리 < 5개○: bubble or peeling <5 pieces
△: 5개 ≤ 기포나 박리 < 10개△: 5 ≤ air bubbles or exfoliation <10
X: 10개 ≤ 기포나 박리X: 10 ≤ air bubbles or peeling
3. 밀착력 평가3. Evaluation of adhesion
상기 실시예 5에서 제조된 실시예 5-1, 실시예 5-2, 실시예 5-3 및 비교예 3-1에서 제조된 점착제 형성 적층제를 25 mm × 100mm 크기가 되도록 재단하여 시편을 제조하였다. 이어서, 점착제층에 부착된 이형 PET 필름을 박리하고, JIS Z 0237의 규정에 따라 2 kg의 롤러를 사용하여 점착제층이 형성된 적층제를 무알칼리 유리에 부착시켰다. 적층제가 부착된 무알칼리 유리를 오토클레이브(50, 5 기압)에서 약 20분 동안 압착 처리하고, 항온 항습 조건(23, 50% 상대습도)에서 24 시간 동안 보관하여 샘플을 제조하였다. 그 후, TA 장비(Texture Analyzer, 영국 스테이블 마이크로 시스템사제)를 사용하여, 상기 적층제를 무알칼리 유리로부터 300mm/min의 박리 속도 및 180도의 박리 각도로 박리하면서 밀착력을 측정하고 그 결과를 표 2에 나타내었다.The specimens were prepared by cutting the pressure-sensitive adhesive forming laminates prepared in Example 5-1, Example 5-2, Example 5-3, and Comparative Example 3-1 to 25 mm × 100 mm. It was. Subsequently, the release PET film adhered to the adhesive layer was peeled off, and the lamination agent in which the adhesive layer was formed was attached to the alkali free glass using the roller of 2 kg according to the provision of JIS Z 0237. Samples were prepared by compressing the alkali free glass with the laminating agent in an autoclave (50, 5 atm) for about 20 minutes and storing for 24 hours at constant temperature and humidity conditions (23, 50% relative humidity). After that, using the TA equipment (Texture Analyzer, manufactured by Stable Micro Systems Co., Ltd.), the adhesion was measured while peeling the laminate from an alkali free glass at a peel rate of 300 mm / min and a peel angle of 180 degrees. 2 is shown.
굴곡성 평가용 하드코팅 필름/점착층/PET 적층체Hard Coating Film / Adhesive Layer / PET Laminate for Flexibility Evaluation 사용된 점착제 조성물Adhesive composition used 폴딩특성Folding characteristic 내구성durability
내습열성Moisture and Heat Resistance 내열성Heat resistance
실시예 6-1Example 6-1 실시예 1 제조Example 1 Preparation ○○ ○○ ○○
실시예 6-2Example 6-2 실시예 2 제조Example 2 Preparation ○○ ○○ ○○
실시예 6-3Example 6-3 실시예 3 제조Example 3 Preparation ○○ ○○ ○○
비교예 4-1Comparative Example 4-1 비교예 1 제조Comparative Example 1 Preparation XX ◎◎ ◎◎
점착제층이 형성된 적층체Laminate with pressure-sensitive adhesive layer 사용된 점착제 조성물Adhesive composition used 밀착력Adhesion
실시예 5-1Example 5-1 실시예 1 제조Example 1 Preparation 13N13N
실시예 5-2Example 5-2 실시예 2 제조Example 2 Preparation 11N11N
실시예 5-3Example 5-3 실시예 3 제조Example 3 Preparation 9N9N
비교예 3-1Comparative Example 3-1 비교예 1 제조Comparative Example 1 Preparation 25N25N
상기 표 1 및 2의 실험결과로부터 확인되는 바와 같이, 본 발명의 실시예의 광학 투명 점착제 조성물들은 폴딩특성, 내습열성, 내열성 및 밀착력이 모두 우수한 것으로 확인되었다. 특히 폴딩특성은 비교예의 광학 투명 점착제 조성물들과 비교하여 현저하게 우수한 것으로 확인되었다.As confirmed from the experimental results of Tables 1 and 2, the optically transparent adhesive compositions of Examples of the present invention were confirmed to be excellent in all folding properties, moist heat resistance, heat resistance and adhesion. In particular, the folding properties were found to be remarkably superior compared to the optically transparent adhesive compositions of the comparative example.
반면, 비교예의 광학 투명 점착제 조성물은 유리전이온도(Tg) -75 내지 -55℃인 (메타)아크릴레이트 단량체를 포함하지 않아 폴딩특성이 매우 불량한 결과를 얻었다.On the other hand, the optically transparent pressure-sensitive adhesive composition of the comparative example does not include a (meth) acrylate monomer having a glass transition temperature (Tg) of -75 to -55 ° C, resulting in very poor folding properties.

Claims (13)

  1. 광경화성 (메타)아크릴레이트 공중합체 및 광중합 개시제를 포함하는 광학 투명 점착제 조성물로서,As an optically transparent adhesive composition containing a photocurable (meth) acrylate copolymer and a photoinitiator,
    상기 광경화성 (메타)아크릴레이트 공중합체는,The photocurable (meth) acrylate copolymer,
    공중합체에 포함되는 구성단위 총 중량에 대하여 히드록시기 함유 아크릴계 공중합체 95 내지 99.9 중량% 및 이소시아네이트기 함유 (메타)아크릴레이트계 단량체 0.1 내지 5 중량%를 포함하며,95 to 99.9 wt% of a hydroxy group-containing acrylic copolymer and 0.1 to 5 wt% of an isocyanate group-containing (meth) acrylate monomer based on the total weight of structural units included in the copolymer,
    상기 히드록시기 함유 아크릴계 공중합체와 이소시아네이트기 함유 (메타)아크릴레이트계 단량체가 우레탄 결합을 형성한 것이며,The said hydroxyl group containing acrylic copolymer and the isocyanate group containing (meth) acrylate type monomer formed the urethane bond,
    상기 히드록시기 함유 아크릴계 공중합체는 유리전이온도(Tg)가 -75 내지 -55℃인 에틸렌옥사이드기 함유 (메타)아크릴레이트 단량체 및 히드록시기 함유 알킬 아크릴레이트 단량체를 포함하며, The hydroxy group-containing acrylic copolymer includes an ethylene oxide group-containing (meth) acrylate monomer having a glass transition temperature (Tg) of -75 to -55 ° C and a hydroxy group-containing alkyl acrylate monomer,
    중량평균 분자량이 20만 내지 100만인 것을 특징으로 하는 광학 투명 점착제 조성물.The weight average molecular weight is 200,000-1 million, The optical transparent adhesive composition characterized by the above-mentioned.
  2. 청구항 1에 있어서, 상기 유리전이온도(Tg)가 -75 내지 -55℃인 에틸렌옥사이드기 함유 (메타)아크릴레이트 단량체는 하기 화학식 1로 나타내는 것을 특징으로 하는 광학 투명 점착제 조성물:The optical transparent pressure-sensitive adhesive composition of claim 1, wherein the ethylene oxide group-containing (meth) acrylate monomer having a glass transition temperature (Tg) of -75 to -55 ° C is represented by the following Chemical Formula 1.
    [화학식 1][Formula 1]
    Figure PCTKR2017005951-appb-I000009
    Figure PCTKR2017005951-appb-I000009
    상기 R1은 수소 또는 메틸기이고,R 1 is hydrogen or a methyl group,
    상기 R2는 탄소수 1 내지 4의 직쇄 알킬기이고,R 2 is a linear alkyl group having 1 to 4 carbon atoms,
    상기 a는 1 내지 15의 자연수이다.A is a natural number of 1 to 15.
  3. 청구항 2에 있어서, 상기 유리전이온도(Tg)가 -75 내지 -55℃인 에틸렌옥사이드기 함유 (메타)아크릴레이트 단량체는 하기 화학식 2 내지 4로 이루어진 군으로부터 선택되는 1종 이상을 포함하는 것을 특징으로 하는 광학 투명 점착제 조성물:The ethylene oxide group-containing (meth) acrylate monomer having a glass transition temperature (Tg) of -75 to -55 ° C comprises at least one member selected from the group consisting of the following Chemical Formulas 2 to 4. Optically transparent adhesive composition which consists of:
    [화학식 2][Formula 2]
    Figure PCTKR2017005951-appb-I000010
    Figure PCTKR2017005951-appb-I000010
    [화학식 3][Formula 3]
    Figure PCTKR2017005951-appb-I000011
    Figure PCTKR2017005951-appb-I000011
    [화학식 4][Formula 4]
    Figure PCTKR2017005951-appb-I000012
    Figure PCTKR2017005951-appb-I000012
  4. 청구항 1에 있어서, 상기 히드록시기 함유 알킬 아크릴레이트 단량체는 히드록시 C4~C6의 직쇄 또는 분지쇄 알킬 아크릴레이트 단량체인 것을 특징으로 하는 광학 투명 점착제 조성물.The optically transparent pressure-sensitive adhesive composition of claim 1, wherein the hydroxy group-containing alkyl acrylate monomer is a hydroxy C 4 to C 6 straight or branched chain alkyl acrylate monomer.
  5. 청구항 1에 있어서, 상기 히드록시기 함유 아크릴계 공중합체는 공중합체에 포함된 단량체 총 중량에 대하여 유리전이온도(Tg)가 -75 내지 -55℃인 에틸렌옥사이드기 함유 (메타)아크릴레이트 단량체 50 내지 95 중량% 및 히드록시기 함유 알킬 아크릴레이트 단량체 5 내지 50 중량%를 포함하는 것을 특징으로 하는 광학 투명 점착제 조성물.The hydroxy group-containing acrylic copolymer of claim 1 is 50 to 95 weight of the ethylene oxide group-containing (meth) acrylate monomer having a glass transition temperature (Tg) of -75 to -55 ℃ relative to the total weight of the monomer contained in the copolymer And 50 to 50% by weight of hydroxy group-containing alkyl acrylate monomers.
  6. 청구항 1에 있어서, 상기 광학 투명 점착제 조성물은 광경화성 (메타)아크릴레이트 공중합체 100 중량부를 기준으로 광중합 개시제 0.1 내지 5 중량부를 포함하는 것을 특징으로 하는 광학 투명 점착제 조성물.The optically transparent adhesive composition of claim 1, wherein the optically transparent adhesive composition comprises 0.1 to 5 parts by weight of a photopolymerization initiator based on 100 parts by weight of the photocurable (meth) acrylate copolymer.
  7. 청구항 6에 있어서, 상기 광학 투명 점착제 조성물은 광경화성 (메타)아크릴레이트 공중합체 100 중량부를 기준으로 다관능성 가교제 0.02 내지 5 중량부를 더 포함하는 것을 특징으로 하는 광학 투명 점착제 조성물.The optically transparent adhesive composition according to claim 6, wherein the optically transparent adhesive composition further comprises 0.02 to 5 parts by weight of a multifunctional crosslinking agent based on 100 parts by weight of the photocurable (meth) acrylate copolymer.
  8. 청구항 6 또는 7에 있어서, 상기 광학 투명 점착제 조성물은 광경화성 (메타)아크릴레이트 공중합체 100 중량부를 기준으로 용매 40 내지 85 중량부를 더 포함하는 것을 특징으로 하는 광학 투명 점착제 조성물.The optically transparent adhesive composition of claim 6 or 7, wherein the optically transparent adhesive composition further comprises 40 to 85 parts by weight of a solvent based on 100 parts by weight of the photocurable (meth) acrylate copolymer.
  9. 청구항 7에 있어서, 상기 다관능성 가교제는 열경화성 다관능 이소시아네이트 가교제 또는 다관능 (메타)아크릴레이트 가교제인 것을 특징으로 하는 광학 투명 점착제 조성물.The optically transparent adhesive composition according to claim 7, wherein the multifunctional crosslinking agent is a thermosetting polyfunctional isocyanate crosslinking agent or a polyfunctional (meth) acrylate crosslinking agent.
  10. 청구항 1에 있어서, 상기 이소시아네이트기 함유 (메타)아크릴레이트계 단량체는 이소시아네이토 C1~C10 알킬 아크릴레이트 단량체인 것을 특징으로 하는 광학 투명 점착제 조성물.The optically transparent pressure-sensitive adhesive composition of claim 1, wherein the isocyanate group-containing (meth) acrylate monomer is an isocyanato C 1 to C 10 alkyl acrylate monomer.
  11. 청구항 1의 광학 투명 점착제 조성물을 전사 필름에 코팅하여 제조되는 것을 특징으로 하는 광학 투명 점착제 필름.An optically transparent adhesive film prepared by coating the optical transparent adhesive composition of claim 1 on a transfer film.
  12. 청구항 1의 광학 투명 점착제 조성물로 형성된 점착층을 포함하는 것을 특징으로 하는 평판표시장치.A flat panel display comprising an adhesive layer formed of the optically transparent adhesive composition of claim 1.
  13. 청구항 12에 있어서, 상기 평판표시장치는 플렉서블 디스플레이 장치인 것을 특징으로 하는 평판표시장치.The flat panel display of claim 12, wherein the flat panel display is a flexible display device.
PCT/KR2017/005951 2016-09-13 2017-06-08 Optically clear adhesive composition, optically clear adhesive film comprising same, and flat display device WO2018052178A1 (en)

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