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WO2018062744A1 - Composition adhésive optiquement transparente, film adhésif optiquement transparent la comprenant, et dispositif d'affichage plat - Google Patents

Composition adhésive optiquement transparente, film adhésif optiquement transparent la comprenant, et dispositif d'affichage plat Download PDF

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Publication number
WO2018062744A1
WO2018062744A1 PCT/KR2017/010207 KR2017010207W WO2018062744A1 WO 2018062744 A1 WO2018062744 A1 WO 2018062744A1 KR 2017010207 W KR2017010207 W KR 2017010207W WO 2018062744 A1 WO2018062744 A1 WO 2018062744A1
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Prior art keywords
weight
meth
acrylate
adhesive composition
monomer
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English (en)
Korean (ko)
Inventor
최한영
박일성
유병묵
정경문
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Dongwoo Fine Chem Co Ltd
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Dongwoo Fine Chem Co Ltd
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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
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • 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
    • C09J133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • 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
    • 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
    • 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
    • G02F1/133305—Flexible substrates, e.g. plastics, organic film
    • 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 application 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 optical transparent 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, to provide an optical transparent pressure-sensitive adhesive (OCA) composition that can sufficiently satisfy the folding properties, moist heat resistance, heat resistance and adhesion required in the flexible display device The purpose.
  • OCA optical 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 a.
  • Photocurable (meth) acrylate copolymers Rubber-based (meth) acrylic monomers; And a photopolymerization initiator, comprising:
  • the photocurable (meth) acrylate copolymer is 95 to 99.9% by weight of a hydroxy group-containing acrylic copolymer and 0.1 to 5% by weight of isocyanato group-containing (meth) acrylate monomers based on the total weight of the structural units included in the copolymer It includes, wherein the hydroxyl group-containing acrylic copolymer and isocyanate group-containing (meth) acrylate monomer is a urethane bond,
  • the hydroxy group-containing acrylic copolymer includes 50 to 98% by weight of a C1-C12 linear or branched alkyl (meth) acrylate monomer and 2 to 50% by weight of a hydroxy group-containing polymerizable monomer based on the total weight of the monomers included in the copolymer. And, it provides an optically transparent adhesive composition characterized in that the weight average molecular weight is 200,000 to 1 million.
  • optical transparent pressure-sensitive adhesive film which is prepared by coating the optical transparent pressure-sensitive adhesive composition of the present invention on a transfer film.
  • It provides a flat panel display device comprising an adhesive layer formed of the optically transparent 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.
  • photocurable (meth) acrylate copolymer Rubber-based (meth) acrylic monomers
  • a photopolymerization initiator comprising:
  • the photocurable (meth) acrylate copolymer is 95 to 99.9% by weight of a hydroxy group-containing acrylic copolymer and 0.1 to 5% by weight of isocyanato group-containing (meth) acrylate monomers based on the total weight of the structural units included in the copolymer It includes, wherein the hydroxyl group-containing acrylic copolymer and isocyanate group-containing (meth) acrylate monomer is a urethane bond,
  • the hydroxy group-containing acrylic copolymer includes 50 to 98% by weight of a C1-C12 linear or branched alkyl (meth) acrylate monomer and 2 to 50% by weight of a hydroxy group-containing polymerizable monomer based on the total weight of the monomers included in the copolymer.
  • the present invention relates to an optically transparent adhesive composition, wherein the weight average molecular weight is 200,000 to 1 million.
  • the optically transparent adhesive composition of the present invention comprises a photocurable acrylate copolymer having a polarity and a rubber-based (meth) acryl monomer having a low Tg, and thus has excellent folding properties, moist heat resistance, and adhesion, and a photocurable acrylate copolymer. It is characterized by providing an optical transparent pressure-sensitive adhesive composition excellent in heat resistance and durability by optical crosslinking between the non-polar rubber-based (meth) acrylic monomer.
  • the "(meth) acrylate” means "acrylate” or "methacrylate”.
  • the photocurable (meth) acrylate copolymer copolymerizes a C1 to C12 straight or branched chain alkyl (meth) acrylate monomer and a hydroxy group-containing polymerizable monomer to which a thermosetting functional group (hydroxy group) is introduced at a branched chain or terminal.
  • the structure of the photocurable (meth) acrylate copolymer may be exemplified by the following Chemical Formula 1-1:
  • R1 is a C1-C12 straight or branched alkyl group
  • R2 is a C1-C10 straight or branched alkylene group
  • Each R 3 is independently hydrogen or methyl
  • o and p are each independently a natural number of 2 to 6
  • n each have a value formed according to the range of usage of the monomers described above.
  • the main chain is, for example, through a conventional polymerization method such as solution polymerization, photo polymerization, bulk polymerization, suspension polymerization or emulsion polymerization. Can be prepared.
  • the rubber-based (meth) acryl monomer for example, one or more selected from compounds represented by the following Chemical Formulas 1 to 2 may be used:
  • Each R 1 is independently hydrogen or a methyl group
  • Each R 2 is independently a C 2 to C 6 straight or branched alkylene group
  • Each R 3 is independently a group derived from a diisocyanate compound with an —N (H) —C (O) — group bonded to both sides thereof,
  • Each R 4 is independently a C 2 to C 12 straight or branched alkylene group
  • Rubber-based polymers include rubber monomers and mean polymers having a weight average molecular weight of 500 to 10,000 consisting only of carbon and hydrogen.
  • Examples of the rubber monomer may include butadiene, isobutene, isoprene, and the like.
  • the rubber polymer is not particularly limited as long as it is a polymer having rubber properties.
  • diisocyanate compound examples include HDI (Hexamethylene Diisocyanate), IPDI (Isophorone Diisocyanate), TDI (Toluene Diisocyanate), XDI (Xylylene Diisocyanate), and the like, but are not limited thereto.
  • the compound represented by Chemical Formulas 1 to 2 may be prepared by, for example, the following Scheme 1.
  • C 1 ⁇ C 12 linear or branched alkyl (meth) acrylate monomers contained in the polymerized form of the hydroxy group-containing acrylic copolymer is C 1 ⁇ C 12 of the glass transition temperature (Tg) of -70 ⁇ -50 °C
  • Tg glass transition temperature
  • Straight or branched chain alkyl acrylate monomers may be preferably used, more preferably C 4 to C 12 straight or branched chain alkyl acrylate monomers having a glass transition temperature (Tg) of -70 to -50 ° C may be used. have.
  • C 4 to C 12 straight or branched chain alkyl acrylate monomers having a glass transition temperature (Tg) of -70 to -50 ° C examples include n-butyl acrylate, t-butyl acrylate, sec-butyl acrylate, Pentyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate and the like, and these may be used alone or in combination of two or more thereof. Can be used. Of these, n-butyl acrylate and 2-ethylhexyl acrylate can be preferably used.
  • Tg glass transition temperature
  • hydroxy group-containing polymerizable monomer included in a polymerized form in the hydroxy group-containing acrylic copolymer a monomer containing a hydroxy group and one or more ethylenically unsaturated bonds may be preferably used.
  • a hydroxy group-containing acrylate monomer having a glass transition temperature (Tg) of -60 to -40 ° C may be used.
  • the glass transition temperature (Tg) is -60 ⁇
  • a hydroxy C 4 to C 6 straight or branched chain alkyl acrylate monomer may be preferably used.
  • hydroxy C 4 to C 6 linear or branched alkyl acrylate monomers examples include 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, and the like. It may be used alone or in combination of two or more. Of these, 4-hydroxybutyl acrylate can be preferably used.
  • the monomer having a glass transition temperature (Tg) of the hydroxyl group-containing acrylate monomer in the above is less than -60 °C, it is difficult to exist, when the temperature exceeds -40 °C may cause a problem that the folding properties at low temperatures.
  • C1 ⁇ C12 linear or branched alkyl (meth) acrylate monomer is included in 50 to 98% by weight, hydroxy group-containing polymerizable monomer may be included in 2 to 50% by weight.
  • the C1-C12 linear or branched alkyl (meth) acrylate monomer may be included in 50 to 89% by weight, and the hydroxyl group-containing polymerizable monomer may be included in 11 to 50% by weight.
  • the hydroxyl group-containing polymerizable monomer is included in less than 11% by weight, the hydroxy group which is a hydrophilic group is insufficient in the pressure-sensitive adhesive, the moisture is released from the pressure-sensitive adhesive layer and the moisture is discharged to the interface, resulting in poor adhesion due to damp-heat-resistant conditions. This may occur, when included in excess of 50% by weight, the pressure-sensitive adhesive absorbs excess moisture, expands the volume, and decreases cohesion, which may cause problems such as 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 converted value with respect to standard polystyrene measured by gel permeation chromatograph (GPC).
  • isocyanate (C1-C10) straight or branched chain alkyl (meth) acrylate may be used.
  • (C1-C10) straight or branched chain alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, Nonyl, decanyl, etc. are mentioned, Among these, ethyl, propyl, etc. can be used preferably.
  • the isocyanato group-containing (meth) acrylate monomer may be included in an amount of 0.1 parts by weight to 5.0% by weight based on the total weight of the structural units included in the photocurable (meth) acrylate copolymer.
  • the isocyanato group-containing (meth) acrylate-based monomer is included in less than 0.1% by weight, the cohesion and heat resistance of the pressure-sensitive adhesive composition may be lowered, and when it exceeds 5.0 wt%, the cohesive force of the pressure-sensitive adhesive becomes too strong. Folding characteristics may be degraded.
  • the polybutadiene / isoprene-based / isobutene (meth) acrylic monomer included in the optically transparent adhesive composition of the present invention is 10 to 40 parts by weight, more preferably 15 to 100 parts by weight of the photocurable (meth) acrylate copolymer. To 30 parts by weight.
  • the rubber-based (meth) acryl monomer is included in less than 10 parts by weight, it is difficult to secure the low-temperature folding characteristics, when containing more than 40 parts by weight it is difficult to secure the adhesive force may cause a problem that the heat resistance is lowered.
  • 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 may further contain a silane coupling agent.
  • 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 solids contained in the optically transparent adhesive composition.
  • the rubber-based (meth) acryl monomer may be present in a blended state with 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 a monomer having a low glass transition temperature and a rubber-based (meth) acryl monomer, while appropriately curing the curing system by radical polymerization and the curing system by a crosslinking agent and a thermosetting functional group (hydroxy group). Adopted together, it has the features to ensure moisture heat resistance, heat resistance and durability.
  • 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 was refluxed, and 60 parts by weight of n-butyl acrylate (n-BA) and 40 parts by weight of 4-hydroxybutyl acrylate (4-HBA) were added to a 1 L reactor equipped with a cooling device for easy temperature control. . 120 parts by weight of ethyl acetate (EAc) was added as a solvent, and then nitrogen gas was purged for 60 minutes to remove oxygen. Thereafter, the temperature was maintained at 70, 0.1 parts by weight of AIBN (azobisisobutyronitrile) as a reaction initiator was added thereto, and reacted for 12 hours to prepare an acrylic polymer (A1) having a weight average molecular weight of 450,000.
  • EAc ethyl acetate
  • AIBN azobisisobutyronitrile
  • n-butyl acrylate (n-BA) and 11 parts by weight of 4-hydroxybutyl acrylate (4-HBA) in Preparation Example 1 carried out the polymerization reaction in the same manner as the weight average An acrylic polymer (A2) having a molecular weight of 470,000 was prepared.
  • n-butyl acrylate (n-BA) 60 parts by weight of n-butyl acrylate (n-BA) and 40 parts by weight of 4-hydroxybutyl acrylate (4-HBA) in Preparation Example 1 80 parts by weight of n-butyl acrylate (n-BA) and 2- Except that 20 parts by weight of hydroxyethyl acrylate (2-HEA) was used, the polymerization was carried out in the same manner to prepare an acrylic polymer (A3) having a weight average molecular weight of 450,000.
  • a photocurable (meth) acrylate copolymer (B2) was prepared in the same manner as in Production Example 2-1, except that the acrylic polymer (A2) was used.
  • a photocurable (meth) acrylate copolymer (B3) was prepared in the same manner as in Production Example 2-1, except that the acrylic polymer (A3) was used.
  • a photocurable (meth) acrylate copolymer (B4) was prepared in the same manner as in Production Example 2-1, except that the acrylic polymer (A4) was used.
  • 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.
  • n 15 to 25.
  • the pressure-sensitive adhesive composition was prepared in the same manner as in Example 1, except that the rubber-based (meth) acrylic monomer represented by the following Formula 4 was used instead of the rubber-based (meth) acrylic monomer represented by the formula (3). .
  • n 15 to 25.
  • TEAI-1000 manufactured by "Japanese Soda” was used as the compound of Formula 3.
  • a polyfunctional crosslinking agent (Coronate L, manufactured by Japan NPU), 100 parts by weight of the photocurable acrylate copolymer (B3) prepared in Preparation Example 2-3, a photopolymerization initiator (hydroxycyclohexylphenyl ketone, irgacure 184 , 0.2 parts by weight of Swiss Chivas Specialty Chemical (manufactured) and 0.2 parts by weight of 3-glycidoxypropyltrimethoxyl silane (Shin-Etsu Co., Ltd. KBM-403) were prepared to prepare an adhesive composition.
  • a photopolymerization initiator hydroxycyclohexylphenyl ketone, irgacure 184
  • Swiss Chivas Specialty Chemical manufactured
  • 3-glycidoxypropyltrimethoxyl silane Shin-Etsu Co., Ltd. KBM-403
  • a polyfunctional crosslinking agent (Coronate L, manufactured by NPU, Japan), a photopolymerization initiator (hydroxycyclohexylphenyl ketone, irgacure 184 based on 100 parts by weight of the photocurable acrylate copolymer (B4) prepared in Preparation Example 2-4.
  • a photopolymerization initiator hydroxycyclohexylphenyl ketone, irgacure 184 based on 100 parts by weight of the photocurable acrylate copolymer (B4) prepared in Preparation Example 2-4.
  • 0.2 parts by weight of Swiss Chivas Specialty Chemical manufactured
  • 0.2 parts by weight of 3-glycidoxypropyltrimethoxyl silane Shin-Etsu Co., Ltd. KBM-403
  • Each of the optically transparent adhesive compositions prepared in Examples 1, 2, Comparative Example 1 and Comparative Example 2 was applied on a 50 ⁇ m-thick PET film coated with a silicone release agent such that the thickness after curing was 100 ⁇ m, and 100 After drying for 5 minutes in Example 3-1 (using the optically transparent adhesive composition of Example 1), Example 3-2 (using the optically transparent adhesive composition of Example 2), Comparative Example 3-1 (Comparative Example 1 Using an optically transparent adhesive composition) and the optically transparent adhesive film of Comparative Example 3-2 (using the optically transparent adhesive composition of the comparative example 2) were prepared.
  • a pressure-sensitive adhesive layer was applied to a PET film (100um PET manufactured by Mitsubishi Corporation) having a thickness of 100 ⁇ m. Laminating and irradiating the amount of light of 1000mJ / cm 2 using a UV lamp (fusion yarn) in the release film direction of Example 4-1, Example 4-2, Comparative Example 4-1 and Comparative Example 4-2 The laminated body in which the adhesive layer was formed was manufactured.
  • Example 4-1, Example 4-2, Comparative Example 4-1, and Comparative Example 4-2 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 the hard coating film for evaluation of flexibility prepared in Preparation Example 3 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 5-1, Example 5-2, Comparative Example 5-1 and Comparative Example The hard coat film / adhesive layer / PET (100 micrometers) laminated body for the flexibility evaluation of 5-2 was produced.
  • Example 5-1, Example 5-2, Comparative Example 5-1 and Comparative Example 5-2 prepared in Example 5 to the hard coating film / adhesive layer / PET laminate for the evaluation of the above evaluation method Therefore, the folding characteristics are shown in Table 1 below.
  • Example 5-1 The hard coating film / adhesive layer / PET laminate for evaluation of flexibility of Example 5-1, Example 5-2, Comparative Example 5-1 and Comparative Example 5-2 prepared in Example 5 at a temperature of 80 hours After standing for a while to observe the occurrence of bubbles or peeling to evaluate the heat resistance and the results are shown in Table 1 below.
  • Example 5-1, Example 5-2, Comparative Example 5-1 and Comparative Example 5-2 prepared in Example 5 to the hard coating film / adhesive layer / PET laminate for evaluation of the temperature of 60 and 90% After leaving for 1,000 hours under conditions 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 Examples 4-1, 4-2, Comparative Example 4-1, and Comparative Example 4-2 to a size of 25 mm ⁇ 100 mm. 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. 1 is shown.
  • Adhesive Forming Laminate Adhesive composition used Adhesion Example 4-1 Example 1 Preparation 14N Example 4-2 Example 2 Preparation 12N Comparative Example 4-1 Comparative Example 1 Preparation 23N Comparative Example 4-2 Comparative Example 2 Preparation 21N
  • the optically transparent pressure-sensitive adhesive composition of the embodiment of the present invention was confirmed that all excellent folding properties, heat-and-moisture 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.
  • adhesion it was confirmed that the rubber-based (meth) acryl monomer was included, rather than the comparative example.
  • 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.

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Abstract

La présente invention concerne une composition adhésive optiquement transparente, un film adhésif optiquement transparent la comprenant, ainsi qu'un dispositif d'affichage plat, cette composition comprenant un copolymère de (méth)acrylate, durcissable par rayonnement, un monomère (méth)acrylique à base de caoutchouc, et un initiateur de photopolymérisation, et étant caractérisée en ce que le copolymère de (méth)acrylate, durcissable par rayonnement, comprend, sur la base du poids total des éléments constitutifs contenus dans le copolymère, 95 à 99,9 % en poids d'un copolymère acrylique contenant un groupe hydroxyle et 0,1 à 5 % en poids d'un monomère à base de (méth)acrylate contenant un groupe isocyanate, en ce que le copolymère acrylique contenant un groupe hydroxyle et le monomère à base de (méth)acrylate contenant un groupe isocyanate forment une liaison uréthane, et en ce que le copolymère acrylique contenant un groupe hydroxyle comprend, sur la base du poids total des monomères contenus dans le copolymère, 50 à 98 % en poids d'un monomère de (méth)acrylate d'alkyle linéaire ou ramifié en C 1 -C 12 et 2 à 50 % en poids d'un monomère polymérisable contenant un groupe hydroxyle, et possède un poids moléculaire moyen en poids de 200.000 à 1.000.000.
PCT/KR2017/010207 2016-09-28 2017-09-18 Composition adhésive optiquement transparente, film adhésif optiquement transparent la comprenant, et dispositif d'affichage plat Ceased WO2018062744A1 (fr)

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WO2020177111A1 (fr) * 2019-03-07 2020-09-10 Dow Global Technologies Llc Composition adhésive exempte de formaldéhyde

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KR102847589B1 (ko) * 2020-06-30 2025-08-20 산진 옵토일렉트로닉스 (쑤저우) 컴퍼니 리미티드 아크릴계 점착제 조성물, 그 열 경화물을 포함하는 아크릴계 점착필름, 이를 구비한 편광판 및 자동차용 광학소자

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JP2012172094A (ja) * 2011-02-23 2012-09-10 Toyo Ink Sc Holdings Co Ltd 成形用樹脂組成物、シート、粘着シート、シートの製造方法及び成型体
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WO2020177111A1 (fr) * 2019-03-07 2020-09-10 Dow Global Technologies Llc Composition adhésive exempte de formaldéhyde
US11485886B2 (en) 2019-03-07 2022-11-01 Dow Global Technologies Llc Formaldehyde free adhesive composition

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