WO2015080346A1 - Composition adhésive, film adhésif formé à partir de cette dernière et dispositif d'affichage optique le comprenant - Google Patents

Composition adhésive, film adhésif formé à partir de cette dernière et dispositif d'affichage optique le comprenant Download PDF

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WO2015080346A1
WO2015080346A1 PCT/KR2014/001684 KR2014001684W WO2015080346A1 WO 2015080346 A1 WO2015080346 A1 WO 2015080346A1 KR 2014001684 W KR2014001684 W KR 2014001684W WO 2015080346 A1 WO2015080346 A1 WO 2015080346A1
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pressure
sensitive adhesive
film
weight
meth
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PCT/KR2014/001684
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English (en)
Korean (ko)
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조익환
김찬우
김기용
김지희
문성현
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제일모직 주식회사
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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
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • 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
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer

Definitions

  • the present invention relates to an adhesive composition, an adhesive film formed therefrom, and an optical display device including the same.
  • Optical clear adhesive (OCA) film is an adhesive film used for interlayer adhesion or the touch screen attachment of cellular phones for laminating components in optical displays.
  • the capacitive touchpad of the optical display device is attached to the window or the film by an adhesive film to detect a change in capacitance of the window or the film.
  • the adhesive film is laminated between the window glass and the TSP (touch screen panel) sensor glass.
  • OCA film transmits more than 97% of light and functions as glass, but it has the advantage of improving the screen clarity and adhesiveness compared to the conventional double-sided tape.
  • OCA film can be used not only for mobile phones but also for tablet PCs and TVs with medium and large display screens.
  • An object of the present invention is to provide a pressure-sensitive adhesive film that has good step filling capability, good durability reliability, and can be free of bubbles in the lamination process.
  • Another object of the present invention is to provide a pressure-sensitive adhesive composition capable of improving durability, cutting properties, embedding characteristics, and minimizing an increase in ITO resistance while satisfying a low dielectric constant (dielectric constant of 3.5 or less).
  • Still another object of the present invention is to provide a pressure-sensitive adhesive composition capable of simultaneously increasing cationic polymerization and radical polymerization to improve the crosslinked structure of the pressure-sensitive adhesive, thereby reducing the decrease in storage modulus even at high temperatures and increasing the reactivity of the silane.
  • Still another object of the present invention is to provide a pressure-sensitive adhesive composition in which end lift, bubble, warpage, etc. due to outgassing do not occur.
  • the pressure-sensitive adhesive composition of the present invention includes an alicyclic group-containing (meth) acrylic copolymer, an epoxy compound, an initiator, and a crosslinking agent, and the epoxy compound is about 5 to 35 to 100 parts by weight of the alicyclic group-containing (meth) acrylic copolymer. It may be included in parts by weight.
  • the pressure-sensitive adhesive film of the present invention may include or be formed of the pressure-sensitive adhesive composition.
  • the optical display device of the present invention may include the adhesive film.
  • the present invention provides a pressure-sensitive adhesive film that has good step filling ability, good durability, and no bubble generation in the lamination process.
  • the present invention provides a pressure-sensitive adhesive composition that can improve durability, cutting properties, embedding characteristics, and minimize an increase in ITO resistance while satisfying a low dielectric constant (dielectric constant of 3.5 or less).
  • the present invention improves the crosslinked structure of the pressure-sensitive adhesive by simultaneously causing cationic polymerization and radical polymerization, thereby providing a pressure-sensitive adhesive composition having a low rate of decrease in storage modulus even at a high temperature and increasing the reactivity of the silane.
  • the present invention provides a pressure-sensitive adhesive composition that does not cause end lifting, bubbles, warpage, etc. due to outgassing.
  • FIG. 1 is a cross-sectional view of an optical display device according to an exemplary embodiment of the present invention.
  • the pressure-sensitive adhesive composition of one embodiment of the present invention includes an alicyclic group-containing (meth) acrylic copolymer, an epoxy compound, an initiator, and a crosslinking agent, and the epoxy compound is about 5 to 100 parts by weight based on 100 parts by weight of the alicyclic group-containing (meth) acrylic copolymer. It may be included in 35 parts by weight. If the epoxy-based compound is included in less than 5 parts by weight bubbles may occur when the film is laminated, if more than 35 parts by weight may be poor durability and reliability. Specifically, the epoxy compound may be included in an amount of about 10 to 30 parts by weight based on 100 parts by weight of the alicyclic group-containing (meth) acrylic copolymer.
  • the alicyclic group-containing (meth) acrylic copolymer comprises a monomer mixture comprising an alkyl (meth) acrylate having an alkyl group of (a1) C7-C20, (a2) an alicyclic containing (meth) acrylate and a monomer containing a hydroxyl group (a3) It may be a copolymer of.
  • Alkyl (meth) acrylates having an alkyl group of C7-C20 may comprise a (meth) acrylic acid ester having an alkyl group of linear or branched unsubstituted C7-C20.
  • an alkyl (meth) acrylate having an alkyl group of C7-C10 may have the effect of increasing the initial adhesive force and the wettability to the substrate.
  • Alkyl (meth) acrylate having an alkyl group of C7-C20 is about 40 to 65% by weight of the monomer mixture or (meth) acrylic copolymer, specifically about 45 to 60% by weight, for example about 45,46,47 , 48,49,50,51,52,53,54,55,56,57,58,59,60,61,62,63,64,65% by weight, in the above range under heat and moisture resistance conditions No bubbles or lifting occurs, and may have excellent adhesion and excellent durability.
  • Alicyclic containing (meth) acrylate is C3-C20 alicyclic containing (meth) acrylate of C3-C10, for example.
  • there is isobornyl (meth) acrylate, bornyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, and the like but are not necessarily limited to these alone or It can be applied by mixing two or more kinds.
  • a cycloaliphatic containing (meth) acrylate of C10-C15 may have the effect of increasing durability.
  • the alicyclic containing (meth) acrylate is about 10 to 30% by weight of the monomer mixture or (meth) acrylic copolymer, specifically about 15 to 25% by weight, for example about 15,16,17,18,19, 20, 21, 22, 23, 24, 25% by weight may be included. In the above range, heat / durability may be increased and adhesion may be increased.
  • the hydroxyl group-containing monomer is 2-hydroxyethyl (meth) acrylate which has a hydroxyl group, 4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate , 6-hydroxyhexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, chloro-2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, etc.
  • a (meth) acrylate having an alkyl group of C 1 -C 5 having a hydroxyl group there may be an effect of improving adhesion and increasing durability.
  • the hydroxyl group-containing monomer is about 10 to 40% by weight of the monomer mixture or (meth) acrylic copolymer, specifically about 15 to 25% by weight, for example about 15,16,17,18,19,20,21,22 It can be included in the range, 23, 24, 25% by weight and has a synergistic effect in the above range, excellent durability and does not generate bubbles in the humidity conditions.
  • the alicyclic group-containing (meth) acrylic copolymer may further lower the curing shrinkage rate by further including a heteroalicyclic group.
  • the (meth) acrylic copolymer having an alicyclic group and a heteroalicyclic group includes (a1) alkyl (meth) acrylate having an alkyl group of C7-C20, (a2) cycloaliphatic containing (meth) acrylate, (a3) It may be a copolymer of a monomer mixture containing a hydroxyl group-containing monomer and (a4) heteroalicyclic (meth) acrylate.
  • the heterocycloaliphatic containing (meth) acrylate may include a (meth) acrylic monomer having a monocyclic heteroalicyclic group having C 4 -C 6 having nitrogen, oxygen or sulfur.
  • a (meth) acrylic monomer having a monocyclic heteroalicyclic group having C 4 -C 6 having nitrogen, oxygen or sulfur may contain (meth) acryloyl morpholine and the like.
  • the heterocycloaliphatic containing (meth) acrylate is about 0.1 to 10% by weight, specifically about 1 to 5% by weight, for example about 1,2,3,4,5% by weight in the monomer mixture or the (meth) acrylic copolymer It may be included as, the curing shrinkage in the above range may be low and good reliability.
  • the alicyclic group-containing (meth) acrylic copolymer may further include a carboxylic acid group, thereby improving durability and increasing adhesion to the substrate, thereby improving durability.
  • the (meth) acrylic copolymer having an alicyclic group and a carboxylic acid group includes an alkyl (meth) acrylate having an alkyl group of (a1) C7-C20, (a2) an alicyclic containing (meth) acrylate, and a (a3) hydroxyl group. It may be a copolymer of a monomer mixture comprising a monomer and a monomer containing a (a5) carboxylic acid group.
  • the carboxylic acid group-containing monomer may be (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, and these may be applied alone or in combination of two or more kinds.
  • the monomer containing a carboxylic acid group may be included in 0-3% by weight of the monomer mixture or the (meth) acrylic copolymer.
  • the adhesion strength increase, the durability improvement effect, and the surface corrosion inhibition effect of the transparent electrode film may be expressed.
  • the (meth) acrylic copolymer may be polymerized together with the addition of other copolymerizable monomers in addition to the above-mentioned monomers.
  • it may be a (meth) acrylate having a pyrrolidoneyl group, a (meth) acrylate having a phosphate group, or the like.
  • the (meth) acrylic copolymer may have a glass transition temperature (Tg) of -35 ° C to -10 ° C, preferably -30 ° C to -13 ° C. It is excellent in workability in the said range, and excellent in durability and adhesive force.
  • Tg glass transition temperature
  • the (meth) acrylic copolymer may have a viscosity of 25 ° C of 1600 to 8000 cPs, preferably 1500 to 5000 cPs, more preferably 1500 to 3000 cPs.
  • the (meth) acrylic copolymer has a weight average molecular weight of 1 million to 3 million g / mol, preferably 1.5 million to 2.5 million g / mol, for example, 1.5 million, 1.6 million, 1.7 million, 1.8 million, and 1.9 million , 2 million, 2.1 million, 2.2 million, 2.3 million, 2.4 million and 2.5 million g / mol.
  • the adhesive composition may be cured to have durability even after being left for a long time under high temperature and high humidity conditions in manufacturing the adhesive film, and may have excellent adhesiveness.
  • the (meth) acrylic copolymer may be prepared by a conventional method. Specifically, it may be prepared by mixing the monomer mixture and the radical radical initiator and solution polymerization, suspension polymerization, photopolymerization, bulk polymerization, or emulsion polymerization. Specifically, solution polymerization may be performed at 50 to 100 ° C. by adding an optical radical initiator to the monomer mixture, and the optical radical initiator may be an acetophenone-based radical including 2,2-dimethoxy-2-phenylacetophenone and the like. A photoinitiator can be used.
  • the photo radical initiator may be applied at about 0.01-3 parts by weight, preferably about 0.01-1 part by weight based on 100 parts by weight of the monomer mixture for preparing the (meth) acrylic copolymer. Low light leakage and excellent durability can be obtained in the above range.
  • the (meth) acrylic copolymer may be prepared by completely polymerizing the monomer mixture, or the polymerization may be completed after partial polymerization of the monomer mixture and further addition of an initiator and a crosslinking agent. Partial polymerization polymerizes the monomer mixture to polymerize until a 25 ° C. viscosity becomes a viscous liquid on the order of about 1,000-50,000 cPs, preferably about 1,000 to 6,000 cps, more preferably about 1,500 to 3,000 cps. The coating is easy in the viscosity range, there is an excellent workability.
  • the epoxy compound has two or more epoxy groups and is cured by a photo cationic initiator, which may be included in an adhesive film to increase durability.
  • the epoxy compound is an epoxy compound having an alicyclic group, and may include two or more, for example, two to four alicyclic groups having one or more epoxy groups.
  • the effect of the adhesive film of this invention can be heightened further.
  • the epoxy compound may be glycidyl such as tetramethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A diglycidyl ether, or a mixture thereof.
  • Epoxy esters such as ethers, bisphenol A-diepoxy-acrylic acid adducts, and mixtures thereof, monomers and oligomers of alicyclic epoxy, cyclo aliphatic epoxy, mixtures thereof, and the like, but are not limited thereto.
  • the alicyclic epoxy system may be, but is not limited to, the following Chemical Formula 1a to Chemical Formula 1e:
  • the epoxy compound may be included in an amount of about 5 to 35 parts by weight, specifically about 10 to 30 parts by weight, based on 100 parts by weight of the (meth) acrylic copolymer, and no bubbles are generated when the film is laminated in the above range, and the reliability may be high. have.
  • the initiator may comprise one or more of an optical radical initiator, a photo cationic initiator, and may preferably comprise a mixture of an optical radical initiator and a photo cationic initiator.
  • the photo radical initiator cures the (meth) acrylic copolymer
  • the photo cationic initiator cures the epoxy compound. Therefore, the cationic polymerization and the radical polymerization are simultaneously performed to improve the crosslinked structure of the pressure-sensitive adhesive, whereby the decrease in storage modulus is small even at high temperatures, and the reactivity of the silane can be increased.
  • the photo radical initiator may be included in an amount of about 0.001 to 5 parts by weight, preferably about 0.01 to 3 parts by weight, and more preferably about 0.01 to 1 part by weight, based on 100 parts by weight of the monomer mixture or (meth) acrylic copolymer. In the above range (meth) acrylate-based compound may be sufficiently cured and improve the reactivity of the photocationic polymerization initiator.
  • the photo cationic initiator may use a conventional photo cationic initiator capable of carrying out a photocurable reaction.
  • Examples include, but are not limited to, onium salts such as aromatic diazonium salts, aromatic iodine aluminum salts, aromatic sulfonium salts, iron-arene complexes, mixtures thereof, and the like.
  • diaryl such as diphenyl iodonium, 4-methoxy diphenyl iodonium, bis (4-methylphenyl) iodonium, bis (4-tert- butylphenyl) iodonium, bis (dodecylphenyl) iodonium, etc.
  • Triarylsulfonium such as iodonium, triphenylsulfonium, diphenyl-4-thiophenoxyphenylsulfonium, bis [4- (diphenylsulfonio) -phenyl] sulphide, bis [4- (di (4- (2-hydroxyethyl) phenyl) sulfonio) -phenyl] sulfide, ⁇ 5-2,4- (cyclopentadienyl) [1,2,3,4,5,6- ⁇ ]- (Methylethyl) -benzene] -iron (1+) etc. are mentioned.
  • anionic examples include borate (BF 4 -) tetrafluoroborate, phosphate (PF 6 -) hexafluoropropane, antimonate hexafluorophosphate (SbF 6 -), are Senate hexafluorophosphate (AsF 6 -), hexamethylene Chloro antimonate (SbCl 6 ⁇ ) and the like.
  • the photo cationic initiator may be included in an amount of about 0.01 to 3 parts by weight, preferably about 0.5 to 1.5 parts by weight, based on 100 parts by weight of the epoxy compound, and the polymerization of the epoxy compound may be sufficiently performed in the above range and the remaining amount of the initiator remains. Can be prevented.
  • the crosslinking agent may be preferably a polyfunctional (meth) acrylate capable of curing with an active energy ray.
  • the polyfunctional (meth) acrylates include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentylglycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, neopentylglycol adipate di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, Ethylene oxide modified di (meth) acrylate, di (meth) acryloxy ethyl isocyanurate, allylated cyclohexyl di (meth) acrylate, tricyclodecanedimethanol (meth) acrylate, dimethylol dicyclopentan
  • Isocyanate monomers and trimethylolpropane tri (meth) acrylate 6-functional acrylates such as reactants, etc., but are not limited thereto.They may be used alone or in combination of two or more thereof.
  • the polyfunctional (meth) of polyhydric alcohol having 2-20 hydroxyl groups ) Acrylates Preferably, the polyfunctional (meth) of polyhydric alcohol having 2-20 hydroxyl groups ) Acrylates.
  • the crosslinking agent may be included in an amount of about 0.01 to 1 part by weight, specifically about 0.05 to 1 part by weight, specifically about 0.1 to 1 part by weight, based on 100 parts by weight of the (meth) acrylic copolymer, and the effects of the pressure-sensitive adhesive film of the present invention in the above range. May appear.
  • the pressure-sensitive adhesive composition is about 5 to 35 parts by weight of an epoxy compound, about 0.01 to 3 parts by weight of an optical radical initiator, about 0.01 to 1 part by weight of a crosslinking agent, and epoxy based on 100 parts by weight of the (meth) acrylic copolymer on a solids basis. It may include about 0.01 to 3 parts by weight of the photo cationic initiator based on 100 parts by weight of the system compound, there may be no problems such as step filling, durability, no bubbles, outgas generation.
  • the pressure-sensitive adhesive composition may optionally contain a silane coupling agent (silane compound), a curing accelerator, an ionic liquid, a lithium salt, an inorganic filler, a softener, an antioxidant, an antioxidant, a stabilizer, a tackifying resin, a modified resin (polyol resin, Phenolic resins, acrylic resins, polyester resins, polyolefin resins, epoxy resins, epoxidized polybutadiene resins, etc.), leveling agents, antifoaming agents, plasticizers, dyes, pigments (such as colored pigments, extender pigments), treatment agents, sunscreen agents, Conventional additives such as fluorescent brighteners, dispersants, thermal stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, lubricants and solvents may be further included.
  • the silane coupling agent may further include an epoxy group-containing silane coupling agent, but is not limited thereto.
  • the epoxy group-containing silane coupling agent may improve the adhesion and adhesion stability between the pressure-sensitive adhesive and the glass substrate to improve heat resistance and moisture resistance, and to improve adhesion reliability even when the adhesive is left for a long time under high temperature and / or high humidity conditions. It can be.
  • radical polymerization and cationic polymerization may occur at the same time, so that the reactivity of the silane (silane-based coupling agent) may be increased.
  • the epoxy group-containing silane coupling agent may be included in an amount of about 0.1 to 30 parts by weight based on 100 parts by weight of the (meth) acrylic copolymer.
  • an oligomeric siloxane represented by the following formula (1) may be used as the epoxy group-containing silane coupling agent.
  • R 1 , R 2 and R 3 are each independently an alkyl group having 1 to 5 carbon atoms
  • R 4 and R 5 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms
  • n is an integer of 3-25
  • m is an integer of 1-10.
  • R 1 , R 2 and R 3 may be methyl, ethyl or propyl groups.
  • the oligomeric siloxane may have a viscosity of 25 ° C. of about 15 to 40 cps, preferably 20 to 35 cps. In the above range, the coating property may be good.
  • the oligomeric siloxane may have a refractive index of about 1.4 to 1.5, and may be suitably applied to the optical member in the above range.
  • the oligomeric siloxane may have an alkoxy group content in the molecule of about 30 to 60 weight percent, preferably about 35 to 55 weight percent. It has excellent durability, adhesion and reworkability in the above range.
  • the oligomeric siloxane may have an epoxy equivalent weight of about 250 to 450 g / eq, preferably about 300 to 400 g / eq. It has excellent adhesion and re-peelability in the above range.
  • the content of the epoxy group-containing silane coupling agent is about 0.01 to 5 parts by weight, preferably about 0.1 to 1 part by weight based on 100 parts by weight of the alicyclic group-containing (meth) acrylic copolymer. In the above range, substrate adhesion and durability, long-term storage characteristics and the like are good.
  • the pressure-sensitive adhesive composition may be used for adhesion of an optical film including a polarizing film and a transparent electrode film.
  • the pressure-sensitive adhesive film of an embodiment of the present invention may be formed of the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive film may include the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition may be prepared by coating and drying a release film (eg, polyester, polyethylene terephthalate film).
  • the pressure-sensitive adhesive film is a state in which the curing of the pressure-sensitive adhesive composition is not completely, and may include the (meth) acrylic copolymer, an epoxy compound, an initiator, a crosslinking agent and the like.
  • the pressure-sensitive adhesive film may include a cured product of the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition may be UV cured after coating on a release film (eg, polyester, polyethylene terephthalate film). UV curing may be performed at conditions of about 0.1-40 mW / cm 2 , about 1-5 minutes. Preferably, it can be cured in a state where oxygen is blocked.
  • the coating thickness is not particularly limited, and may be about 50 ⁇ m to 2 mm, preferably about 50 ⁇ m to 1.5 mm, and the final adhesive film may be used in the optical display device.
  • the thickness (thickness except a release film) of an adhesive film is not specifically limited, It may be about 10 micrometers-2 mm, Preferably it is about 100 micrometers-1.5 mm, It can be used for an optical display apparatus in the said range.
  • the adhesive film may be used as an optical clear adhesive (OCA) film or a touch panel film.
  • OCA optical clear adhesive
  • the pressure-sensitive adhesive film was laminated at a thickness of 1 mm or more, and the dielectric constant measured under the conditions of 400 kHz using an LCR meter (manufacturer: agilent product name: E4980A) was about 3.5 or less, preferably about 3.5 to 3.0, In the above range, the reliability and touch sensitivity are excellent.
  • the pressure-sensitive adhesive film has a resistance change ratio ( ⁇ R) represented by Equation 1 below about 0 to less than 5%, preferably greater than about 0 to less than 4%, more preferably about 0 to 3%, and optical display within the above range. It can be used in the device.
  • ⁇ R resistance change ratio
  • P 2 is the resistance after leaving the adhesive film at 60 °C / 90% relative humidity for 240 hours
  • P 1 is the initial resistance of the adhesive film.
  • the adhesive film may have a storage modulus of about 1 ⁇ 10 5 to 5 ⁇ 10 7 dyne / cm 2 at 30 ° C., preferably about 1 ⁇ 10 6 to 5 ⁇ 10 7 dyne / cm 2 , and a storage modulus at 80 ° C.
  • the cross-linked structure of the adhesive film is excellent in the above range, it is possible to prevent the generation of micro bubbles due to outgassing, such as PC Sheet, PC Film.
  • the storage modulus was measured using an ARES (Advanced Reometric Expansion System) (manufacturer: TA) by performing a frequency sweep test (frequency: 1 Hz reference) at a temperature of 30 °C and 80 °C.
  • ARES Advanced Reometric Expansion System
  • the adhesive film may have a peel strength of about 1,950 gf / 25mm to 3,000 gf / 25mm measured according to the physical property evaluation method of the following Examples.
  • An optical display device may include an adhesive film according to an embodiment of the present invention.
  • the optical display device is an optical film;
  • an adhesive film attached to one or both surfaces of the optical film, and the adhesive film may include the adhesive film of one embodiment of the present invention.
  • Optical films include touch panels, windows, polarizing plates, color filters, retardation films, elliptical polarizing films, reflective films, antireflection films, compensation films, brightness enhancement films, alignment films, light diffusion films, glass scattering prevention films, surface protection films, Transparent electrode films such as plastic LCD substrates, indium tin oxide (ITO), fluorinated tin oxide (FTO), aluminum dopped zinc oxide (AZO), carbon nanotube (CNT), Ag nanowire, and graphene Can be mentioned.
  • ITO indium tin oxide
  • FTO fluorinated tin oxide
  • AZO aluminum dopped zinc oxide
  • CNT carbon nanotube
  • Ag nanowire Ag nanowire
  • graphene graphene
  • FIG. 1 is a cross-sectional view of an organic light emitting diode display according to an exemplary embodiment of the present invention.
  • the organic light emitting diode display 100 includes a substrate 10, an encapsulation layer 20 encapsulating the OLED element 15, an OLED element 15 formed on the substrate 10, and encapsulation.
  • a transparent conductor including a second transparent conductive layer 30 formed below, a polarizing plate 45 formed on the first transparent conductive layer 40, and a second adhesive film 50 formed on the polarizing plate 45. May include a window 55 formed on an upper portion of the second adhesive film 50, and at least one of the first adhesive film 25 and the second adhesive film 50 may be an adhesive film of an embodiment of the present invention. Can be.
  • the substrate 10 may be a substrate (eg, a TFT substrate) commonly used in an organic light emitting diode display, and specifically, may be a glass substrate, a polyimide of a plastic material, an epoxy, an acrylic, a silicon substrate, or the like. It may be a substrate having flexibility.
  • the device for OLED 15 is commonly used in an organic light emitting display device, and although not shown in FIG. 1, includes an organic light emitting film formed between a first electrode, a second electrode, and a first electrode and a second electrode.
  • the organic light emitting layer may be formed by sequentially stacking a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, but is not limited thereto.
  • the encapsulation layer 20 may be formed of an inorganic, organic or inorganic / organic mixture by protecting the OLED element 15 from external moisture or oxygen.
  • the transparent conductor is conductive to generate an electrical signal with respect to the stimulus from the outside, and includes a substrate 35, a first transparent conductive layer 40 and a second transparent conductive layer 30 formed on both surfaces of the substrate 35. can do.
  • the substrate 35 may be an optically transparent film (eg, a polyester including polycarbonate, polyethylene terephthalate, etc.) or a glass plate, and the first transparent conductive layer 40 and the second transparent conductive layer 30 may be the same or different.
  • a transparent conductive film having conductivity it may be an indium tin oxide (ITO) film, or a film containing a metal nanowire, although not shown in Figure 1, the first transparent conductive layer 40, and / Alternatively, the second transparent conductive layer 30 may be patterned.
  • ITO indium tin oxide
  • the first adhesive film 25 adheres the encapsulation layer 20 and the second transparent conductive layer 30, and the second adhesive film 50 adheres the first transparent conductive layer 40 and the window 55.
  • the polarizer 45 may serve as an anti-reflection in the organic light emitting display, and may include a polarizer, a protective film and / or a retardation film formed on the polarizer, although not shown in FIG.
  • the window 55 serves as a display, and may be formed of a glass or plastic material, or may be formed of a flexible material.
  • the touch panel may be attached to a window or an optical film by using the adhesive film on the touch pad.
  • it may be applied as a pressure-sensitive adhesive film to a conventional polarizing film as in the prior art.
  • Silane coupling agent Siloxane epoxy silane (X-41-1059A: product made by Shintsu), (KBM-403, Shinetsu)
  • EHA ethylhexyl acrylate
  • IBOA isobornyl acrylate
  • HSA hydroxy ethyl acrylate
  • 2,2-dimethoxy-2-phenyl as an optical radical initiator
  • a mixture was prepared by mixing 0.04 parts by weight of acetophenone (product name: Irgacure TM 651, manufactured by Ciba Japan) in a glass container.
  • the resulting pressure-sensitive adhesive composition was coated on a 50 ⁇ m thick polyester film (release film) to form an adhesive film with a thickness of 175 ⁇ m.
  • a 50 ⁇ m thick polyester film (release film) was covered on the adhesive film, and then a low pressure lamp (sylvania Lamp BL360) was used on both sides of the release film for about 3 minutes.
  • a high-pressure metal halide lamp manufactured by litzen, device name: UV curing machine
  • UV ultraviolet-ray
  • Example 2 The same method as Example 1 except that an epoxy group-containing siloxane coupling agent (product name: X-41-1059A, manufacturer: Shinetsu) was used instead of the epoxy group-containing silane coupling agent (product name: KBM-403, manufacturer: Shinetsu).
  • An adhesive composition and an adhesive film were prepared.
  • the mixture was mixed well in a glass vessel, the dissolved oxygen was replaced with nitrogen gas, and the mixture was partially polymerized by irradiating ultraviolet light using a low pressure lamp for a few minutes to obtain a viscous liquid having a viscosity of about 1,500 cP.
  • (E) the remaining amount of (C1), (D), (B), (C2) was added to the content described in Table 1 (unit: parts by weight) and then mixed to prepare a pressure-sensitive adhesive composition. .
  • the resulting composition was coated on a 50 ⁇ m thick polyester film (release film, polyethylene terephthalate film) to prepare a transparent adhesive sheet 1 including a pressure sensitive adhesive film 1 having a thickness of 175 ⁇ m.
  • the OCA film was laminated on the ITO film, and 2000mj was irradiated on the metal halide lamp.
  • Example 1 Except that the cationic photoinitiator CPI210S and epoxy compound CY179 was not used in Example 1, an adhesive composition and an adhesive film were prepared in the same manner as in Example 1.
  • Bubble generation at lamination The adhesive film 2 was laminated on the ITO film, autoclave, and then bubble generation was visually evaluated. When no bubbles occurred at all, it was evaluated as X, and when one or more bubbles were generated, it was evaluated as ⁇ .
  • Hardening shrinkage (%) The hardening shrinkage was calculated by measuring the specific gravity of the liquid composition before photocuring and the specific gravity of the solid after curing with DME-220E (Shinko, Japan). 5 g of the composition was coated in a thickness of about 10 ⁇ m ⁇ 2 ⁇ m and then UV cured (100 mW / cm 2 X 10 seconds) with a metal halide lamp to prepare a film (thickness: 8 to 12 ⁇ m, width of 1.5 to 2.5 cm, length of 1.5 to 2.5 cm). It was performed by.
  • the cure shrinkage rate can be calculated according to the following formula (1).
  • Cure Shrinkage (%) [(Solid specific gravity after curing-specific gravity of liquid composition before curing)] / Specific gravity of liquid composition before curing x 100
  • Resistance change rate ( ⁇ R,%) Adhesion film 2 was attached to ITO PET, and electrodes were formed using silver paste on both sides to prepare a sample. Thereafter, the initial resistance (P 1 ) was measured for the prepared sample, and the sample was left for 60 hours at 60 ° C./90% relative humidity, and then the resistance (P 2 ) was measured. The resistance was measured using a Checkman portable resistance, voltage, and current meter (manufacturer: Taekwang Electronics). Then, the resistance change rate ( ⁇ R,%) was measured by substituting the resistance value measured under each condition as follows.
  • Peeling strength (gf / 25 mm): Using a 50 ⁇ m thick PET film (backing film), the prepared adhesive film is attached to the ITO film, 30 minutes after the attachment of the Texture Analyzer : TA.XT_Plus, manufacturer: Stable Micro System), the peel force was measured at 300mm / min speed.
  • Example 3 to Example 5 attached to ITO and irradiated 2000mj to the metal halide lamp and after 30 minutes was measured the peel force in the same manner.
  • Dielectric constant It measured on the conditions of 400 kHz using the LCR meter (manufacturer: agilent product name: E4980A). The pressure-sensitive adhesive was prepared by measuring 1mm.
  • the pressure-sensitive adhesive film of the present invention has no problem of bubble generation when laminated, and the durability was good.
  • bubbles or lifting occurred due to the outgassing of the PC which was not surface-treated under the reliability conditions.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention porte sur : une composition adhésive contenant un copolymère à base (méth)acrylique contenant un groupe alicyclique, un composé à base d'époxyde, un initiateur et un agent de réticulation, la teneur du composé à base d'époxyde étant approximativement 5-35 parties en poids pour 100 parties en poids du copolymère à base (méth)acrylique contenant un groupe alicyclique ; un film adhésif la comprenant ; et un dispositif d'affichage optique le comprenant.
PCT/KR2014/001684 2013-11-28 2014-02-28 Composition adhésive, film adhésif formé à partir de cette dernière et dispositif d'affichage optique le comprenant WO2015080346A1 (fr)

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CN106229037A (zh) * 2016-08-10 2016-12-14 深圳市国华光电科技有限公司 一种柔性复合透明导电膜及其制备方法
CN106405718A (zh) * 2016-12-07 2017-02-15 西北大学 一种基于石墨烯栅带结构的电控太赫兹偏振片及使用方法
CN111362589A (zh) * 2020-04-29 2020-07-03 东莞南玻太阳能玻璃有限公司 一种耐候双层高增透镀膜玻璃及其制备方法
CN114672267A (zh) * 2018-10-10 2022-06-28 三星Sdi株式会社 粘着膜、包含其的光学构件以及包含其的光学显示器
US11502272B2 (en) 2017-10-23 2022-11-15 Lg Chem, Ltd. Optical film having antistatic layers, optical film preparation method and organic light-emitting electronic device preparation method
CN115537124A (zh) * 2022-09-28 2022-12-30 新纶电子材料(常州)有限公司 可后固化的光学粘合剂、oca光学胶及其制备方法

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KR101943694B1 (ko) * 2015-12-11 2019-01-29 삼성에스디아이 주식회사 편광판용 점착 필름, 이를 포함하는 편광판 및 이를 포함하는 광학표시장치
KR102467421B1 (ko) * 2015-12-23 2022-11-16 삼성디스플레이 주식회사 표시 장치 및 이의 제조 방법
KR101941194B1 (ko) * 2016-12-09 2019-04-12 한국생산기술연구원 디스플레이용 점접착 소재 및 이의 제조방법
KR102294140B1 (ko) * 2018-07-19 2021-08-27 산진 옵토일렉트로닉스 (쑤저우) 컴퍼니 리미티드 편광판, 이를 위한 편광판용 접착제 조성물 및 이를 포함하는 화상표시장치
KR102486600B1 (ko) * 2020-02-20 2023-01-09 삼성에스디아이 주식회사 점착 필름, 이를 포함하는 비산 방지 필름 및 이를 포함하는 광학표시장치

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CN106229037A (zh) * 2016-08-10 2016-12-14 深圳市国华光电科技有限公司 一种柔性复合透明导电膜及其制备方法
CN106405718A (zh) * 2016-12-07 2017-02-15 西北大学 一种基于石墨烯栅带结构的电控太赫兹偏振片及使用方法
US11502272B2 (en) 2017-10-23 2022-11-15 Lg Chem, Ltd. Optical film having antistatic layers, optical film preparation method and organic light-emitting electronic device preparation method
CN114672267A (zh) * 2018-10-10 2022-06-28 三星Sdi株式会社 粘着膜、包含其的光学构件以及包含其的光学显示器
CN114672267B (zh) * 2018-10-10 2024-03-12 三星Sdi株式会社 粘着膜、包含其的光学构件以及包含其的光学显示器
CN111362589A (zh) * 2020-04-29 2020-07-03 东莞南玻太阳能玻璃有限公司 一种耐候双层高增透镀膜玻璃及其制备方法
CN115537124A (zh) * 2022-09-28 2022-12-30 新纶电子材料(常州)有限公司 可后固化的光学粘合剂、oca光学胶及其制备方法
CN115537124B (zh) * 2022-09-28 2024-04-05 新纶电子材料(常州)有限公司 可后固化的光学粘合剂、oca光学胶及其制备方法

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