WO2018056743A1 - Composition adhésive - Google Patents

Composition adhésive Download PDF

Info

Publication number
WO2018056743A1
WO2018056743A1 PCT/KR2017/010455 KR2017010455W WO2018056743A1 WO 2018056743 A1 WO2018056743 A1 WO 2018056743A1 KR 2017010455 W KR2017010455 W KR 2017010455W WO 2018056743 A1 WO2018056743 A1 WO 2018056743A1
Authority
WO
WIPO (PCT)
Prior art keywords
block
group
weight
parts
adhesive composition
Prior art date
Application number
PCT/KR2017/010455
Other languages
English (en)
Korean (ko)
Inventor
박근호
손상하
윤성수
지한나
권수지
윤정애
김수정
주창환
김경오
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020170121896A external-priority patent/KR102024256B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201780049565.0A priority Critical patent/CN109563390B/zh
Priority to EP17853457.4A priority patent/EP3489320B1/fr
Priority to US16/333,842 priority patent/US10968372B2/en
Priority to JP2019503728A priority patent/JP6710316B2/ja
Publication of WO2018056743A1 publication Critical patent/WO2018056743A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • 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
    • 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
    • G02F1/13363—Birefringent elements, e.g. for optical compensation

Definitions

  • the present application relates to an adhesive composition, an optical laminate, a polarizing plate, and a display device.
  • a liquid crystal display device (hereinafter referred to as "LCD device”) usually includes a liquid crystal panel and an optical film containing a liquid crystal component injected between two transparent substrates.
  • an optical film there exists a polarizing film, retardation film, a brightness improving film, etc.
  • the adhesive for optical films can be used in order to laminate
  • acrylic polymer rubber, urethane resin, silicone resin, or ethylene vinyl acetate (EVA) resin may be used.
  • EVA ethylene vinyl acetate
  • an acrylic copolymer having excellent characteristics is widely used. It is used.
  • One object of the present application is to provide a pressure-sensitive adhesive composition for forming a pressure-sensitive adhesive layer that can improve durability and warpage characteristics even at high temperatures of 100 ° C. or higher and / or 65 ° C. and 95% high humidity.
  • Another object of the present application is to provide an optical laminate, a polarizing plate, and a display device having excellent durability and warpage characteristics even at high temperature and / or high humidity conditions.
  • the present application relates to an adhesive composition.
  • the adhesive composition may include a block copolymer.
  • block copolymer in the present application may refer to a copolymer including blocks of different polymerized monomers.
  • the block copolymer may include a first block having a glass transition temperature of 50 ° C. or more and a second block having a glass transition temperature of ⁇ 10 ° C. or less.
  • the "glass transition temperature of the block" constituting the block copolymer may mean a glass transition temperature calculated according to the method described in the following Examples.
  • the glass transition temperature of the first block may be 50 ° C or higher, 60 ° C or higher, 70 ° C or higher, 75 ° C or higher, or 80 ° C or higher.
  • the upper limit of the first block glass transition temperature is not particularly limited, but may be, for example, about 150 ° C. or less, 140 ° C. or less, 130 ° C. or less, 120 ° C. or less, or about 110 ° C. or less.
  • the glass transition temperature of the second block may be -10 ° C or less, -20 ° C or less, -30 ° C or less, or -35 ° C or less.
  • the lower limit of the second block glass transition temperature is not particularly limited, but may be, for example, -80 ° C or higher, -70 ° C or higher, or -60 ° C or higher.
  • the copolymer including both blocks satisfying the glass transition temperature range may form a fine phase separation structure in the pressure-sensitive adhesive. Since the block copolymer exhibits appropriate cohesion and stress relaxation property with temperature change, it is possible to form an adhesive that maintains excellent physical properties required for an optical film such as interfacial adhesion, durability reliability, light leakage prevention property, and reworkability. Can be.
  • the block copolymer of the present application including the two blocks may be a diblock copolymer or a triblock copolymer.
  • a diblock copolymer may be advantageous.
  • the number average molecular weight (Mn) of the first block of the block copolymer may range from 10,000 to 250,000.
  • the number average molecular weight of the first block may be, for example, the number average molecular weight of the polymer prepared by polymerizing only the monomers forming the first block.
  • the number average molecular weight referred to in the present application can be measured, for example, using the GPC (Gel Permeation Chromatograph) according to the method given in the Examples.
  • the number average molecular weight (Mn) of the first block is, for example, the lower limit is 10,000 or more, 15,000 or more, 20,000 or more, 25,000 or more, 30,000 or more, 35,000 or more, 40,000 or more, 45,000 or more, or 50,000 or more. Can be. And the upper limit may be 250,000 or less, 200,000 or less, 180,000 or less, 150,000 or less, 130,000 or less, or 100,000 or less.
  • the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the first block may range from 1.0 to 3.0. have. More specifically, the lower limit of the PDI value of the first block may be 1.0 or more, 1.1 or more, 1.2 or more, 1.3 or more, 1.4 or more or 1.5 or more, and an upper limit thereof may be 3.0 or less, 2.8 or less, 2.6 or less, 2.4 or less or 2.2 or less. Can be.
  • the block copolymer may have a number average molecular weight (Mn) of 500,000 or less. More specifically, the number average molecular weight (Mn) of the block copolymer is, for example, the lower limit of 100,000 or more, 110,000 or more, 120,000 or more, 130,000 or more, 140,000 or more, 150,000 or more, 160,000 or more, 170,000 or more, 180,000 or more, At least 190,000, at least 200,000, at least 210,000, at least 220,000, at least 230,000, at least 240,000, or at least 250,000. And the upper limit may be 500,000 or less, 450,000 or less, 400,000 or less, or 350,000 or less.
  • the pressure-sensitive adhesive when adjusting the molecular weight characteristics of the block copolymer, it is possible to form the pressure-sensitive adhesive to maintain excellent properties required in the optical film, such as interfacial adhesion, durability reliability, light leakage prevention properties and reworkability.
  • the block copolymer may be a crosslinkable copolymer having a crosslinkable functional group. More specifically, the block copolymer may include a polymer unit derived from a compound capable of providing a crosslinkable functional group in the first block and / or the second block.
  • crosslinkable functional group a hydroxyl group, a carboxyl group, an epoxy group, an isocyanate group, or a nitrogen containing functional group is mentioned, for example. If such a crosslinkable functional group can be provided to a 1st block and / or a 2nd block, the kind of specific compound will not be restrict
  • hydroxy group containing monomers such as hydroxy group alkyl (meth) acrylate or hydroxy alkylene glycol (meth) acrylate, etc .; (Meth) acrylic acid, 2- (meth) acryloyloxy acetic acid, 3- (meth) acryloyloxy propyl acid, 4- (meth) acryloyloxy butyl acid, acrylic acid duplex, itaconic acid, maleic acid and Carboxyl group-containing monomers, such as maleic anhydride, or nitrogen-containing monomers, such as (meth) acrylamide, N-vinyl pyrrolidone, or N-vinyl caprolactam, etc. can be used individually or in mixture of 2 or more types.
  • the first block having a relatively high glass transition temperature may form a hard segment having relatively rigid properties in the block copolymer.
  • the first block may be present in a glass state at room temperature, and may serve to impart cohesion to the pressure-sensitive adhesive including the block copolymer.
  • the kind or content of the monomer for forming the first block is not particularly limited.
  • the first block may include a polymerized unit derived from (meth) acrylic acid ester.
  • the "polymerization unit” may mean a state in which the predetermined monomer is polymerized and contained in a main chain or side chain of a resin, a polymer, or a polymerization reaction product formed by polymerization of a predetermined monomer which is one impression.
  • alkyl (meth) acrylate As the (meth) acrylic acid ester used for forming the first block, for example, alkyl (meth) acrylate can be used. In consideration of cohesion, glass transition temperature and tack control, alkyl (meth) acrylates having alkyl groups of 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms may be used. have.
  • Examples of such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth ) Acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-octyl (meth) acrylate, iso Bornyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and lauryl (meth) acrylate, and the like, and the glass transition temperature of one or more of the above is ensured. It can be selected to use.
  • the first block may include a crosslinkable functional group.
  • the first block may include a polymerized unit derived from 80 to 99.9 parts by weight of the (meth) acrylic acid ester, and a polymerized unit derived from 0.1 to 20 parts by weight of the compound capable of providing a crosslinkable functional group.
  • the first block may include a polymerized unit derived from 80 to 99 parts by weight of the (meth) acrylic acid ester, and a polymerized unit derived from 1 to 20 parts by weight of the compound capable of providing a crosslinkable functional group.
  • "parts by weight” may mean a weight ratio between components.
  • the first block may include 80 parts by weight to 99.9 parts by weight of polymerized units of the (meth) acrylic acid ester monomer and 0.1 parts by weight to 20 parts by weight of polymerized units capable of providing a crosslinkable functional group.
  • the ratio (A: B) based on the weight of the (meth) acrylic acid ester monomer (A) and the compound (B) capable of providing a crosslinkable functional group forming the polymerized unit of the first block is 80 to 99.9: It may mean the case of 0.1 to 20.
  • the first block which is a hard segment, includes a crosslinkable functional group
  • the first block including a crosslinkable functional group can provide excellent durability reliability and stress relaxation property to the pressure-sensitive adhesive even under high temperature conditions of 100 ° C. or more.
  • the pressure-sensitive adhesive including the first block can maintain excellent warp prevention and light leakage prevention characteristics of the optical film.
  • the second block having a relatively low glass transition temperature may form a soft segment having relatively soft physical properties in the block copolymer.
  • the second block may have molecular flowability at room temperature, and may play a role of providing stress relaxation property to the pressure-sensitive adhesive including the block copolymer.
  • the kind or content of the monomer for forming the second block is not particularly limited.
  • the second block may include a polymerized unit derived from (meth) acrylic acid ester.
  • (meth) acrylic acid ester used to form the second block for example, as in the first block, an alkyl (meth) acrylate can be used.
  • the second block may include a crosslinkable functional group.
  • the crosslinkable functional group in the second block, it is possible to form a pressure-sensitive adhesive having excellent cohesive force and stress relaxation property according to temperature change, and excellent physical properties such as interface adhesion, durability reliability, light leakage prevention property and reworkability. Can be.
  • the type of crosslinkable functional group may be the same as described above.
  • each of the first block and the second block may include a crosslinkable functional group.
  • each of the first block and the second block may have a polymer unit derived from the following Chemical Formula 1 compound capable of providing a crosslinkable functional group.
  • Q is hydrogen or an alkyl group
  • a and B are each independently an alkylene group or an alkylidene group
  • n is an integer within the range of 0 to 10.
  • the carbon number of B in each [—O—B—] unit may be the same or different.
  • alkyl group refers to a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms.
  • the alkyl group may be optionally substituted with one or more substituents.
  • Examples of the alkyl group in Formula 1 may include a linear or branched alkyl group having 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms.
  • Q when Q is an alkyl group in Formula 1, Q may be an alkyl group having 1 to 4 carbon atoms.
  • alkylene group or alkylidene group is a straight, branched chain or ring having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms. It may mean an alkylene group or an alkylidene group on the phase, which may be optionally substituted by one or more substituents.
  • a and B may be each independently a linear alkylene group having 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms.
  • n in Formula 1 may be, for example, 0 to 7, 0 to 5, 0 to 3 or 0 to 2.
  • 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) ) Acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate or 2-hydroxypropylene glycol (meth) acrylate, and the like can be exemplified, but the compounds listed above It is not particularly limited.
  • the carbon number of A and B contained in the polymerized unit derived from Formula 1 included in each block may be different from each other.
  • the sum of the number of carbon atoms of the alkylene groups of A and B contained in the polymerization unit derived from the formula (1) included in the second block (hereinafter referred to as the number of side chain carbons in the second block) is derived from the formula (1) included in the first block.
  • the carbon number of A and B is 4 to 10 in the polymer unit derived from Formula 1 included in the second block
  • the carbon number of A and B in the polymer unit derived from Formula 1 included in the first block is 4 or less, for example 1-3.
  • the inventors of the present application when the sum of the carbon number of the alkylene group or alkylidene group of A and B contained in the polymerized unit derived from the formula (1) included in the second block as described above is larger than that of the first block, soft It has been found that the reactivity of the second block, which is a block, is faster and that the crosslinked structure formed by the soft block can contribute to the cohesion of the pressure-sensitive adhesive. In addition, the crosslinking of the first block which is formed somewhat later for the same reason may provide excellent interfacial adhesion.
  • the remaining hardener or crosslinker forms a crosslinked structure on the interface of the optical member that is the adhesive together with the crosslinkable functional group of the hard block having a slow reactivity, thereby forming the adhesive and the optical member that is the adherend.
  • Excellent interfacial adhesion can be provided.
  • the crosslinking properties of this first block allow the pressure sensitive adhesive to have some good stress relaxation while maintaining durability under high temperature and high humidity conditions.
  • the second block may include a crosslinkable functional group and an aromatic group at the same time.
  • the second block may include the crosslinkable functional group described above or a polymerized unit derived from Chemical Formula 1, and may include a polymerized unit derived from a compound capable of providing an aromatic group at the same time.
  • the compound capable of providing an aromatic group in the second block may be, for example, a compound including a vinyl group and an aromatic group.
  • the kind of the compound may be, for example, styrene or a compound corresponding to Chemical Formula 2, but is not particularly limited thereto.
  • the compound including the vinyl group and the aromatic group may be represented by the following formula (2).
  • R1 is hydrogen or an alkyl group
  • R2 is an alkylene group or an alkylidene group
  • m is an integer between 0 and 5
  • X is a single bond, an oxygen atom or a sulfur atom
  • Ar is an aryl group.
  • a single bond in relation to X means a case where R 2 and Ar are directly connected as a separate atom does not exist in a portion connected by X.
  • an aryl group means a monovalent moiety derived from a compound or a derivative thereof containing a structure in which benzene or two or more benzenes are condensed or bonded.
  • the aryl group may be, for example, an aryl group having 6 to 22 carbon atoms, 6 to 16 carbon atoms, or 6 to 13 carbon atoms, and for example, a phenyl group, phenylethyl group, phenylpropyl group, benzyl group, benzyloxy group, and phenoxy group.
  • Tolyl group xylyl group (xylyl group), phenylthio group, naphthyl group or naphthyloxy group and the like.
  • m may be, for example, 0 to 4, 0 to 3, 0 to 2, or may be 0 or 1.
  • the aromatic group when the aromatic group is included in the second block, the aromatic group may not be included in the first block but may be included only in the second block. Including the aromatic group in the second block can form an adhesive in which the aromatic group is properly oriented in a constant direction and excellent in light leakage preventing characteristics. In particular, when the pressure-sensitive adhesive is exposed to high temperature or high temperature and high humidity conditions, optical compensation may be performed by the aromatic group, thereby reducing light leakage.
  • the second block may provide a polymerized unit derived from 20 to 98 parts by weight of the (meth) acrylic acid ester, a polymerized unit derived from 1 to 40 parts by weight of a compound capable of providing a crosslinkable functional group, and an aromatic group. It may include a polymer unit derived from 1 to 40 parts by weight of the compound.
  • the second block may provide a polymerized unit derived from 60 to 98 parts by weight of the (meth) acrylic acid ester, a polymerized unit derived from 1 to 35 parts by weight of a compound capable of providing a crosslinkable functional group, and an aromatic group. It may include a polymerized unit derived from 1 to 35 parts by weight of the compound.
  • the second block may include an alkyl (meth) acrylate having an alkyl group having 1 to 3 carbon atoms as a polymerized unit derived from (meth) acrylic acid ester.
  • the second block may include polymerized units derived from 50 parts by weight or less or 45 parts by weight or less of alkyl (meth) acrylate having an alkyl group having 1 to 3 carbon atoms.
  • the lower limit of the alkyl (meth) acrylate content having an alkyl group having 1 to 3 carbon atoms is not particularly limited, but may be, for example, 5 parts by weight or more.
  • the second block includes an alkyl (meth) acrylate monomer having an alkyl group having 1 to 3 carbon atoms in the above range, it may further contribute to improving the durability and the bending property of the pressure-sensitive adhesive. Specifically, durability may be improved when the degree of chemical crosslinking is high, but when the degree is too high, there may be a problem in which the bending property deteriorates. In view of this, since the alkyl (meth) acrylate having an alkyl group having 1 to 3 carbon atoms is more easily cross-linked than an alkyl (meth) acrylate having 4 or more carbon atoms in the alkyl group, chemical crosslinking is possible.
  • the second block may further include a polymerized unit derived from a compound capable of providing a crosslinkable functional group and a polymerized unit derived from a compound capable of providing an aromatic group.
  • the second block may provide a polymerized unit derived from an alkyl (meth) acrylate having an alkyl group having 1 to 3 carbon atoms, a polymerized unit derived from an alkyl (meth) acrylate having an alkyl group having 4 or more carbon atoms, and a crosslinkable functional group.
  • the polymerized unit derived from the compound capable of providing the polymerized unit derived from the compound and the aromatic group may be further included.
  • the content between the monomers or compounds used to form the second block may be adjusted within the same range as in the content range between the polymerized units derived from the monomers or compounds described above with respect to the second block composition.
  • the block polymer of the present application may include 5 parts by weight to 50 parts by weight of the first block of the configuration and 50 parts by weight to 95 parts by weight of the second block of the configuration. In another example, the block polymer of the present application may include 10 parts by weight to 30 parts by weight of the first block of the configuration and 70 parts by weight to 90 parts by weight of the second block of the configuration.
  • the first block and / or the second block may further include any comonomer as necessary, and the monomer may be included in each block as a polymer unit.
  • the comonomer include (meth) acrylonitrile, (meth) acrylamide, N-methyl (meth) acrylamide, N-butoxy methyl (meth) acrylamide, N-vinyl pyrrolidone or N-vinyl capro Nitrogen-containing monomers such as lactams and the like; Alkoxy alkylene glycol (meth) acrylic acid ester, alkoxy dialkylene glycol (meth) acrylic acid ester, alkoxy trialkylene glycol (meth) acrylic acid ester, alkoxy tetraalkylene glycol (meth) acrylic acid ester, alkoxy polyethylene glycol (meth) acrylic acid Esters, phenoxy alkylene glycol (meth) acrylic acid esters, phenoxy dialkylene glycol (meth) acrylic acid esters, phenoxy trialkylene
  • Such comonomers may be included in the polymer by selecting one or more kinds thereof as necessary.
  • Polymerized units derived from such comonomers may be included, for example, in a proportion of 20 parts by weight or less, or 0.1 to 15 parts by weight in each block.
  • the method for producing the block copolymer is not particularly limited, and known methods can be used.
  • the block polymer may be polymerized by LRP (Living Radical Polymerization).
  • LRP Living Radical Polymerization
  • an anionic polymerization method or an organic alkali metal compound synthesized in the presence of an inorganic acid such as an alkali metal or a salt of an alkaline earth metal is polymerized using an organic rare earth metal complex as a polymerization initiator or an organic alkali metal compound as a polymerization initiator.
  • Anion polymerization method synthesized in the presence of an organoaluminum compound using an initiator, atomic transfer radical polymerization method (ATRP) using an atomic transfer radical polymerization agent as a polymerization control agent, and an atomic transfer radical polymerization agent as a polymerization control agent are used.
  • ARRP Electron Transfer
  • ATRP Atomic Radical Polymerization
  • ICR Initiators for continuous activator regeneration
  • RAFT Reversible Addition of Inorganic Reductants
  • RAFT Reversible addition-cleavage chain transfer using cleavage chain transfer agents And the polymerization
  • RAFT organic Tel method of using the tellurium compound as an initiator of the like
  • a suitable method is selected from among the method may be that the block copolymer produced.
  • the adhesive composition of the present application may include one or more crosslinking agents capable of reacting with the crosslinkable functional groups of the block copolymer to form a chemical crosslinked structure.
  • the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent or a metal chelate crosslinking agent.
  • an isocyanate crosslinking agent when the crosslinkable functional group is a hydroxy group, an isocyanate crosslinking agent may be used. Specifically, an isocyanate crosslinking agent having at least two functional groups capable of reacting with the crosslinkable functional group of the block copolymer may be used.
  • an isocyanate crosslinking agent for example, diisocyanate compounds, such as tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoborone diisocyanate, tetramethyl xylene diisocyanate, or naphthalene diisocyanate; Or a compound obtained by reacting the diisocyanate compound with a polyol. Trimethylol propane may be used as the polyol.
  • the adhesive composition may include a crosslinking agent in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the block copolymer. More specifically, the lower limit of the crosslinking agent content may be 0.05 part by weight or more or 0.10 part by weight or more, and an upper limit thereof may be 10 parts by weight or 5 parts by weight or less.
  • the degree of crosslinking of the block copolymer may be appropriately controlled, and through this, the gel fraction, cohesion, cohesion, and durability of the pressure-sensitive adhesive may be excellently maintained, but the content is appropriately adjusted in consideration of the bending property. It is desirable to.
  • the adhesive composition of the present application may include a plasticizer.
  • the plasticizer may impart stress relaxation to the pressure-sensitive adhesive.
  • the plasticizer of the present application may include polyalkylene glycol, to impart excellent adhesion, re-peelability, light leakage relief and durability to the pressure-sensitive adhesive.
  • the antistatic performance of the pressure-sensitive adhesive can be further improved.
  • the polyalkylene glycol can chelate the cationic group of the antistatic agent, inhibit the ion association of the antistatic agent and improve the uniformity of the distribution of the antistatic agent, so that even when the adhesive is exposed to high temperature and / or high humidity conditions for a long time This is because the change over time of the antistatic performance can be suppressed.
  • the plasticizer may be represented by the following formula (3).
  • Z may be an alkylene group having 2 to 8 carbon atoms.
  • Z may be an alkylene group having 2 to 4 carbon atoms.
  • L may be a number between 2 and 50.
  • L can be 2 to 40, 2 to 30, 2 to 20, or 2 to 10.
  • Y1 and Y2 are each independently hydrogen, a hydroxyl group, an alkyl group, an alkoxy group, (C ⁇ O) R 3 or (C ⁇ O) R 4, and at least one of Y 1 and Y 2 is a functional group including a carbonyl group .
  • Y 1, which is a functional group including a carbonyl group may be (C ⁇ O) R 3
  • Y 2, which is a functional group including a carbonyl group may be O (C ⁇ O) R 4.
  • R3 and R4 may each independently be an alkyl group, an alkenyl group, or an aryl group.
  • the alkyl group may mean an alkyl group having 2 to 20 carbon atoms, 2 to 18 carbon atoms or 2 to 16 carbon atoms
  • an alkenyl group may be an alkenyl group having 2 to 20 carbon atoms, 2 to 18 carbon atoms, or 2 to 16 carbon atoms
  • the aryl group may be an aryl group having 6 to 25 carbon atoms, 6 to 20 carbon atoms, 6 to 15 carbon atoms, or 6 to 12 carbon atoms.
  • an alkyl group, alkylene group or alkenyl group may refer to an alkyl group which is linear, branched or cyclic and may be substituted by one or more substituents as necessary.
  • the range of the alkyl group may include a haloalkyl group to be described later.
  • an aryl group may mean a benzene, a compound comprising a benzene structure, or a monovalent moiety derived from any one of the foregoing.
  • Specific examples of the aryl group may include, but are not limited to, a phenyl group, benzyl group, biphenyl group or naphthalenyl group.
  • the category of the aryl group may include a functional group commonly referred to as an aryl group as well as a so-called aralkyl group or an arylalkyl group.
  • an epoxy group such as halogen, haloalkyl group, glycidyl group, glycidylalkyl group, glycidoxyalkyl group or alicyclic epoxy group such as chlorine or fluorine, Acryloyl group, methacryloyl group, isocyanate group, thiol group, alkyl group, alkoxy group or aryl group and the like can be exemplified, but is not limited thereto.
  • One or more plasticizers may be used among the plasticizers represented by Formula 3 above.
  • the plasticizer may be polyethylene glycol bis (2-ethylhexanoate), polypropylene glycol bis (2-ethylhexanoate), polyethylene glycol monooleate, polypropylene glycol monooleate, polyethylene glycol diol Eight, polypropylene glycol dioleate, polyethylene glycol dibenzoate, polypropylene glycol dibenzoate, polyethylene glycol monolaurate, polypropylene glycol monolaurate, polyethylene glycol dilaurate, polypropylene glycol dilaurate, polyethylene glycol Distearate, polypropylene glycol distearate, polyethylene glycol monostearate or polypropylene glycol monostearate may be used.
  • the plasticizer may have a number average molecular weight (Mn) of about 100 to about 1,000.
  • the lower limit of the number average molecular weight of the plasticizer may be, for example, 200 or more, 300 or more or 400 or more.
  • the upper limit of the number average molecular weight of the plasticizer may be, for example, 900 or less, 800 or less, or 700 or less.
  • the plasticizer may be included in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the block copolymer.
  • the lower limit of the amount of the plasticizer may be, for example, 0.1 part by weight or more, 1 part by weight or more, or 1.5 parts by weight or more.
  • the upper limit of the content of the plasticizer may be, for example, 7 parts by weight or less, 5 parts by weight or less, or 3 parts by weight or less.
  • the pressure-sensitive adhesive composition of the present application may further include an antistatic agent.
  • an antistatic agent for example, an ionic compound may be used.
  • the ionic compound include organic salts and inorganic salts.
  • a metal salt containing a metal ion as a cation can be used.
  • Metal salts may include, for example, alkali metal cations or alkaline earth metal cations.
  • As the cation lithium ions (Li + ), sodium ions (Na + ), potassium ions (K + ), rubidium ions (Rb + ), cesium ions (Cs + ), beryllium ions (Be 2 + ), magnesium ions ( Mg 2+), there is a calcium ion (Ca + 2), strontium ion (a kind or two kinds or more, such as Sr 2 +) and barium ion (Ba + 2) can be exemplified.
  • an ionic compound containing an organic cation can be used.
  • an onium cation can be exemplified.
  • the term onium cation means an ion that is positively charged, including a structure in which at least a portion of the charge is localized in atoms such as nitrogen (N), phosphorus (P), and / or sulfur (S). can do.
  • the onium cation may be a cyclic or acyclic compound, and in the cyclic case, may be an aromatic or non-aromatic compound.
  • the onium cation may further include other atoms such as oxygen or carbon atoms in addition to the nitrogen, phosphorus and / or sulfur.
  • the onium cation may be optionally substituted with a substituent such as halogen, alkyl group or aryl group.
  • a substituent such as halogen, alkyl group or aryl group.
  • the acyclic compound may include one or four or more substituents, and the substituents may be cyclic or acyclic substituents, aromatic or non-aromatic substituents.
  • anion contained in the ionic compound such as inorganic salts or organic salts are PF 6 -, AsF -, NO2 -, fluoride (F -), chloride (Cl -), bromide (Br -), iodide (I -), perchlorate (ClO 4 -), hydroxide (OH -), carbonate (CO 3 2-), nitrate (NO 3 -), methanesulfonate trifluoroacetate carbonate (CF 3 SO 3 -), sulfonate (SO 4 -), phosphate (PF 6 -) hexafluoropropane, methyl benzene sulfonate (CH 3 (C 6 H 4 ) SO 3 -), p- toluenesulfonate (CH 3 C 6 H 4 SO 3 -) , Tetraborate (B 4 O 7 2- ), carboxybenzenesulfonate (COOH (C 6 H 4 ) SO,
  • an anion or bisfluorosulfonylimide represented by the following general formula (4) may be used as the anion.
  • D is a nitrogen atom or a carbon atom
  • G is a carbon atom or a sulfur atom
  • R f is a perfluoroalkyl group
  • m is 1 or 2
  • n is 2 or 3.
  • Anions or bis (fluorosulfonyl) imides of formula (4) exhibit high electronegativity due to perfluoroalkyl group (R f ) or fluorine group, and also include unique resonance structures, forming weak bonds with cations At the same time, it has hydrophobicity. Therefore, while an ionic compound shows the outstanding compatibility with other components of compositions, such as a polymer, it can provide high antistatic property even with a small amount.
  • R f in Formula 4 may be a perfluoroalkyl group having 1 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, in which case the perfluoroalkyl group is linear, branched, or cyclic. It may have a structure.
  • the anion of the formula (4) may be a sulfonyl metide, sulfonyl imide, carbonyl metide or carbonyl imide anion, and specifically, tristrifluoromethanesulfonylmethide and bistrifluoromethanesulfide Ponylimide, bisperfluorobutanesulfonylimide, bispentafluoroethanesulfonylimide, tristrifluoromethanecarbonylmide, bisperfluorobutanecarbonylimide or bispentafluoroethanecarbonyl It may be a kind of imide or the like or a mixture of two or more thereof.
  • the ratio of the antistatic agent can be adjusted in consideration of the desired antistatic properties and the like.
  • the composition based on 100 parts by weight of the block copolymer, 0.1 to 20 parts by weight, 0.1 to 15 parts by weight, 0.1 to 10 parts by weight, 0.1 to 5 parts by weight, 0.1 It may include parts by weight to 3 parts by weight, or 0.5 parts by weight to 3 parts by weight of the antistatic agent.
  • the pressure-sensitive adhesive composition may further include a silane coupling agent.
  • a silane coupling agent the silane coupling agent which has a beta-cyano group or an acetoacetyl group can be used, for example.
  • Such a silane coupling agent can impart excellent adhesiveness and adhesion stability to the pressure-sensitive adhesive and can impart durability reliability at high temperature and high humidity conditions.
  • silane coupling agent which has a beta-cyano group or an acetoacetyl group
  • the compound represented by following formula (5) or 6 can be used, for example.
  • R5 is a beta-cyanoacetyl group or a beta-cyanoacetylalkyl group
  • R7 is an acetoacetyl group or an acetoacetylalkyl group
  • R6 is an alkoxy group
  • n is 1 to 3 It is a number.
  • the alkoxy group may be an alkoxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, and the alkoxy group is linear, branched or cyclic. It may be a phase.
  • n in Chemical Formulas 5 and 6 may be, for example, 1 to 3, 1 to 2, or 1.
  • Examples of the compound represented by Formulas 5 and 6 include acetoacetylpropyl trimethoxy silane, acetoacetylpropyl triethoxy silane, beta-cyanoacetylpropyl trimethoxy silane or beta-cyanoacetylpropyl tri Oxy silane and the like, but are not limited thereto.
  • the pressure-sensitive adhesive composition may include 0.01 to 5 parts by weight, or 0.01 to 1 part by weight of a silane coupling agent based on 100 parts by weight of the block copolymer, and may effectively impart the desired physical properties to the pressure-sensitive adhesive within this range.
  • the adhesive composition may further contain a tackifier as necessary.
  • a tackifier for example, a hydrocarbon resin or a hydrogenated substance thereof, a rosin resin or a hydrogenated substance thereof, a rosin ester resin or a hydrogenated substance thereof, a terpene resin or a hydrogenated substance thereof, a terpene phenol resin or a hydrogenated substance thereof, a polymerized rosin resin or One kind or a mixture of two or more kinds such as a polymerized rosin ester resin may be used, but is not limited thereto.
  • the tackifier may be included in the adhesive composition in an amount of 100 parts by weight or less based on 100 parts by weight of the block copolymer.
  • the adhesive composition may further include additives such as an epoxy resin, a curing agent, an ultraviolet stabilizer, an antioxidant, a colorant, a reinforcing agent, a filler, an antifoaming agent, a surfactant, or a plasticizer.
  • additives such as an epoxy resin, a curing agent, an ultraviolet stabilizer, an antioxidant, a colorant, a reinforcing agent, a filler, an antifoaming agent, a surfactant, or a plasticizer.
  • additives such as an epoxy resin, a curing agent, an ultraviolet stabilizer, an antioxidant, a colorant, a reinforcing agent, a filler, an antifoaming agent, a surfactant, or a plasticizer.
  • the specific kind or content of the additive is not particularly limited.
  • the pressure-sensitive adhesive composition may be a pressure-sensitive adhesive composition for a protective film.
  • the protective film can be used, for example, in applications for protecting the surface of various optical films.
  • the adhesive composition may be an adhesive composition for an optical film.
  • the pressure-sensitive adhesive composition for an optical film may be formed by laminating 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 the optical film or a laminate thereof such as a liquid crystal panel. It can be used for attachment to adherends.
  • the pressure-sensitive adhesive composition may be a pressure-sensitive adhesive composition used for attaching the polarizing film to the liquid crystal panel as the pressure-sensitive adhesive composition for a polarizing plate.
  • the present application is directed to a pressure-sensitive adhesive optical laminate.
  • Exemplary optical laminates include optical films; And an adhesive layer present on at least one surface of the optical film.
  • the pressure-sensitive adhesive layer may be, for example, a pressure-sensitive adhesive layer for attaching the optical film to a liquid crystal panel or the like of another LCD device or another optical film.
  • the pressure-sensitive adhesive layer may include the pressure-sensitive adhesive composition of the present application described above.
  • the pressure-sensitive adhesive composition may be included in the pressure-sensitive adhesive layer in a state of implementing a crosslinked structure.
  • the optical film a polarizing plate, a polarizer, a retardation film, a brightness enhancing film, or the like, or a laminate in which two or more kinds are stacked may be exemplified.
  • the terms polarizer and polarizer refer to objects that are distinguished from each other. That is, the polarizer refers to the film, sheet or device itself exhibiting a polarizing function, and the polarizing plate means an optical element including other elements together with the polarizer.
  • a polarizer protective film or a retardation layer may be exemplified, but is not limited thereto.
  • the present application also relates to a pressure-sensitive adhesive polarizing plate.
  • the polarizing plate may have, for example, a structure in which the optical film is a polarizer in the adhesive optical laminate.
  • the kind of polarizer contained in a polarizing plate is not specifically limited,
  • the polarizer is a functional film capable of extracting only light vibrating in one direction from incident light while vibrating in various directions.
  • a polarizer may be, for example, a form in which a dichroic dye is adsorbed in a polyvinyl alcohol-based resin film.
  • Polyvinyl alcohol-type resin which comprises a polarizer can be obtained by gelatinizing polyvinylacetate-type resin, for example.
  • the polyvinylacetate resin which can be used may include not only a homopolymer of vinyl acetate but also a copolymer of vinyl acetate and other monomers copolymerizable with the above.
  • Examples of the monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and a mixture of one or two or more kinds of acrylamides having an ammonium group, but are not limited thereto. no.
  • the degree of gelation of the polyvinyl alcohol-based resin is usually 85 mol% to 100 mol%, preferably 98 mol% or more.
  • the polyvinyl alcohol-based resin may be further modified, for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used.
  • the degree of polymerization of the polyvinyl alcohol-based resin may be about 1,000 to 10,000 or about 1,500 to 5,000.
  • the polarizer is a step of stretching (ex. Uniaxial stretching) the polyvinyl alcohol resin film as described above, a step of dyeing the polyvinyl alcohol resin film with a dichroic dye, adsorbing the dichroic dye, and a dichroic dye adsorbed.
  • the polyvinyl alcohol-based resin film can be produced through a process of treating with a boric acid aqueous solution and a process of washing with water after treating with a boric acid aqueous solution.
  • the dichroic dye iodine or a dichroic organic dye may be used.
  • the polarizing plate may further include a protective film attached to one side or both sides of the polarizer, in which case, the pressure-sensitive adhesive layer may be formed on one side or both sides of the protective film. In one example, the pressure-sensitive adhesive layer may be formed on the side opposite to the polarizer of the protective film.
  • the type of protective film is not particularly limited, and includes, for example, a cellulose film such as triacetyl cellulose (TAC); Polyester film such as polycarbonate film or PET (poly (ethylene terephthalet)); Polyether sulfone-based film; Alternatively, a film having a laminated structure of one layer or two or more layers, such as a polyethylene film, a polypropylene film or a polyolefin-based film produced using a resin having a cyclo or norbornene structure, an ethylene-propylene copolymer, or the like can be used. In consideration of securing moisture barrier properties, PET-based and polyolefin-based films may be used, and in consideration of securing durability, acrylic films may be used.
  • TAC triacetyl cellulose
  • Polyester film such as polycarbonate film or PET (poly (ethylene terephthalet)); Polyether sulfone-based film
  • the polarizer may also further include one or more functional layers selected from the group consisting of protective layers, reflective layers, antiglare layers, retardation plates, wide viewing angle compensation films, and brightness enhancement films.
  • a method of forming an adhesive layer on the polarizing plate or the optical film is not particularly limited.
  • the adhesive composition may be directly coated on a polarizing plate and cured to form a crosslinked structure, or a release film may be formed. After coating and curing the pressure-sensitive adhesive composition on the release-treated surface to form a crosslinked structure, a method of transferring it may be used.
  • the method of coating the pressure-sensitive adhesive composition is not particularly limited, and for example, a method of applying the pressure-sensitive adhesive composition by conventional means such as a bar coater may be used.
  • the crosslinking agent included in the adhesive composition is preferably controlled from the crosslinking reaction of the functional group from the viewpoint of performing a uniform coating process, whereby the crosslinking agent is used to form a crosslinked structure in the curing and aging process after the coating operation. It can form to improve the cohesive force of the pressure-sensitive adhesive, improve the adhesive properties and cuttability (cuttability).
  • the coating process is also preferably carried out after sufficiently removing the bubble-inducing components such as volatile components or reaction residues in the adhesive composition, so that the crosslinking density or molecular weight of the adhesive is too low, the elastic modulus is lowered, and at a high temperature. Bubbles existing between the glass plate and the adhesive layer may be increased to prevent a problem of forming scatterers therein.
  • the method of curing the pressure-sensitive adhesive composition to implement a crosslinked structure is not particularly limited.
  • the crosslinking reaction between the block copolymer included in the coating layer and the multifunctional crosslinking agent may be induced, and the like may be performed by maintaining the coating layer at an appropriate temperature.
  • the present application also relates to a display device.
  • the display device is an LCD
  • the device may include a liquid crystal panel and the polarizing plate or the optical laminate attached to one side or both sides of the liquid crystal panel.
  • the polarizing plate or the optical laminate may be attached to the liquid crystal panel by the pressure-sensitive adhesive described above.
  • the liquid crystal panel may include, for example, a first substrate, a pixel electrode, a first alignment layer, a liquid crystal layer, a second alignment layer, a common electrode, and a second substrate sequentially formed.
  • the first substrate and the second substrate may be a glass substrate.
  • the polarizing plate or the optical laminate may be attached to the glass substrate through the pressure-sensitive adhesive layer described above.
  • the device may further comprise a light source on the side opposite to the viewer side of the liquid crystal panel.
  • an active driving circuit including a TFT (Thin Film Transistor), wiring, and the like may be formed on the first substrate on the light source side as a driving element electrically connected to the transparent pixel electrode.
  • the pixel electrode may include, for example, indium tin oxide (ITO) or the like, and may function as an electrode for each pixel.
  • the first or second alignment layer may include, for example, a material such as polyimide, but is not limited thereto.
  • the liquid crystal panel in the apparatus may be, for example, a passive matrix panel such as twisted nematic (TN) type, super twisted nematic (STN) type, ferroelectic (F) type or polymer dispersed (PD) type; Active matrix panels, such as two-terminal or three-terminal; All known panels, such as an In Plane Switching (IPS) panel and a Vertical Alignment (VA) panel, can be applied.
  • TN twisted nematic
  • STN super twisted nematic
  • F ferroelectic
  • PD polymer dispersed
  • Active matrix panels such as two-terminal or three-terminal
  • All known panels such as an In Plane Switching (IPS) panel and a Vertical Alignment (VA) panel, can be applied.
  • IPS In Plane Switching
  • VA Vertical Alignment
  • the upper and lower substrates such as the color filter substrate or the array substrate in the liquid crystal display device
  • the upper and lower substrates are not particularly limited, and a configuration known in the art may be employed without limitation.
  • the present application may provide an adhesive composition which can improve durability and warpage characteristics even at high temperatures of 100 ° C. or higher and / or 65 ° C. and 95% high humidity when used for a protective film or an optical film. .
  • FIG. 1 is a schematic view for explaining a bending characteristic evaluation method in connection with the experimental example of the present application.
  • FIG. 2 is a schematic view for explaining a light leakage evaluation method in connection with an experimental example of the present application.
  • the number average molecular weight (Mn) and molecular weight distribution (PDI) of the block or block copolymer were measured using a gel permeation chromatograph (GPC), and the GPC measurement conditions are as follows. In the preparation of the calibration curve, measurement results were converted using standard polystyrene (manufactured by Aglient system).
  • Aglient GPC Aglient 1200 series, U.S.
  • the polarizing plates prepared in Examples and Comparative Examples were cut to have a width of about 106 mm and a length of about 142 mm, and were attached to a 7 inch commercial liquid crystal panel. Thereafter, the panel with a polarizing plate was stored in an autoclave (50 ° C., 5 atmospheres) for about 20 minutes to prepare a sample.
  • the samples were allowed to stand at 65 ° C. and 95% relative humidity for 500 hours, and then observed the occurrence of bubbles and peeling at the adhesive interface and evaluated by the following criteria.
  • heat resistance after the sample was kept at 100 ° C. for 500 hours, the occurrence of bubbles and peeling was also observed to evaluate the following criteria.
  • T g glass transition temperature
  • Wn is a weight fraction of a block copolymer or a monomer applied to each block of the copolymer
  • Tn represents a glass transition temperature when each monomer forms a homopolymer.
  • the right side in Equation A is the sum of the calculated values after calculating all the monomers (Wn / Tn) obtained by dividing the weight fraction of the monomers used by the glass transition temperature when the monomers form a homopolymer. to be.
  • Flexural properties were evaluated using the Strip measurement method (Glass bending measurement).
  • STN sodalime glass (4 x 41 cm 2 , 0.4t) for bending. If there is no foreign substance, use it as it is without washing. If there is any foreign substance, clean it using EAc and IPA solvent and dry it using Air-gun.
  • a polarizing plate (coated product) to which the pressure-sensitive adhesive is attached is prepared in a size of 3.5 ⁇ 40.5 cm 2 with a long MD direction. Attach the specimen to the prepared bending glass using a laminator. After measuring the degree of bending (initial value) in the attached state, it is stored for 72 hours at 100 °C heat-resistant conditions.
  • a pressure-sensitive adhesive formed from the pressure-sensitive adhesive compositions of Examples and Comparative Examples was laminated and cut to a size of 1 cm in width and 5 cm in length to prepare a specimen.
  • Adhesion surface of this specimen is attached to 0.7t thick soda-lime glass with 1cm X 1cm size and fixed to jig and mounted so that beam of AXO SCAN equipment can be perpendicular to the adhesion surface.
  • the specimen is then pulled out and subjected to stress deformation on the adhesive surface to record and record the in-plane-retardation value according to the applied force.
  • Optical compensation can be achieved by aligning the photocompensation monomers as stress is applied.
  • is close to 0 in the range of 4 or less, it means that the light leakage reduction effect is excellent in the endurance condition. .
  • Panel type LCD module for TN
  • Light leakage observation method Visual observation while driving the LCD module was evaluated based on the following criteria.
  • the adhesive polarizing plate prepared in Example or Comparative Example was cut to have a width of 25 mm and a length of 100 mm to prepare a specimen. Subsequently, the release PET film attached to the pressure-sensitive adhesive layer is peeled off, and the pressure-sensitive adhesive polarizing plate is attached to the glass (soda lime glass) using a roller of 2 kg in accordance with JIS Z 0237. Samples were prepared by pressing the glass with a polarizing plate for about 20 minutes in an autoclave (50 ° C., 5 atmospheres) and storing for 24 hours at constant temperature and humidity conditions (23 ° C., 50% relative humidity).
  • the TA force (Texture Analyzer, manufactured by Stable Micro Systems Co., Ltd.) was used to measure the peeling force while peeling the polarizing plate from the glass at a peel rate of 0.3 m / min and a peel angle of 180 °.
  • the specimens were prepared by cutting the polarizing plates prepared in Examples and Comparative Examples to have a length of 25 mm and a length of 100 mm. Thereafter, the specimen is attached to a PET (Poly (ethylene terephtalate)) film through a pressure-sensitive adhesive layer to prepare a laminate, and the laminate is maintained on a glass substrate so that the PET film is thereafter maintained at room temperature for three days. After the adhesion to the double-sided tape on the PET film was peeled at a peeling speed of 10 mm / sec and a peel angle of 180 ° at room temperature while measuring the adhesive force between the polarizing plate and the PET film to evaluate the interfacial adhesion.
  • PET Poly (ethylene terephtalate)
  • EBiB ethyl 2-bromoisobutyrate
  • MMA methyl methacrylate
  • BMA butyl methacrylate
  • HEMA hydroxyethyl methacrylate
  • Block copolymers were prepared by exposing the reaction mixture to oxygen and terminating the reaction by dilution in an appropriate solvent when the conversion of monomers (BA) reached 80% or more (in the process V-65 takes into account its half-life). Appropriately divided to the end of the reaction).
  • a block copolymer was prepared in the same manner as in Preparation Example 1, except that the type of the raw material used in the polymerization of the first block and the second block was adjusted as shown in Table 1 below.
  • V-65 was added to the reactor, and a chain extension reaction was performed (polymerizing the first block at both ends of the second block).
  • the conversion rate of the monomer (MMA) reaches 80% or more
  • the reaction mixture is exposed to oxygen, diluted with an appropriate solvent to terminate the reaction, and the number average molecular weight (Mn) is 88,000, and the molecular weight distribution (Mw / Mn) is 2.71.
  • Phosphorous triblock copolymer was prepared.
  • the weight ratio of the first block: the second block: the first block is about 15:70:15 (V-65 is appropriately divided and added to the end of the reaction in consideration of the half-life thereof).
  • a triblock copolymer (B5) was prepared in the same manner as in Preparation Example 7, except that the kind of raw material used in the polymerization of the first block and the second block was adjusted as shown in Table 2 below.
  • a triblock copolymer (B6, B7) was prepared in the same manner as in Preparation Example 7, except that the first block was prepared first and the second block was prepared at both ends.
  • a monomer mixture composed of 98.5 parts by weight of n-butylacrylate (BA) and 1.5 parts by weight of hydroxybutyl acrylate was added to a 1 L reactor equipped with a refrigeration device for nitrogen gas reflux and easy temperature control. . Thereafter, 150 parts by weight of ethyl acetate (EAc) was added as a solvent. After purging with nitrogen gas for about 60 minutes to remove oxygen, 0.09 parts by weight of AIBN (azobisisobutyronitrile), which is a reaction initiator, was maintained at a temperature of 60 ° C., and reacted for about 8 hours to react with a random copolymer (B8). ) was prepared. The number average molecular weight of the prepared random copolymer (B8) was 400,000, and the molecular weight distribution was 5.0.
  • AIBN azobisisobutyronitrile
  • TDI crosslinking agent (Coronate L, manufactured by Japan NPU), 0.01 parts by weight of DBTDL (Dibutyltin dilaurate), and 0.2 parts by weight of a silane coupling agent (SCA) based on 100 parts by weight of the block copolymer (A1) prepared in Preparation Example 1.
  • SCA silane coupling agent
  • the pressure-sensitive adhesive composition (coating liquid) and the pressure-sensitive adhesive polarizing plate were prepared in the same manner as in Example 1 except that each component and the ratio were adjusted as shown in Table 4 in the preparation of the pressure-sensitive adhesive composition (coating liquid).

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

La présente invention porte sur une composition adhésive, sur un stratifié optique, sur une plaque polarisante et sur un dispositif d'affichage. La composition adhésive selon la présente invention peut améliorer les caractéristiques de flexion de la plaque polarisante ainsi que sa durabilité.
PCT/KR2017/010455 2016-09-23 2017-09-22 Composition adhésive WO2018056743A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201780049565.0A CN109563390B (zh) 2016-09-23 2017-09-22 压敏粘合剂组合物
EP17853457.4A EP3489320B1 (fr) 2016-09-23 2017-09-22 Composition adhésive
US16/333,842 US10968372B2 (en) 2016-09-23 2017-09-22 Pressure-sensitive adhesive composition
JP2019503728A JP6710316B2 (ja) 2016-09-23 2017-09-22 粘着組成物

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2016-0121976 2016-09-23
KR20160121976 2016-09-23
KR1020170121896A KR102024256B1 (ko) 2016-09-23 2017-09-21 점착 조성물
KR10-2017-0121896 2017-09-21

Publications (1)

Publication Number Publication Date
WO2018056743A1 true WO2018056743A1 (fr) 2018-03-29

Family

ID=61690933

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/010455 WO2018056743A1 (fr) 2016-09-23 2017-09-22 Composition adhésive

Country Status (1)

Country Link
WO (1) WO2018056743A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020132713A (ja) * 2019-02-15 2020-08-31 積水化学工業株式会社 粘着テープ

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0782542A (ja) * 1993-09-09 1995-03-28 Sekisui Chem Co Ltd 偏光板もしくは位相差板用粘着剤
JP3997271B2 (ja) * 2005-11-21 2007-10-24 綜研化学株式会社 光学フィルム用粘着剤組成物および粘着シート、ならびにこれを用いた光学部材
KR20080094282A (ko) * 2007-04-19 2008-10-23 주식회사 엘지화학 아크릴계 점착제 조성물
KR20140147753A (ko) * 2013-06-19 2014-12-30 주식회사 엘지화학 점착제 조성물
KR20160085759A (ko) * 2013-11-15 2016-07-18 닛토덴코 가부시키가이샤 광학 필름용 수분산형 점착제 조성물, 점착제층, 점착형 광학 필름 및 화상 표시 장치
KR20160121976A (ko) 2015-04-13 2016-10-21 김태용 홀 소자를 이용한 다중 출력 전류센서
KR20170121896A (ko) 2016-04-26 2017-11-03 삼화페인트공업주식회사 속건형 무용제 에폭시 도장 장치의 이용 방법 및 이를 이용한 시공 방법

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0782542A (ja) * 1993-09-09 1995-03-28 Sekisui Chem Co Ltd 偏光板もしくは位相差板用粘着剤
JP3997271B2 (ja) * 2005-11-21 2007-10-24 綜研化学株式会社 光学フィルム用粘着剤組成物および粘着シート、ならびにこれを用いた光学部材
KR20080094282A (ko) * 2007-04-19 2008-10-23 주식회사 엘지화학 아크릴계 점착제 조성물
KR20140147753A (ko) * 2013-06-19 2014-12-30 주식회사 엘지화학 점착제 조성물
KR20160085759A (ko) * 2013-11-15 2016-07-18 닛토덴코 가부시키가이샤 광학 필름용 수분산형 점착제 조성물, 점착제층, 점착형 광학 필름 및 화상 표시 장치
KR20160121976A (ko) 2015-04-13 2016-10-21 김태용 홀 소자를 이용한 다중 출력 전류센서
KR20170121896A (ko) 2016-04-26 2017-11-03 삼화페인트공업주식회사 속건형 무용제 에폭시 도장 장치의 이용 방법 및 이를 이용한 시공 방법

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020132713A (ja) * 2019-02-15 2020-08-31 積水化学工業株式会社 粘着テープ
JP7348729B2 (ja) 2019-02-15 2023-09-21 積水化学工業株式会社 粘着テープ

Similar Documents

Publication Publication Date Title
WO2012128597A2 (fr) Composition à base d'un agent adhésif
WO2012128596A2 (fr) Composition adhésive
WO2010008241A2 (fr) Afficheur à cristaux liquides
KR102024256B1 (ko) 점착 조성물
WO2017099537A1 (fr) Composition adhésive
WO2013095064A1 (fr) Composition adhésive
WO2010120105A2 (fr) Composition adhésive
WO2013180524A1 (fr) Composition adhésive
WO2014204249A1 (fr) Composition adhésive
WO2014204253A1 (fr) Composition adhésive
WO2014204255A1 (fr) Composition d'adhésif
WO2016021895A1 (fr) Composition adhésive
WO2014204215A1 (fr) Composition d'adhésif
WO2014204217A1 (fr) Composition d'adhésif
WO2016099187A1 (fr) Composition adhésive
WO2014204211A1 (fr) Composition adhésive
WO2014204212A1 (fr) Composition adhésive
WO2014204254A1 (fr) Composition adhésive
WO2018043851A1 (fr) Plaque polarisante et dispositif d'affichage optique la comprenant
WO2012128594A2 (fr) Composition adhésive pour un film optique
WO2018056743A1 (fr) Composition adhésive
WO2015076548A1 (fr) Composition adhésive
WO2019054751A1 (fr) Stratifié optique
WO2015080536A1 (fr) Composition adhésive
WO2020022804A1 (fr) Composition adhésive

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17853457

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019503728

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2017853457

Country of ref document: EP

Effective date: 20190225

NENP Non-entry into the national phase

Ref country code: DE