WO2015141986A1 - Adhesive composition and polarizing plate comprising same - Google Patents

Adhesive composition and polarizing plate comprising same Download PDF

Info

Publication number
WO2015141986A1
WO2015141986A1 PCT/KR2015/002435 KR2015002435W WO2015141986A1 WO 2015141986 A1 WO2015141986 A1 WO 2015141986A1 KR 2015002435 W KR2015002435 W KR 2015002435W WO 2015141986 A1 WO2015141986 A1 WO 2015141986A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
group
adhesive composition
acrylic copolymer
weight
Prior art date
Application number
PCT/KR2015/002435
Other languages
French (fr)
Korean (ko)
Inventor
최한영
Original Assignee
동우 화인켐 주식회사
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
Application filed by 동우 화인켐 주식회사 filed Critical 동우 화인켐 주식회사
Publication of WO2015141986A1 publication Critical patent/WO2015141986A1/en

Links

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6283—Polymers of nitrogen containing compounds having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • C08G18/8029—Masked aromatic polyisocyanates
    • 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
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • G02F1/133528—Polarisers
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements

Definitions

  • the present invention relates to an adhesive composition and a polarizing plate including the same, and more particularly, to an adhesive composition having high adhesive strength and excellent durability, a polarizing plate and a liquid crystal display device including the same.
  • a liquid crystal display device includes a liquid crystal panel including a liquid crystal cell and a polarizing plate bonded to both surfaces of the liquid crystal cell via an adhesive layer.
  • the pressure-sensitive adhesive for bonding the liquid crystal cell and the polarizing plate is light leakage caused by the durability of heat resistance, moisture heat resistance, thermal shock resistance, cold resistance, etc.
  • the antistatic property for the prevention of static electricity generated when the release film is removed for the polarizing plate bonding must be satisfied at the same time.
  • Japanese Laid-Open Patent Publication No. 2008-285670 discloses an adhesive composition containing an acrylic resin obtained by copolymerizing an (meth) acrylic acid alkyl ester with an ionic liquid containing a polymerizable unsaturated group. It is described as having excellent performance.
  • the ionic liquid containing a polymerizable unsaturated group is insufficient in solubility in an organic solvent, making it difficult to copolymerize various ionic compounds, and the copolymer is uniformly produced when using an ionic monomer having insufficient solubility. There is a problem that the coating is non-uniform because it is not manufactured.
  • the present invention is to solve the above problems, one object of the present invention is to provide a pressure-sensitive adhesive composition with high adhesive strength and excellent durability.
  • Another object of the present invention is to provide a polarizing plate in which the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is laminated.
  • Still another object of the present invention is to provide a liquid crystal display device having the polarizing plate on at least one side of a liquid crystal cell.
  • Another object of the present invention is to provide a method for uniformly preparing an acrylic copolymer containing various ionic functional groups.
  • the present invention provides a pressure-sensitive adhesive composition
  • a pressure-sensitive adhesive composition comprising an acrylic copolymer containing a tertiary amine group and an ionic functional group-containing acrylic copolymer prepared by a nucleophilic substitution reaction of a compound containing a leaving group.
  • the acrylic copolymer containing the tertiary amine group may be prepared by copolymerization of a (meth) acrylate monomer and a monomer simultaneously containing an unsaturated double bond and a tertiary amine group in a molecule.
  • the compound containing a leaving group may be a compound of formula (I).
  • R is an alkyl group of C 1 -C 6 , an alkenyl group or an aralkyl group of C 2 -C 6 ,
  • X is a leaving group
  • the present invention provides a polarizing plate in which the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is laminated.
  • the present invention provides a liquid crystal display device having the polarizing plate on at least one side of the liquid crystal cell.
  • the present invention provides a method for producing an ionic functional group-containing acrylic copolymer comprising the step of nucleophilic substitution reaction of the acrylic copolymer containing the tertiary amine group and the compound containing the leaving group.
  • the pressure-sensitive adhesive composition comprising an ionic functional group-containing acrylic copolymer according to the present invention can be introduced into a variety of ionic functional groups in the acrylic copolymer, the copolymer is uniformly produced, the coating can be formed uniformly, the adhesive force is high Excellent durability
  • One embodiment of the present invention relates to a pressure-sensitive adhesive composition
  • a pressure-sensitive adhesive composition comprising an ionic functional group-containing acrylic copolymer prepared by the nucleophilic substitution reaction of an acrylic copolymer containing a tertiary amine group and a compound containing a leaving group.
  • the acrylic copolymer containing the tertiary amine group may be prepared by copolymerization of a (meth) acrylate monomer and a monomer simultaneously containing an unsaturated double bond and a tertiary amine group in a molecule.
  • the monomer containing the unsaturated double bond and the tertiary amine group simultaneously in the molecule may be a (meth) acrylate containing a tertiary amine group.
  • Specific examples may be one or more selected from compounds of Formulas 1 to 6 below.
  • the monomer containing the unsaturated double bond and the tertiary amine group at the same time in the molecule is preferably contained in 1 to 20% by weight, based on 100% by weight of the acrylic copolymer containing the tertiary amine group, it is 2 to 10% by weight More preferred. If the content is less than 1% by weight, the content of the resulting ionic functional groups are insufficient to secure durability, and if the content is more than 20% by weight, the stability of the coating solution may be insufficient due to the remaining amine groups.
  • the (meth) acrylate monomer may be a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms.
  • Specific examples include n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, Ethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, pentyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl ( Meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, la
  • the (meth) acrylate monomer is preferably contained in 80 to 99% by weight, more preferably 90 to 95% by weight relative to 100% by weight of the total monomers used in the production of the acrylic copolymer. If the content is less than 80% by weight, the adhesive force is not sufficient, and when the content is more than 99% by weight, cohesion may be lowered.
  • the acrylic copolymer containing a tertiary amine group has a (meth) acrylate monomer, a monomer containing an unsaturated double bond and a tertiary amine group simultaneously in a molecule, and a functional group capable of crosslinking with these. It may be a copolymer of monomers.
  • Examples of the monomer having a crosslinkable functional group include a monomer having a hydroxy group, a monomer having a carboxyl group, a monomer having an amide group, and the like as a component that imparts cohesion or adhesive strength by chemical bonding with a crosslinking agent. It can mix and use species.
  • 2-hydroxyethyl (meth) acrylate As a monomer which has a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate, 2-hydroxypropylene glycol (meth) acrylate, hydroxyalkylene glycol having 2 to 4 carbon atoms of an alkylene group ( Methacrylate, etc. are mentioned, Among these, 2-hydroxyethyl (meth) acrylate is preferable.
  • Monovalent acids such as (meth) acrylic acid and a crotonic acid; Diacids such as maleic acid, itaconic acid and fumaric acid, and monoalkyl esters thereof; 3- (meth) acryloylpropionic acid; Amberic anhydride ring-opening adduct of 2-hydroxyalkyl (meth) acrylate of 2-3 carbon atoms of alkyl group, Ambernoic acid ring-opening adduct of hydroxyalkylene glycol (meth) acrylate of 2-4 carbon atoms of alkylene group And the compound which ring-opened and added amber acid anhydride to the caprolactone adduct of 2-hydroxyalkyl (meth) acrylate of 2-3 carbon atoms of an alkyl group, Among these, (meth) acrylic acid is preferable.
  • Examples of the monomer having an amide group include (meth) acrylamide, N-isopropylacrylamide, N-tert-butylacrylamide, and of these, (meth) acrylamide is preferable.
  • the monomer which has a crosslinkable functional group is contained in 1 to 20 weight% with respect to 100 weight% of total monomers used for manufacture of an acryl-type copolymer, and it is more preferable that it is 1 to 10 weight%. If the content is less than 1% by weight cohesion may be lowered, if more than 20% by weight may be reduced cohesion.
  • polymerizable monomers in addition to the monomers may be further included in a range that does not lower the adhesion, such as 10% by weight or less, preferably 5% by weight or less.
  • the production method of the copolymer is not particularly limited, and may be prepared using a method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization, which are commonly used in the art, and solution polymerization is preferable.
  • a solvent, a polymerization initiator, a chain transfer agent for molecular weight control, and the like, which are usually used in the polymerization may be used.
  • the acrylic copolymer has a weight average molecular weight (polystyrene equivalent) measured by gel permeation chromatography (GPC) in general of 50,000 to 2,000,000, preferably 1,000,000 to 2,000,000.
  • GPC gel permeation chromatography
  • the compound containing a leaving group may be a compound of formula (I).
  • R is an alkyl group of C 1 -C 6 , an alkenyl group or an aralkyl group of C 2 -C 6 ,
  • X is a leaving group
  • an alkyl group of C 1 -C 6 means a straight or branched monovalent hydrocarbon having 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, i-propyl, n-butyl , i-butyl, t-butyl, n-pentyl, n-hexyl and the like.
  • an alkenyl group of C 2 -C 6 means a straight or branched unsaturated hydrocarbon composed of 2 to 6 carbon atoms having one or more carbon-carbon double bonds, for example ethyleneyl, propenyl, moiety. Tenyl, pentenyl, and the like, but are not limited thereto.
  • an aralkyl group refers to a complex group in which an aryl group (aromatic hydrocarbon group) is bonded to carbon of an alkyl group, and examples thereof include, but are not limited to, benzyl, phenethyl, and the like.
  • the C 1 -C 6 alkyl group, C 2 -C 6 alkenyl group and aralkyl group is one or more hydrogen is C 1 -C 6 alkyl group, C 2 -C 6 alkenyl group, C 2 -C 6 Alkynyl group, C 3 -C 10 cycloalkyl group, C 3 -C 10 heterocycloalkyl group, C 3 -C 10 heterocycloalkyloxy group, C 1 -C 6 haloalkyl group, C 1 -C 6 It may be substituted with an alkoxy group, a C 1 -C 6 thioalkoxy group, an aryl group, an acyl group, hydroxy, thio, halogen, amino, alkoxycarbonyl, carboxy, carbamoyl, cyano, nitro and the like. .
  • R is a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, or benzyl, optionally substituted with halogen,
  • X is halide, methanesulfonate, trifluoromethanesulfonate, benzenesulfonate or p-toluenesulfonate.
  • Representative compounds of the compound containing the leaving group may be selected from the compounds of the formulas (7) to (14).
  • One embodiment of the present invention relates to a method for producing an ionic functional group-containing acrylic copolymer comprising nucleophilic substitution reaction of an acrylic copolymer containing a tertiary amine group and a compound containing a leaving group.
  • the nucleophilic substitution reaction of the acryl-based copolymer containing the tertiary amine group and the compound containing the leaving group is carried out, for example, as shown in Scheme 1 below. Copolymers are prepared.
  • the nucleophilic substitution reaction can be easily carried out according to methods known in the art.
  • the pressure-sensitive adhesive composition according to an embodiment of the present invention may further include a crosslinking agent and a silane coupling agent.
  • the said crosslinking agent is a component for strengthening the cohesion force of an adhesive by crosslinking a copolymer suitably,
  • the kind is not specifically limited.
  • an isocyanate type compound, an epoxy type compound, etc. are mentioned, These can be used individually or in mixture of 2 or more types.
  • isocyanate compound tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate, naphthalene Diisocyanate compounds such as diisocyanate; Diisocyanate obtained from 2 moles of an adduct obtained by reacting 3 moles of a diisocyanate compound with 1 mole of a polyhydric alcohol compound such as trimethylolpropane, an isocyanurate obtained by self-condensing 3 moles of the diisocyanate compound, and 3 moles of the diisocyanate compound And polyfunctional isocyanate compounds containing three functional groups such as biuret, triphenylmethanetriisocyanate, and methylenebistriisocyanate, in which the remaining 1
  • epoxy compounds examples include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol.
  • melamine type compound can be used individually or in mixture of 2 or more types together with an isocyanate type compound and an epoxy type compound.
  • Hexamethylol melamine, hexamethoxymethylmelamine, hexabutoxymethylmelamine, etc. are mentioned as a melamine type compound.
  • the crosslinking agent may be included in an amount of 0.1 to 15 parts by weight, and more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the acrylic copolymer based on the solid content. If the content is less than 0.1 part by weight, the cohesion force becomes small due to insufficient crosslinking degree, which may cause durability deterioration such as lifting and damage of cutting property. If the content is more than 15 parts by weight, problem of relaxation of residual stress may occur due to excessive crosslinking reaction. have.
  • the type of the silane coupling agent is not particularly limited, and for example, vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-sty Aryltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-amin
  • the silane coupling agent is preferably included in an amount of 0.01 to 5 parts by weight, and more preferably 0.05 to 2.5 parts by weight based on 100 parts by weight of the acrylic copolymer based on the solid content. If the content is less than 0.01 parts by weight, the adhesion with the substrate to be bonded under a damp-heat environment may be lowered. If the content is more than 5 parts by weight, bubbles or peeling may occur, which may lower durability.
  • the pressure-sensitive adhesive composition according to an embodiment of the present invention in addition to the components described above, in order to adjust the adhesion, cohesion, viscosity, elastic modulus, glass transition temperature, antistatic properties, etc. required according to the use, tackifying resin, antioxidant, It may further include additives such as corrosion inhibitors, leveling agents, surface lubricants, dyes, pigments, antifoaming agents, fillers, light stabilizers, antistatic agents.
  • the adhesive composition of this invention can be used also as an adhesive for surface protection films as well as the adhesive for polarizing plates for bonding with a liquid crystal cell.
  • it can be used as a protective film, a reflective sheet, a structural adhesive sheet, a photo adhesive sheet, a lane display adhesive sheet, an optical adhesive product, an adhesive for an electronic component, as well as a general commercial adhesive sheet product and a medical patch.
  • One embodiment of the present invention relates to a polarizing plate in which a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is laminated.
  • the thickness of the pressure-sensitive adhesive layer can be adjusted according to the adhesive force, it is usually preferably from 3 to 100 ⁇ m, more preferably from 10 to 100 ⁇ m.
  • Such a polarizing plate can be applied to all conventional liquid crystal display devices, and in particular, a liquid crystal display device including a liquid crystal panel in which the polarizing plate on which the pressure-sensitive adhesive layer is laminated is bonded to at least one surface of a liquid crystal cell can be configured.
  • one embodiment of the present invention relates to a liquid crystal display device having the polarizing plate on at least one side of a liquid crystal cell.
  • n-butyl acrylate BA
  • HOA hydroxyethyl acrylate
  • dimethylaminoethyl acrylate 100 parts by weight was added.
  • purging nitrogen gas for 1 hour to remove oxygen it was maintained at 62 °C.
  • AIBN azobisisobutyronitrile
  • An ionic functional group-containing acrylic copolymer was prepared in the same manner as in Preparation Example 1, except that 5 parts by weight of methyl trifluoromethanesulfonate was used.
  • An ionic functional group-containing acrylic copolymer was prepared in the same manner as in Preparation Example 1, except that 3 parts by weight of methyl trifluoromethanesulfonate was used.
  • An ionic functional group-containing acrylic copolymer was prepared in the same manner as in Preparation Example 1, except that 1 part by weight of methyl trifluoromethanesulfonate was used.
  • An ionic functional group-containing acrylic copolymer was prepared in the same manner as in Preparation Example 4, except that 1 part by weight of iodine methane of Formula 7 was used instead of 1 part by weight of methyl trifluoromethanesulfonate.
  • An ionic functional group-containing acrylic copolymer was prepared in the same manner as in Preparation Example 1, except that 7 parts by weight of the compound of Formula 13 was used instead of 7 parts by weight of methyl trifluoromethanesulfonate.
  • n-butyl acrylate (BA) 90 parts by weight of n-butyl acrylate (BA), 2 parts by weight of hydroxyethyl acrylate (HEA), 90 parts by weight of n-butyl acrylate (BA) instead of 8 parts by weight of dimethylaminoethyl acrylate, hydroxyethyl acryl 2 parts by weight of HEA, Using 8 parts by weight, but proceeding in the same manner as in Preparation Example 1, the ionization reaction did not proceed further.
  • Each component was mixed in the composition shown in Table 1 below (unit: parts by weight), and diluted with ethyl acetate to prepare a pressure-sensitive adhesive composition having a solid content concentration of 15%.
  • the pressure-sensitive adhesive composition prepared above was applied on a release film coated with a silicone release agent to have a thickness of 25 ⁇ m, and dried at 100 ° C. for 1 minute to form a pressure-sensitive adhesive layer.
  • a pressure-sensitive adhesive polarizing plate was prepared by laminating the pressure-sensitive adhesive layer prepared above on an iodine-based polarizing plate having a thickness of 185 ⁇ m by adhesive processing.
  • Crosslinking agent Coronate-L (Japan Urethane Co., Ltd.)
  • Silane coupling agent KBM-403 (Shin-Etsu Corporation)
  • the polarizing plates of Examples 1 to 11 including the ionic functional group-containing acrylic copolymer according to the present invention are compared to the polarizing plates of Comparative Examples 1 and 3 including the acrylic copolymer in which the ionization reaction was not performed.
  • the heat resistance and the heat and humidity resistance were remarkably excellent.
  • Comparative Example 2 including the ionic functional group-containing acrylic copolymer prepared by polymerizing the ionic monomer, the heat resistance and the heat and humidity resistance was low. This is interpreted because the copolymer is not uniformly prepared, so that the coating is nonuniform and bubbles and peeling are likely to be generated.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polarising Elements (AREA)

Abstract

The present invention provides: an adhesive composition, which contains an acrylic copolymer containing an ionic functional group prepared by the nucleophilic substitution reaction of an acrylic copolymer containing a tertiary amine group and a compound containing a leaving group; a polarizing plate comprising the same; and a liquid crystal display device. The adhesive composition according to the present invention has high adhesive strength and excellent durability.

Description

점착제 조성물 및 이를 포함하는 편광판 Adhesive composition and polarizing plate comprising same
본 발명은 점착제 조성물 및 이를 포함하는 편광판에 관한 것으로, 보다 상세하게는 점착력이 높고 내구성이 우수한 점착제 조성물, 이를 포함하는 편광판 및 액정표시장치에 관한 것이다.The present invention relates to an adhesive composition and a polarizing plate including the same, and more particularly, to an adhesive composition having high adhesive strength and excellent durability, a polarizing plate and a liquid crystal display device including the same.
액정표시장치(Liquid crystal display device, LCD)는 액정셀과 상기 액정셀의 양면에 점착제층을 매개로 접합된 편광판을 포함하는 액정패널을 구비한다.A liquid crystal display device (LCD) includes a liquid crystal panel including a liquid crystal cell and a polarizing plate bonded to both surfaces of the liquid crystal cell via an adhesive layer.
액정셀과 편광판의 접합을 위한 점착제는 내열성, 내습열성, 열충격성, 내한성 등의 내구성과, 접합 오류 또는 이물의 혼입 등의 경우 실시하는 리워크, 내열조건에서 편광판의 수축응력에 의해 발생되는 빛샘에 대한 억제성, 편광판 접합을 위해 이형필름의 제거 시에 발생되는 정전기의 방지를 위한 대전방지성 등을 동시에 만족시켜야 한다. 이 중에서도 특히 내구성과 리워크성을 만족시키기 위해서 요구되는 점착제의 특성이 서로 상충되기 때문에 이들 모두를 만족시키는 것은 완전히 해결되지 못하고 있다.The pressure-sensitive adhesive for bonding the liquid crystal cell and the polarizing plate is light leakage caused by the durability of heat resistance, moisture heat resistance, thermal shock resistance, cold resistance, etc. In order to prevent the antistatic property, the antistatic property for the prevention of static electricity generated when the release film is removed for the polarizing plate bonding must be satisfied at the same time. Among these, since the characteristics of the pressure-sensitive adhesive required for satisfying durability and reworkability are in conflict with each other, satisfying all of them has not been completely solved.
일본 공개특허 제2008-285670호에는 (메타)아크릴산 알킬에스테르와 중합성 불포화기를 함유하는 이온성 액체를 공중합하여 얻어지는 아크릴계 수지를 함유하는 점착제 조성물이 개시되어 있으며, 이러한 점착제 조성물이 점착 성능과 대전방지능이 우수한 것으로 기재되어 있다. 그러나 중합성 불포화기를 함유하는 이온성 액체는 유기용매에 대한 용해성이 충분한 종류가 부족하여 다양한 이온성 화합물의 공중합이 어렵고, 용해성이 충분하지 않은 이온성 단량체를 이용하여 제조할 경우 공중합체가 균일하게 제조되지 않아 코팅이 불균일한 문제점이 있다.Japanese Laid-Open Patent Publication No. 2008-285670 discloses an adhesive composition containing an acrylic resin obtained by copolymerizing an (meth) acrylic acid alkyl ester with an ionic liquid containing a polymerizable unsaturated group. It is described as having excellent performance. However, the ionic liquid containing a polymerizable unsaturated group is insufficient in solubility in an organic solvent, making it difficult to copolymerize various ionic compounds, and the copolymer is uniformly produced when using an ionic monomer having insufficient solubility. There is a problem that the coating is non-uniform because it is not manufactured.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로, 본 발명의 한 목적은 점착력이 높고 내구성이 우수한 점착제 조성물을 제공하는 것이다.The present invention is to solve the above problems, one object of the present invention is to provide a pressure-sensitive adhesive composition with high adhesive strength and excellent durability.
본 발명의 다른 목적은 상기 점착제 조성물로 이루어진 점착제층이 적층된 편광판을 제공하는 것이다.Another object of the present invention is to provide a polarizing plate in which the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is laminated.
본 발명의 또 다른 목적은 액정셀의 적어도 한 면에 상기 편광판이 구비된 액정표시장치를 제공하는 것이다.Still another object of the present invention is to provide a liquid crystal display device having the polarizing plate on at least one side of a liquid crystal cell.
본 발명의 또 다른 목적은 다양한 이온성 작용기를 함유하는 아크릴계 공중합체를 균일하게 제조하는 방법을 제공하는 것이다.Another object of the present invention is to provide a method for uniformly preparing an acrylic copolymer containing various ionic functional groups.
한편으로, 본 발명은 3차 아민기를 함유하는 아크릴계 공중합체와 이탈기를 함유한 화합물의 친핵성 치환반응에 의해서 제조되는 이온성 작용기 함유 아크릴계 공중합체를 포함하는 점착제 조성물을 제공한다.On the other hand, the present invention provides a pressure-sensitive adhesive composition comprising an acrylic copolymer containing a tertiary amine group and an ionic functional group-containing acrylic copolymer prepared by a nucleophilic substitution reaction of a compound containing a leaving group.
본 발명의 일 실시형태에서, 상기 3차 아민기를 함유하는 아크릴계 공중합체는 (메타)아크릴레이트 단량체와, 불포화 이중결합과 3차 아민기를 분자 내에 동시에 함유하는 단량체의 공중합에 의하여 제조할 수 있다.In one embodiment of the present invention, the acrylic copolymer containing the tertiary amine group may be prepared by copolymerization of a (meth) acrylate monomer and a monomer simultaneously containing an unsaturated double bond and a tertiary amine group in a molecule.
본 발명의 일 실시형태에서, 상기 이탈기를 함유한 화합물은 하기 화학식 I의 화합물일 수 있다.In one embodiment of the present invention, the compound containing a leaving group may be a compound of formula (I).
[화학식 I][Formula I]
R-XR-X
상기 화학식에서, In the above formula,
R은 C1-C6의 알킬기, C2-C6의 알케닐기 또는 아랄킬기이고,R is an alkyl group of C 1 -C 6 , an alkenyl group or an aralkyl group of C 2 -C 6 ,
X는 이탈기이다.X is a leaving group.
다른 한편으로, 본 발명은 상기 점착제 조성물로 이루어진 점착제층이 적층된 편광판을 제공한다.On the other hand, the present invention provides a polarizing plate in which the pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is laminated.
또 다른 한편으로, 본 발명은 액정셀의 적어도 한 면에 상기 편광판이 구비된 액정표시장치를 제공한다.On the other hand, the present invention provides a liquid crystal display device having the polarizing plate on at least one side of the liquid crystal cell.
또 다른 한편으로, 본 발명은 3차 아민기를 함유하는 아크릴계 공중합체와 이탈기를 함유한 화합물을 친핵성 치환반응시키는 단계를 포함하는 이온성 작용기 함유 아크릴계 공중합체의 제조방법을 제공한다. On the other hand, the present invention provides a method for producing an ionic functional group-containing acrylic copolymer comprising the step of nucleophilic substitution reaction of the acrylic copolymer containing the tertiary amine group and the compound containing the leaving group.
본 발명에 따른 이온성 작용기 함유 아크릴계 공중합체를 포함하는 점착제 조성물은 다양한 이온성 작용기가 아크릴계 공중합체에 도입될 수 있고, 공중합체가 균일하게 제조되어 코팅이 균일하게 형성될 수 있으며, 점착력이 높고 내구성이 우수하다.The pressure-sensitive adhesive composition comprising an ionic functional group-containing acrylic copolymer according to the present invention can be introduced into a variety of ionic functional groups in the acrylic copolymer, the copolymer is uniformly produced, the coating can be formed uniformly, the adhesive force is high Excellent durability
이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 일 실시형태는 3차 아민기를 함유하는 아크릴계 공중합체와 이탈기를 함유한 화합물의 친핵성 치환반응에 의해서 제조되는 이온성 작용기 함유 아크릴계 공중합체를 포함하는 점착제 조성물에 관한 것이다.One embodiment of the present invention relates to a pressure-sensitive adhesive composition comprising an ionic functional group-containing acrylic copolymer prepared by the nucleophilic substitution reaction of an acrylic copolymer containing a tertiary amine group and a compound containing a leaving group.
본 발명의 일 실시형태에서, 상기 3차 아민기를 함유하는 아크릴계 공중합체는 (메타)아크릴레이트 단량체와, 불포화 이중결합과 3차 아민기를 분자 내에 동시에 함유하는 단량체의 공중합에 의하여 제조할 수 있다.In one embodiment of the present invention, the acrylic copolymer containing the tertiary amine group may be prepared by copolymerization of a (meth) acrylate monomer and a monomer simultaneously containing an unsaturated double bond and a tertiary amine group in a molecule.
본 발명의 일 실시형태에서, 상기 불포화 이중결합과 3차 아민기를 분자 내에 동시에 함유하는 단량체는 3차 아민기를 함유하는 (메타)아크릴레이트일 수 있다. 구체적인 예로는, 하기 화학식 1 내지 6의 화합물로부터 선택된 1종 이상일 수 있다.In one embodiment of the present invention, the monomer containing the unsaturated double bond and the tertiary amine group simultaneously in the molecule may be a (meth) acrylate containing a tertiary amine group. Specific examples may be one or more selected from compounds of Formulas 1 to 6 below.
[화학식 1][Formula 1]
Figure PCTKR2015002435-appb-I000001
Figure PCTKR2015002435-appb-I000001
[화학식 2][Formula 2]
Figure PCTKR2015002435-appb-I000002
Figure PCTKR2015002435-appb-I000002
[화학식 3][Formula 3]
Figure PCTKR2015002435-appb-I000003
Figure PCTKR2015002435-appb-I000003
[화학식 4][Formula 4]
Figure PCTKR2015002435-appb-I000004
Figure PCTKR2015002435-appb-I000004
[화학식 5][Formula 5]
Figure PCTKR2015002435-appb-I000005
Figure PCTKR2015002435-appb-I000005
[화학식 6][Formula 6]
Figure PCTKR2015002435-appb-I000006
Figure PCTKR2015002435-appb-I000006
상기 불포화 이중결합과 3차 아민기를 분자 내에 동시에 함유하는 단량체는 상기 3차 아민기를 함유하는 아크릴계 공중합체 100중량%에 대하여 1 내지 20중량%로 포함되는 것이 바람직하고, 2 내지 10중량%인 것이 보다 바람직하다. 함량이 1중량% 미만인 경우 생성되는 이온성 작용기의 함량이 부족하여 내구성 확보가 부족하고, 20중량% 초과인 경우 잔존하는 아민기에 의하여 코팅액의 경시 안정성이 부족해질 수 있다.The monomer containing the unsaturated double bond and the tertiary amine group at the same time in the molecule is preferably contained in 1 to 20% by weight, based on 100% by weight of the acrylic copolymer containing the tertiary amine group, it is 2 to 10% by weight More preferred. If the content is less than 1% by weight, the content of the resulting ionic functional groups are insufficient to secure durability, and if the content is more than 20% by weight, the stability of the coating solution may be insufficient due to the remaining amine groups.
본 발명의 일 실시형태에서, 상기 (메타)아크릴레이트 단량체는 탄소수 1-12의 알킬기를 갖는 (메타)아크릴레이트 단량체일 수 있다. 구체적인 예로는 n-부틸(메타)아크릴레이트, 2-부틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 2-에틸부틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, 메틸(메타)아크릴레이트, n-프로필(메타)아크릴레이트, 이소프로필(메타)아크릴레이트, 펜틸(메타)아크릴레이트, n-옥틸(메타)아크릴레이트, 이소옥틸(메타)아크릴레이트, n-노닐(메타)아크릴레이트, 이소노닐(메타)아크릴레이트, 데실(메타)아크릴레이트, 라우릴(메타)아크릴레이트 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다. 이 중에서 n-부틸아크릴레이트, 2-에틸헥실아크릴레이트 또는 이들의 혼합물이 바람직하다.In one embodiment of the present invention, the (meth) acrylate monomer may be a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms. Specific examples include n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, Ethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, pentyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl ( Meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, and the like. Can be used. Among these, n-butyl acrylate, 2-ethylhexyl acrylate, or a mixture thereof is preferable.
상기 (메타)아크릴레이트 단량체는 아크릴계 공중합체의 제조에 사용되는 총 단량체 100중량%에 대하여 80 내지 99중량%로 포함되는 것이 바람직하고, 90 내지 95중량%인 것이 보다 바람직하다. 함량이 80중량% 미만인 경우 점착력이 충분하지 못하고, 99중량% 초과인 경우 응집력이 저하될 수 있다.The (meth) acrylate monomer is preferably contained in 80 to 99% by weight, more preferably 90 to 95% by weight relative to 100% by weight of the total monomers used in the production of the acrylic copolymer. If the content is less than 80% by weight, the adhesive force is not sufficient, and when the content is more than 99% by weight, cohesion may be lowered.
본 발명의 일 실시형태에서, 상기 3차 아민기를 함유하는 아크릴계 공중합체는 (메타)아크릴레이트 단량체와, 불포화 이중결합과 3차 아민기를 분자 내에 동시에 함유하는 단량체, 및 이들과 가교 가능한 관능기를 갖는 단량체의 공중합체일 수 있다.In one embodiment of the present invention, the acrylic copolymer containing a tertiary amine group has a (meth) acrylate monomer, a monomer containing an unsaturated double bond and a tertiary amine group simultaneously in a molecule, and a functional group capable of crosslinking with these. It may be a copolymer of monomers.
상기 가교 가능한 관능기를 갖는 단량체는 하기 가교제와의 화학 결합에 의해 응집력 또는 점착 강도를 부여하는 성분으로서, 히드록시기를 갖는 단량체, 카르복시기를 갖는 단량체, 아미드기를 갖는 단량체 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Examples of the monomer having a crosslinkable functional group include a monomer having a hydroxy group, a monomer having a carboxyl group, a monomer having an amide group, and the like as a component that imparts cohesion or adhesive strength by chemical bonding with a crosslinking agent. It can mix and use species.
히드록시기를 갖는 단량체로는 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 6-히드록시헥실(메타)아크릴레이트, 2-히드록시에틸렌글리콜(메타)아크릴레이트, 2-히드록시프로필렌글리콜(메타)아크릴레이트, 알킬렌기의 탄소수가 2-4인 히드록시알킬렌글리콜(메타)아크릴레이트 등을 들 수 있으며, 이 중에서 2-히드록시에틸(메타)아크릴레이트가 바람직하다.As a monomer which has a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate, 2-hydroxypropylene glycol (meth) acrylate, hydroxyalkylene glycol having 2 to 4 carbon atoms of an alkylene group ( Methacrylate, etc. are mentioned, Among these, 2-hydroxyethyl (meth) acrylate is preferable.
카르복시기를 갖는 단량체로는 (메타)아크릴산, 크로톤산 등의 1가산; 말레인산, 이타콘산, 푸마르산 등의 2가산 및 이들의 모노알킬에스테르; 3-(메타)아크릴로일프로피온산; 알킬기의 탄소수가 2-3인 2-히드록시알킬(메타)아크릴레이트의 무수호박산 개환 부가체, 알킬렌기의 탄소수가 2-4인 히드록시알킬렌글리콜(메타)아크릴레이트의 무수호박산 개환 부가체, 알킬기의 탄소수가 2-3인 2-히드록시알킬(메타)아크릴레이트의 카프로락톤 부가체에 무수호박산을 개환 부가시킨 화합물 등을 들 수 있으며, 이 중에서 (메타)아크릴산이 바람직하다.As a monomer which has a carboxy group, Monovalent acids, such as (meth) acrylic acid and a crotonic acid; Diacids such as maleic acid, itaconic acid and fumaric acid, and monoalkyl esters thereof; 3- (meth) acryloylpropionic acid; Amberic anhydride ring-opening adduct of 2-hydroxyalkyl (meth) acrylate of 2-3 carbon atoms of alkyl group, Ambernoic acid ring-opening adduct of hydroxyalkylene glycol (meth) acrylate of 2-4 carbon atoms of alkylene group And the compound which ring-opened and added amber acid anhydride to the caprolactone adduct of 2-hydroxyalkyl (meth) acrylate of 2-3 carbon atoms of an alkyl group, Among these, (meth) acrylic acid is preferable.
아미드기를 갖는 단량체로는 (메타)아크릴아미드, N-이소프로필아크릴아미드, N-3차부틸아크릴아미드 등을 들 수 있으며, 이 중에서 (메타)아크릴아미드가 바람직하다.Examples of the monomer having an amide group include (meth) acrylamide, N-isopropylacrylamide, N-tert-butylacrylamide, and of these, (meth) acrylamide is preferable.
가교 가능한 관능기를 갖는 단량체는 아크릴계 공중합체의 제조에 사용되는 총 단량체 100중량%에 대하여 1 내지 20중량%로 포함되는 것이 바람직하고, 1 내지 10중량%인 것이 보다 바람직하다. 함량이 1중량% 미만인 경우 응집력이 저하될 수 있고, 20중량% 초과인 경우 점착력이 저하될 수 있다.It is preferable that the monomer which has a crosslinkable functional group is contained in 1 to 20 weight% with respect to 100 weight% of total monomers used for manufacture of an acryl-type copolymer, and it is more preferable that it is 1 to 10 weight%. If the content is less than 1% by weight cohesion may be lowered, if more than 20% by weight may be reduced cohesion.
또한, 상기 단량체들 이외에 다른 중합성 단량체가 점착력을 저하시키지 않는 범위, 예컨대 10중량% 이하, 바람직하게는 5중량% 이하로 더 포함될 수 있다.In addition, other polymerizable monomers in addition to the monomers may be further included in a range that does not lower the adhesion, such as 10% by weight or less, preferably 5% by weight or less.
공중합체의 제조방법은 특별히 한정되지 않으며, 당해 분야에서 통상적으로 사용되는 괴상중합, 용액중합, 유화중합 또는 현탁중합 등의 방법을 이용하여 제조할 수 있으며, 용액중합이 바람직하다. 또한, 중합 시 통상 사용되는 용매, 중합개시제, 분자량 제어를 위한 연쇄이동제 등을 사용할 수 있다.The production method of the copolymer is not particularly limited, and may be prepared using a method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization, which are commonly used in the art, and solution polymerization is preferable. In addition, a solvent, a polymerization initiator, a chain transfer agent for molecular weight control, and the like, which are usually used in the polymerization, may be used.
상기 아크릴계 공중합체는 겔투과크로마토그래피(Gel permeation chromatography, GPC)에 의해 측정된 중량평균분자량(폴리스티렌 환산)이 통상 50,000 내지 2,000,000이며, 바람직하게는 1,000,000 내지 2,000,000이다.The acrylic copolymer has a weight average molecular weight (polystyrene equivalent) measured by gel permeation chromatography (GPC) in general of 50,000 to 2,000,000, preferably 1,000,000 to 2,000,000.
본 발명의 일 실시형태에서, 상기 이탈기를 함유한 화합물은 하기 화학식 I의 화합물일 수 있다.In one embodiment of the present invention, the compound containing a leaving group may be a compound of formula (I).
[화학식 I][Formula I]
R-XR-X
상기 화학식에서, In the above formula,
R은 C1-C6의 알킬기, C2-C6의 알케닐기 또는 아랄킬기이고,R is an alkyl group of C 1 -C 6 , an alkenyl group or an aralkyl group of C 2 -C 6 ,
X는 이탈기이다.X is a leaving group.
본 명세서에서 사용되는 C1-C6의 알킬기는 탄소수 1 내지 6개로 구성된 직쇄형 또는 분지형의 1가 탄화수소를 의미하며, 예를 들어 메틸, 에틸, n-프로필, i-프로필, n-부틸, i-부틸, t-부틸, n-펜틸, n-헥실 등이 포함되나 이에 한정되는 것은 아니다.As used herein, an alkyl group of C 1 -C 6 means a straight or branched monovalent hydrocarbon having 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, i-propyl, n-butyl , i-butyl, t-butyl, n-pentyl, n-hexyl and the like.
본 명세서에서 사용되는 C2-C6의 알케닐기는 하나 이상의 탄소-탄소 이중결합을 갖는 탄소수 2 내지 6개로 구성된 직쇄형 또는 분지형 불포화 탄화수소를 의미하며, 예를 들어 에틸렌일, 프로펜일, 부텐일, 펜텐일 등이 포함되나 이에 한정되는 것은 아니다.As used herein, an alkenyl group of C 2 -C 6 means a straight or branched unsaturated hydrocarbon composed of 2 to 6 carbon atoms having one or more carbon-carbon double bonds, for example ethyleneyl, propenyl, moiety. Tenyl, pentenyl, and the like, but are not limited thereto.
본 명세서에서 사용되는 아랄킬기(aralkyl group)는 아릴기(방향족 탄화수소기)가 알킬기의 탄소에 결합되어 형성된 복합기를 의미하며, 예를 들어 벤질, 페네틸 등이 포함되나 이에 한정되는 것은 아니다. As used herein, an aralkyl group refers to a complex group in which an aryl group (aromatic hydrocarbon group) is bonded to carbon of an alkyl group, and examples thereof include, but are not limited to, benzyl, phenethyl, and the like.
상기 C1-C6의 알킬기, C2-C6의 알케닐기 및 아랄킬기는 한 개 또는 그 이상의 수소가 C1-C6의 알킬기, C2-C6의 알케닐기, C2-C6의 알키닐기, C3-C10의 사이클로알킬기, C3-C10의 헤테로사이클로알킬기, C3-C10의 헤테로사이클로알킬옥시기, C1-C6의 할로알킬기, C1-C6의 알콕시기, C1-C6의 티오알콕시기, 아릴기, 아실기, 히드록시, 티오(thio), 할로겐, 아미노, 알콕시카르보닐, 카르복시, 카바모일, 시아노, 니트로 등으로 치환될 수 있다.The C 1 -C 6 alkyl group, C 2 -C 6 alkenyl group and aralkyl group is one or more hydrogen is C 1 -C 6 alkyl group, C 2 -C 6 alkenyl group, C 2 -C 6 Alkynyl group, C 3 -C 10 cycloalkyl group, C 3 -C 10 heterocycloalkyl group, C 3 -C 10 heterocycloalkyloxy group, C 1 -C 6 haloalkyl group, C 1 -C 6 It may be substituted with an alkoxy group, a C 1 -C 6 thioalkoxy group, an aryl group, an acyl group, hydroxy, thio, halogen, amino, alkoxycarbonyl, carboxy, carbamoyl, cyano, nitro and the like. .
본 발명의 일 실시형태에서, In one embodiment of the invention,
R은 할로겐으로 치환되거나 치환되지 않은 C1-C6의 알킬기, C2-C6의 알케닐기 또는 벤질이고,R is a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, or benzyl, optionally substituted with halogen,
X는 할라이드, 메탄술포네이트, 트리플루오로메탄술포네이트, 벤젠술포네이트 또는 p-톨루엔술포네이트이다.X is halide, methanesulfonate, trifluoromethanesulfonate, benzenesulfonate or p-toluenesulfonate.
상기 이탈기를 함유한 화합물 중 대표적인 화합물은 하기 화학식 7 내지 14의 화합물에서 선택될 수 있다.Representative compounds of the compound containing the leaving group may be selected from the compounds of the formulas (7) to (14).
[화학식 7][Formula 7]
Figure PCTKR2015002435-appb-I000007
Figure PCTKR2015002435-appb-I000007
[화학식 8][Formula 8]
Figure PCTKR2015002435-appb-I000008
Figure PCTKR2015002435-appb-I000008
[화학식 9][Formula 9]
Figure PCTKR2015002435-appb-I000009
Figure PCTKR2015002435-appb-I000009
[화학식 10][Formula 10]
Figure PCTKR2015002435-appb-I000010
Figure PCTKR2015002435-appb-I000010
[화학식 11][Formula 11]
Figure PCTKR2015002435-appb-I000011
Figure PCTKR2015002435-appb-I000011
[화학식 12][Formula 12]
Figure PCTKR2015002435-appb-I000012
Figure PCTKR2015002435-appb-I000012
[화학식 13][Formula 13]
Figure PCTKR2015002435-appb-I000013
Figure PCTKR2015002435-appb-I000013
[화학식 14][Formula 14]
Figure PCTKR2015002435-appb-I000014
Figure PCTKR2015002435-appb-I000014
본 발명의 일 실시형태는 3차 아민기를 함유하는 아크릴계 공중합체와 이탈기를 함유한 화합물을 친핵성 치환반응시키는 단계를 포함하는 이온성 작용기 함유 아크릴계 공중합체의 제조방법에 관한 것이다.One embodiment of the present invention relates to a method for producing an ionic functional group-containing acrylic copolymer comprising nucleophilic substitution reaction of an acrylic copolymer containing a tertiary amine group and a compound containing a leaving group.
본 발명의 일 실시형태에서, 3차 아민기를 함유하는 아크릴계 공중합체와 이탈기를 함유한 화합물을 친핵성 치환반응시키면, 예를 들어 하기 반응식 1에 도시된 바와 같이 이온성 작용기, 즉 암모늄염 작용기 함유 아크릴계 공중합체가 제조된다. In one embodiment of the present invention, the nucleophilic substitution reaction of the acryl-based copolymer containing the tertiary amine group and the compound containing the leaving group is carried out, for example, as shown in Scheme 1 below. Copolymers are prepared.
[반응식 1]Scheme 1
Figure PCTKR2015002435-appb-I000015
Figure PCTKR2015002435-appb-I000015
상기 친핵성 치환반응은 당해 분야에 공지된 방법에 따라 용이하게 수행할 수 있다.The nucleophilic substitution reaction can be easily carried out according to methods known in the art.
본 발명의 일 실시형태에 따른 점착제 조성물은 가교제 및 실란커플링제를 추가로 포함할 수 있다.The pressure-sensitive adhesive composition according to an embodiment of the present invention may further include a crosslinking agent and a silane coupling agent.
본 발명의 일 실시형태에서, 상기 가교제는 공중합체를 적절히 가교함으로써 점착제의 응집력을 강화하기 위한 성분으로서, 그 종류는 특별히 한정되지 않는다. 예컨대, 이소시아네이트계 화합물, 에폭시계 화합물 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.In one embodiment of this invention, the said crosslinking agent is a component for strengthening the cohesion force of an adhesive by crosslinking a copolymer suitably, The kind is not specifically limited. For example, an isocyanate type compound, an epoxy type compound, etc. are mentioned, These can be used individually or in mixture of 2 or more types.
이소시아네이트계 화합물로는 톨릴렌디이소시아네이트, 자일렌디이소시아네이트, 2,4-디페닐메탄디이소시아네이트, 4,4-디페닐메탄디이소시아네이트, 헥사메틸렌디이소시아네이트, 이소포론디이소시아네이트, 테트라메틸자일렌디이소시아네이트, 나프탈렌디이소시아네이트 등의 디이소시아네이트 화합물; 트리메틸올프로판 등의 다가 알콜계 화합물 1몰에 디이소시아네이트 화합물 3몰을 반응시킨 부가체, 디이소시아네이트 화합물 3몰을 자기 축합시킨 이소시아누레이트체, 디이소시아네이트 화합물 3몰 중 2몰로부터 얻어지는 디이소시아네이트 우레아에 나머지 1몰의 디이소시아네이트가 축합된 뷰렛체, 트리페닐메탄트리이소시아네이트, 메틸렌비스트리이소시아네이트 등의 3개의 관능기를 함유하는 다관능 이소시아네이트 화합물 등을 들 수 있다.As the isocyanate compound, tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate, naphthalene Diisocyanate compounds such as diisocyanate; Diisocyanate obtained from 2 moles of an adduct obtained by reacting 3 moles of a diisocyanate compound with 1 mole of a polyhydric alcohol compound such as trimethylolpropane, an isocyanurate obtained by self-condensing 3 moles of the diisocyanate compound, and 3 moles of the diisocyanate compound And polyfunctional isocyanate compounds containing three functional groups such as biuret, triphenylmethanetriisocyanate, and methylenebistriisocyanate, in which the remaining 1 mole of diisocyanate is condensed to urea.
에폭시계 화합물로는 에틸렌글리콜디글리시딜에테르, 디에틸렌글리콜디글리시딜에테르, 폴리에틸렌글리콜디글리시딜에테르, 프로필렌글리콜디글리시딜에테르, 트리프로필렌글리콜디글리시딜에테르, 폴리프로필렌글리콜디글리시딜에테르, 네오펜틸글리콜디글리시딜에테르, 1,6-헥산디올디글리시딜에테르, 폴리테트라메틸렌글리콜디글리시딜에테르, 글리세롤디글리시딜에테르, 글리세롤트리글리시딜에테르, 디글리세롤폴리글리시딜에테르, 폴리글리세롤폴리글리시딜에테르, 레졸신디글리시딜에테르, 2,2-디브로모네오펜틸글리콜디글리시딜에테르, 트리메틸올프로판트리글리시딜에테르, 펜타에리트리톨폴리글리시딜에테르, 소르비톨폴리글리시딜에테르, 아디핀산디글리시딜에스테르, 프탈산디글리시딜에스테르, 트리스(글리시딜)이소시아누레이트, 트리스(글리시독시에틸)이소시아누레이트, 1,3-비스(N,N-글리시딜아미노메틸)시클로헥산, N,N,N',N'-테트라글리시딜-m-자일릴렌디아민 등을 들 수 있다.Examples of the epoxy compounds include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol. Diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, Diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, resorcin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, trimethylolpropanetriglycidyl ether, pentaerythritol Polyglycidyl ether, sorbitol polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tris (glycidyl) isocyanur Tris (glycidoxyethyl) isocyanurate, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-m- Xylylenediamine etc. are mentioned.
또한, 이소시아네이트계 화합물, 에폭시계 화합물과 함께 멜라민계 화합물을 단독 또는 2종 이상 혼합하여 추가로 사용할 수 있다.Moreover, melamine type compound can be used individually or in mixture of 2 or more types together with an isocyanate type compound and an epoxy type compound.
멜라민계 화합물로는 헥사메틸올멜라민, 헥사메톡시메틸멜라민, 헥사부톡시메틸멜라민 등을 들 수 있다.Hexamethylol melamine, hexamethoxymethylmelamine, hexabutoxymethylmelamine, etc. are mentioned as a melamine type compound.
상기 가교제는 고형분 함량을 기준으로 상기 아크릴계 공중합체 100중량부에 대하여 0.1 내지 15중량부로 포함되는 것이 바람직하고, 0.1 내지 5중량부로 포함되는 것이 보다 바람직하다. 함량이 0.1중량부 미만인 경우 부족한 가교도로 인해 응집력이 작아지게 되어 들뜸과 같은 내구성 저하가 유발되고 절단성을 해칠 수 있으며, 15중량부 초과인 경우 과다 가교반응에 의해 잔류응력 완화에 문제가 발생할 수 있다.The crosslinking agent may be included in an amount of 0.1 to 15 parts by weight, and more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the acrylic copolymer based on the solid content. If the content is less than 0.1 part by weight, the cohesion force becomes small due to insufficient crosslinking degree, which may cause durability deterioration such as lifting and damage of cutting property. If the content is more than 15 parts by weight, problem of relaxation of residual stress may occur due to excessive crosslinking reaction. have.
본 발명의 일 실시형태에서, 상기 실란커플링제의 종류는 특별히 한정되지 않으며, 예컨대 비닐클로로실란, 비닐트리메톡시실란, 비닐트리에톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필메틸디에톡시실란, 3-글리시독시프로필디에톡시실란, 3-글리시독시프로필트리에톡시실란, p-스티릴트리메톡시실란, 3-메타크릴옥시프로필트리에톡시실란, 3-메타크릴옥시프로필트리메톡시실란, 3-메타크릴옥시프로필메틸디메톡시실란, 3-메타크릴옥시프로필메틸디에톡시실란, 3-아크릴옥시프로필트리메톡시실란, N-2-(아미노에틸)-3-아미노프로필메틸디메톡시실란, N-2-(아미노에틸)-3-아미노프로필트리메톡시실란, N-2-(아미노에틸)-3-아미노프로필메틸트리에톡시실란, 3-아미노프로필트리메톡시실란, 3-아미노프로필트리에톡시실란, 3-트리에톡시실릴-N-(1,3-디메틸부틸리덴)프로필아민, N-페닐-3-아미노프로필트리메톡시실란, 3-클로로프로필트리메톡시실란, 3-머캅토프로필메틸디메톡시실란, 3-머캅토프로필트리메톡시실란, 비스(트리에톡시실릴프로필)테트라설파이드, 3-이소시아네이토프로필트리에톡시실란 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.In one embodiment of the present invention, the type of the silane coupling agent is not particularly limited, and for example, vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-sty Aryltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (Aminoethyl) -3-aminopropylmethyltriethoxysilane, 3-aminopropyltrimethoxysil , 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-chloropropyltri Methoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, etc. are mentioned. have. These can be used individually or in mixture of 2 or more types.
상기 실란커플링제는 고형분 함량을 기준으로 상기 아크릴계 공중합체 100중량부에 대하여 0.01 내지 5중량부로 포함되는 것이 바람직하고, 0.05 내지 2.5중량부로 포함되는 것이 보다 바람직하다. 함량이 0.01중량부 미만인 경우 내습열 환경 하에서 접합되는 기재와의 밀착성이 저하될 수 있으며, 5중량부 초과인 경우 오히려 기포나 박리 현상이 발생하여 내구성이 저하될 수 있다.The silane coupling agent is preferably included in an amount of 0.01 to 5 parts by weight, and more preferably 0.05 to 2.5 parts by weight based on 100 parts by weight of the acrylic copolymer based on the solid content. If the content is less than 0.01 parts by weight, the adhesion with the substrate to be bonded under a damp-heat environment may be lowered. If the content is more than 5 parts by weight, bubbles or peeling may occur, which may lower durability.
본 발명의 일 실시형태에 따른 점착제 조성물은 상기와 같은 성분 이외에, 용도에 따라 요구되는 점착력, 응집력, 점성, 탄성률, 유리전이온도, 대전방지성 등을 조절하기 위하여, 점착성 부여 수지, 산화방지제, 부식방지제, 레벨링제, 표면윤활제, 염료, 안료, 소포제, 충전제, 광안정제, 대전방지제 등의 첨가제를 더 포함할 수 있다.The pressure-sensitive adhesive composition according to an embodiment of the present invention, in addition to the components described above, in order to adjust the adhesion, cohesion, viscosity, elastic modulus, glass transition temperature, antistatic properties, etc. required according to the use, tackifying resin, antioxidant, It may further include additives such as corrosion inhibitors, leveling agents, surface lubricants, dyes, pigments, antifoaming agents, fillers, light stabilizers, antistatic agents.
본 발명의 점착제 조성물은 액정셀과의 접합을 위한 편광판용 점착제뿐만 아니라 표면보호필름용 점착제로서도 사용할 수 있다. 또한, 보호필름, 반사시트, 구조용 점착시트, 사진용 점착시트, 차선표시용 점착시트, 광학용 점착제품, 전자부품용 점착제뿐만 아니라 일반 상업용 점착시트제품, 의료용 패치로도 사용 가능하다.The adhesive composition of this invention can be used also as an adhesive for surface protection films as well as the adhesive for polarizing plates for bonding with a liquid crystal cell. In addition, it can be used as a protective film, a reflective sheet, a structural adhesive sheet, a photo adhesive sheet, a lane display adhesive sheet, an optical adhesive product, an adhesive for an electronic component, as well as a general commercial adhesive sheet product and a medical patch.
본 발명의 일 실시형태는 상기 점착제 조성물로 이루어진 점착제층이 적층된 편광판에 관한 것이다. One embodiment of the present invention relates to a polarizing plate in which a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is laminated.
상기 점착제층의 두께는 그 점착력에 따라 조절될 수 있으며, 통상 3 내지 100㎛인 것이 바람직하며, 10 내지 100㎛인 것이 보다 바람직하다.The thickness of the pressure-sensitive adhesive layer can be adjusted according to the adhesive force, it is usually preferably from 3 to 100㎛, more preferably from 10 to 100㎛.
이러한 편광판은 통상의 액정표시장치에 모두 적용 가능하며, 구체적으로 상기 점착제층이 적층된 편광판을 액정셀의 적어도 한 면에 접합한 액정패널을 포함하는 액정표시장치를 구성할 수 있다.Such a polarizing plate can be applied to all conventional liquid crystal display devices, and in particular, a liquid crystal display device including a liquid crystal panel in which the polarizing plate on which the pressure-sensitive adhesive layer is laminated is bonded to at least one surface of a liquid crystal cell can be configured.
따라서, 본 발명의 일 실시형태는 액정셀의 적어도 한 면에 상기 편광판이 구비된 액정표시장치에 관한 것이다. Accordingly, one embodiment of the present invention relates to a liquid crystal display device having the polarizing plate on at least one side of a liquid crystal cell.
이하, 실시예, 비교예 및 실험예에 의해 본 발명을 보다 구체적으로 설명하고자 한다. 이들 실시예, 비교예 및 실험예는 오직 본 발명을 설명하기 위한 것으로, 본 발명의 범위가 이들에 국한되지 않는다는 것은 당업자에게 있어서 자명하다.Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. These examples, comparative examples and experimental examples are only for illustrating the present invention, it is apparent to those skilled in the art that the scope of the present invention is not limited thereto.
제조예 1: 이온성 작용기 함유 아크릴계 공중합체의 제조Preparation Example 1 Preparation of Ionic Functional Containing Acrylic Copolymer
질소가스가 환류되고 온도조절이 용이하도록 냉각장치를 설치한 1L의 반응기에 n-부틸아크릴레이트(BA) 90중량부, 히드록시에틸아크릴레이트(HEA) 2중량부, 디메틸아미노에틸아크릴레이트 8중량부로 이루어진 단량체 혼합물을 투입한 후, 용제로 에틸아세테이트 100중량부를 투입하였다. 그런 다음, 산소를 제거하기 위하여 질소가스를 1시간 동안 퍼징한 후, 62℃로 유지하였다. 상기 혼합물을 균일하게 한 후, 반응개시제로 아조비스이소부티로니트릴(AIBN) 0.07중량부를 투입하고, 6시간 동안 반응시켜 중량평균분자량 약 100만인 3차 아미노기를 갖는 아크릴계 공중합체를 합성하였다.90 parts by weight of n-butyl acrylate (BA), 2 parts by weight of hydroxyethyl acrylate (HEA), 8 parts by weight of dimethylaminoethyl acrylate in a 1 L reactor equipped with a refrigeration system to allow nitrogen gas to be refluxed and for easy temperature control. After adding the monomer mixture consisting of parts, ethyl acetate as a solvent 100 parts by weight was added. Then, after purging nitrogen gas for 1 hour to remove oxygen, it was maintained at 62 ℃. After the mixture was uniform, 0.07 parts by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator, and reacted for 6 hours to synthesize an acrylic copolymer having a tertiary amino group having a weight average molecular weight of about 1 million.
그런 다음, 메틸트라이플루오로메탄설포네이트(methyl trifluoromethanesulfonate) 7중량부를 추가하고, 동일한 온도에서 24시간 동안 추가 반응시켜 이온성 작용기 함유 아크릴계 공중합체를 제조하였다.Then, 7 parts by weight of methyl trifluoromethanesulfonate was added, and further reacted at the same temperature for 24 hours to prepare an ionic functional group-containing acrylic copolymer.
반응 혼합물 일부를 취하고 질소 블로잉(blowing)하여 용매를 제거한 뒤, NMR을 측정하여 메틸트라이플루오로메탄설포네이트가 잔존하지 않음을 확인하여, 메틸트라이플루오로메탄설포네이트가 아크릴계 공중합체와 반응하여 이온을 형성하였음을 확인하였다.A portion of the reaction mixture was taken and nitrogen blown to remove the solvent, and then NMR was measured to confirm that methyltrifluoromethanesulfonate did not remain, and methyltrifluoromethanesulfonate reacted with the acrylic copolymer to obtain ions. It was confirmed that was formed.
제조예 2: 이온성 작용기 함유 아크릴계 공중합체의 제조Preparation Example 2 Preparation of Ionic Functional Containing Acrylic Copolymer
메틸트라이플루오로메탄설포네이트(methyl trifluoromethanesulfonate) 5중량부를 이용한 것을 제외하고, 상기 제조예 1과 동일하게 진행하여 이온성 작용기 함유 아크릴계 공중합체를 제조하였다.An ionic functional group-containing acrylic copolymer was prepared in the same manner as in Preparation Example 1, except that 5 parts by weight of methyl trifluoromethanesulfonate was used.
제조예 3: 이온성 작용기 함유 아크릴계 공중합체의 제조Preparation Example 3 Preparation of Ionic Functional Containing Acrylic Copolymer
메틸트라이플루오로메탄설포네이트(methyl trifluoromethanesulfonate) 3중량부를 이용한 것을 제외하고, 상기 제조예 1과 동일하게 진행하여 이온성 작용기 함유 아크릴계 공중합체를 제조하였다.An ionic functional group-containing acrylic copolymer was prepared in the same manner as in Preparation Example 1, except that 3 parts by weight of methyl trifluoromethanesulfonate was used.
제조예 4: 이온성 작용기 함유 아크릴계 공중합체의 제조Preparation Example 4 Preparation of Ionic Functional Containing Acrylic Copolymer
메틸트라이플루오로메탄설포네이트(methyl trifluoromethanesulfonate) 1중량부를 이용한 것을 제외하고, 상기 제조예 1과 동일하게 진행하여 이온성 작용기 함유 아크릴계 공중합체를 제조하였다.An ionic functional group-containing acrylic copolymer was prepared in the same manner as in Preparation Example 1, except that 1 part by weight of methyl trifluoromethanesulfonate was used.
제조예 5: 이온성 작용기 함유 아크릴계 공중합체의 제조Preparation Example 5 Preparation of Ionic Functional Containing Acrylic Copolymer
메틸트라이플루오로메탄설포네이트(methyl trifluoromethanesulfonate) 1중량부대신에 화학식 7의 요오드메탄 1중량부를 이용한 것을 제외하고, 상기 제조예 4와 동일하게 진행하여 이온성 작용기 함유 아크릴계 공중합체를 제조하였다.An ionic functional group-containing acrylic copolymer was prepared in the same manner as in Preparation Example 4, except that 1 part by weight of iodine methane of Formula 7 was used instead of 1 part by weight of methyl trifluoromethanesulfonate.
제조예 6: 이온성 작용기 함유 아크릴계 공중합체의 제조Preparation Example 6 Preparation of Ionic Functional Containing Acrylic Copolymer
메틸트라이플루오로메탄설포네이트(methyl trifluoromethanesulfonate) 7중량부대신에 화학식 13의 화합물 7중량부를 이용한 것을 제외하고, 상기 제조예 1와 동일하게 진행하여 이온성 작용기 함유 아크릴계 공중합체를 제조하였다.An ionic functional group-containing acrylic copolymer was prepared in the same manner as in Preparation Example 1, except that 7 parts by weight of the compound of Formula 13 was used instead of 7 parts by weight of methyl trifluoromethanesulfonate.
제조예 7: 이온성 작용기 함유 아크릴계 공중합체의 제조Preparation Example 7 Preparation of Ionic Functional Containing Acrylic Copolymer
n-부틸아크릴레이트(BA) 90중량부, 히드록시에틸아크릴레이트(HEA) 2중량부, 디메틸아미노에틸아크릴레이트 8중량부 대신에 n-부틸아크릴레이트(BA) 94중량부, 히드록시에틸아크릴레이트(HEA) 2중량부, 디메틸아미노에틸아크릴레이트 4중량부를 이용하고, 메틸트라이플루오로메탄설포네이트(methyl trifluoromethanesulfonate) 7중량부 대신에 3중량부를 이용한 것을 제외하고, 상기 제조예 1과 동일하게 진행하여 이온성 작용기 함유 아크릴계 공중합체를 제조하였다.90 parts by weight of n-butyl acrylate (BA), 2 parts by weight of hydroxyethyl acrylate (HEA), 94 parts by weight of n-butyl acrylate (BA) instead of 8 parts by weight of dimethylaminoethyl acrylate, hydroxyethyl acryl 2 parts by weight of HEA, 4 parts by weight of dimethylaminoethyl acrylate, and 3 parts by weight instead of 7 parts by weight of methyl trifluoromethanesulfonate, were used in the same manner as in Preparation Example 1. Proceeding to prepare an ionic functional group-containing acrylic copolymer.
제조예 8: 이온성 작용기 함유 아크릴계 공중합체의 제조Preparation Example 8 Preparation of Ionic Functional Containing Acrylic Copolymer
n-부틸아크릴레이트(BA) 90중량부, 히드록시에틸아크릴레이트(HEA) 2중량부, 디메틸아미노에틸아크릴레이트 8중량부 대신에 n-부틸아크릴레이트(BA) 97중량부, 히드록시에틸아크릴레이트(HEA) 2중량부, 디메틸아미노에틸아크릴레이트 1중량부를 이용하고, 메틸트라이플루오로메탄설포네이트(methyl trifluoromethanesulfonate) 7중량부 대신에 1중량부를 이용한 것을 제외하고, 상기 제조예 1과 동일하게 진행하여 이온성 작용기 함유 아크릴계 공중합체를 제조하였다.90 parts by weight of n-butyl acrylate (BA), 2 parts by weight of hydroxyethyl acrylate (HEA), 97 parts by weight of n-butyl acrylate (BA) instead of 8 parts by weight of dimethylaminoethyl acrylate, hydroxyethyl acryl In the same manner as in Preparation Example 1, except that 2 parts by weight of HEA and 1 part by weight of dimethylaminoethyl acrylate were used, and 1 part by weight was used instead of 7 parts by weight of methyl trifluoromethanesulfonate. Proceeding to prepare an ionic functional group-containing acrylic copolymer.
제조예 9: 이온성 작용기 함유 아크릴계 공중합체의 제조Preparation Example 9 Preparation of Ionic Functional Containing Acrylic Copolymer
n-부틸아크릴레이트(BA) 90중량부, 히드록시에틸아크릴레이트(HEA) 2중량부, 디메틸아미노에틸아크릴레이트 8중량부 대신에 n-부틸아크릴레이트(BA) 82중량부, 히드록시에틸아크릴레이트(HEA) 2중량부, 디메틸아미노에틸아크릴레이트 16중량부를 이용하고, 메틸트라이플루오로메탄설포네이트(methyl trifluoromethanesulfonate) 7 중량부 대신에 14 중량부를 이용한 것을 제외하고, 상기 제조예 1과 동일하게 진행하여 이온성 작용기 함유 아크릴계 공중합체를 제조하였다.90 parts by weight of n-butyl acrylate (BA), 2 parts by weight of hydroxyethyl acrylate (HEA), 82 parts by weight of n-butyl acrylate (BA) instead of 8 parts by weight of dimethylaminoethyl acrylate, hydroxyethyl acryl 2 parts by weight of HEA, 16 parts by weight of dimethylaminoethyl acrylate, and 14 parts by weight instead of 7 parts by weight of methyl trifluoromethanesulfonate, were used in the same manner as in Preparation Example 1. Proceeding to prepare an ionic functional group-containing acrylic copolymer.
제조예 10: 이온성 작용기 함유 아크릴계 공중합체의 제조Preparation Example 10 Preparation of Ionic Functional Containing Acrylic Copolymer
n-부틸아크릴레이트(BA) 90중량부, 히드록시에틸아크릴레이트(HEA) 2중량부, 디메틸아미노에틸아크릴레이트 8중량부 대신에 n-부틸아크릴레이트(BA) 73중량부, 히드록시에틸아크릴레이트(HEA) 2중량부, 디메틸아미노에틸아크릴레이트 25중량부를 이용하고, 메틸트라이플루오로메탄설포네이트(methyl trifluoromethanesulfonate) 7 중량부 대신에 20 중량부를 이용한 것을 제외하고, 상기 제조예 1과 동일하게 진행하여 이온성 작용기 함유 아크릴계 공중합체를 제조하였다.90 parts by weight of n-butyl acrylate (BA), 2 parts by weight of hydroxyethyl acrylate (HEA), 73 parts by weight of n-butyl acrylate (BA) instead of 8 parts by weight of dimethylaminoethyl acrylate, hydroxyethyl acryl 2 parts by weight of HEA, 25 parts by weight of dimethylaminoethyl acrylate and 20 parts by weight instead of 7 parts by weight of methyl trifluoromethanesulfonate were used in the same manner as in Preparation Example 1 above. Proceeding to prepare an ionic functional group-containing acrylic copolymer.
제조예 11: 이온성 작용기 함유 아크릴계 공중합체의 제조Preparation Example 11 Preparation of Ionic Functional Containing Acrylic Copolymer
디메틸아미노에틸아크릴레이트 8중량부 대신에 디에틸아미노에틸아크릴레이트 8중량부를 이용하여, 상기 제조예 1과 동일하게 진행하여 이온성 작용기 함유 아크릴계 공중합체를 제조하였다.Using 8 parts by weight of diethylaminoethyl acrylate instead of 8 parts by weight of dimethylaminoethyl acrylate, the same procedure as in Preparation Example 1 was conducted to prepare an ionic functional group-containing acrylic copolymer.
비교 제조예 1: 아크릴계 공중합체의 제조Comparative Production Example 1 Preparation of Acrylic Copolymer
상기 제조예 1과 동일하게 진행하되, 암모늄염화 반응은 진행하지 않았다.Proceed as in Preparation Example 1, but the ammonium chloride reaction did not proceed.
비교 제조예 2: 이온성 단량체를 이용한 공중합체의 제조Comparative Preparation Example 2 Preparation of Copolymer Using Ionic Monomer
n-부틸아크릴레이트(BA) 90중량부, 히드록시에틸아크릴레이트(HEA) 2중량부, 디메틸아미노에틸아크릴레이트 8중량부 대신에 n-부틸아크릴레이트(BA) 90중량부, 히드록시에틸아크릴레이트(HEA) 2중량부,
Figure PCTKR2015002435-appb-I000016
8중량부를 이용하여, 상기 제조예 1과 동일하게 진행하되, 이온화 반응은 추가적으로 진행하지 않았다.90 parts by weight of n-butyl acrylate (BA), 2 parts by weight of hydroxyethyl acrylate (HEA), 90 parts by weight of n-butyl acrylate (BA) instead of 8 parts by weight of dimethylaminoethyl acrylate, hydroxyethyl acryl 2 parts by weight of HEA,
Figure PCTKR2015002435-appb-I000016
Using 8 parts by weight, but proceeding in the same manner as in Preparation Example 1, the ionization reaction did not proceed further.
비교 제조예 3: 아크릴계 공중합체의 제조Comparative Production Example 3 Preparation of Acrylic Copolymer
n-부틸아크릴레이트(BA) 98중량부, 히드록시에틸아크릴레이트(HEA) 2중량부를 이용하여 상기 제조예 1과 동일하게 진행하되, 이온화 반응은 추가적으로 진행하지 않았다.98 parts by weight of n-butyl acrylate (BA), 2 parts by weight of hydroxyethyl acrylate (HEA) was carried out in the same manner as in Preparation Example 1, but the ionization reaction did not proceed further.
실시예 1 내지 11 및 비교예 1 내지 3: 점착제 부착 편광판의 제조Examples 1 to 11 and Comparative Examples 1 to 3: Preparation of a pressure-sensitive adhesive polarizing plate
하기 표 1의 조성으로 각 성분을 혼합한 후(단위: 중량부), 에틸아세테이트에 희석하여 고형분 농도 15%의 점착제 조성물을 제조하였다. Each component was mixed in the composition shown in Table 1 below (unit: parts by weight), and diluted with ethyl acetate to prepare a pressure-sensitive adhesive composition having a solid content concentration of 15%.
상기에서 제조된 점착제 조성물을 실리콘 이형제가 코팅된 이형필름 상에 두께가 25㎛가 되도록 도포하고, 100℃에서 1분 동안 건조시켜 점착제층을 형성하였다. The pressure-sensitive adhesive composition prepared above was applied on a release film coated with a silicone release agent to have a thickness of 25 μm, and dried at 100 ° C. for 1 minute to form a pressure-sensitive adhesive layer.
두께 185㎛의 요오드계 편광판에 상기 제조된 점착제층을 점착 가공으로 적층하여 점착제 부착 편광판을 제조하였다.A pressure-sensitive adhesive polarizing plate was prepared by laminating the pressure-sensitive adhesive layer prepared above on an iodine-based polarizing plate having a thickness of 185 μm by adhesive processing.
표 1
공중합체 가교제 실란커플링제
실시예 1 제조예 1: 100 0.5 0.5
실시예 2 제조예 2: 100 0.5 0.5
실시예 3 제조예 3: 100 0.5 0.5
실시예 4 제조예 4: 100 0.5 0.5
실시예 5 제조예 5: 100 0.5 0.5
실시예 6 제조예 6: 100 0.5 0.5
실시예 7 제조예 7: 100 0.5 0.5
실시예 8 제조예 8: 100 0.5 0.5
실시예 9 제조예 9: 100 0.5 0.5
실시예 10 제조예 10: 100 0.5 0.5
실시예 11 제조예 11: 100 0.5 0.5
비교예 1 비교 제조예 1: 100 0.5 0.5
비교예 2 비교 제조예 2: 100 0.5 0.5
비교예 3 비교 제조예 3: 100 0.5 0.5
Table 1
Copolymer Crosslinking agent Silane coupling agent
Example 1 Preparation Example 1: 100 0.5 0.5
Example 2 Preparation Example 2: 100 0.5 0.5
Example 3 Preparation Example 3: 100 0.5 0.5
Example 4 Preparation Example 4: 100 0.5 0.5
Example 5 Preparation Example 5: 100 0.5 0.5
Example 6 Preparation Example 6: 100 0.5 0.5
Example 7 Preparation Example 7: 100 0.5 0.5
Example 8 Preparation Example 8: 100 0.5 0.5
Example 9 Preparation Example 9: 100 0.5 0.5
Example 10 Preparation Example 10 100 0.5 0.5
Example 11 Preparation Example 11: 100 0.5 0.5
Comparative Example 1 Comparative Preparation Example 1: 100 0.5 0.5
Comparative Example 2 Comparative Preparation Example 2: 100 0.5 0.5
Comparative Example 3 Comparative Preparation Example 3: 100 0.5 0.5
가교제: 코로네이트-L (일본우레탄사)Crosslinking agent: Coronate-L (Japan Urethane Co., Ltd.)
실란커플링제: KBM-403 (신에츠사)Silane coupling agent: KBM-403 (Shin-Etsu Corporation)
실험예 1: 공중합체 제조 특성 및 내구성 평가Experimental Example 1 Evaluation of Copolymer Preparation Properties and Durability
상기 실시예 및 비교예에서 제조된 점착제 부착 편광판의 물성을 하기의 방법으로 측정하고, 그 결과를 하기 표 2에 나타내었다. The physical properties of the pressure-sensitive adhesive polarizing plate prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Table 2 below.
(1)공중합체 제조 특성(1) copolymer manufacturing characteristics
제조된 공중합체의 균일성 및 겔화 특성을 확인하였다.The homogeneity and gelling properties of the prepared copolymer were confirmed.
<평가기준><Evaluation Criteria>
공중합체 용액의 불균일이 육안으로 확인됨: ×Unevenness of the copolymer solution is visually identified: ×
공중합체 용액의 불균일이 육안으로 확인되지 않음: ○Non-uniformity in the copolymer solution was not observed visually:
(2)내열성/내습열성 평가(2) Heat resistance / humidity heat resistance evaluation
점착제 부착 편광판의 이형필름을 제거하고, 점착제층 표면을 코닝 글라스에 접합한 후, 80℃와 60℃/90RH% 조건에서 각각 300시간 방치한 후 외관을 확인하였다. After removing the release film of the polarizing plate with a pressure-sensitive adhesive, and bonded the surface of the pressure-sensitive adhesive layer to the Corning glass, after standing for 300 hours at 80 ℃ and 60 ℃ / 90 RH% conditions respectively, the appearance was confirmed.
<평가기준><Evaluation Criteria>
기포와 박리현상 3개 이상 시인됨: ×Bubble and Peeling 3 or more admitted: ×
기포와 박리현상 2개 이하 시인됨: ○Less than 2 bubbles and peelings are admitted: ○
기포와 박리현상 미시인됨: ◎Bubbles and Peelings Unidentified: ◎
표 2
구분 공중합체 제조 특성 내열성 내습열성
실시예 1 ○ ◎ ◎
실시예 2 ○ ◎ ◎
실시예 3 ○ ◎ ◎
실시예 4 ○ ○ ◎
실시예 5 ○ ○ ◎
실시예 6 ○ ◎ ◎
실시예 7 ○ ◎ ◎
실시예 8 ○ ○ ◎
실시예 9 ○ ◎ ○
실시예 10 ○ ○ ○
실시예 11 ○ ◎ ◎
비교예 1 ○ × ×
비교예 2 × × ×
비교예 3 ○ × ×
TABLE 2
division Copolymer Preparation Properties Heat resistance Moisture and Heat Resistance
Example 1 ○ ◎ ◎
Example 2 ○ ◎ ◎
Example 3 ○ ◎ ◎
Example 4 ○ ○ ◎
Example 5 ○ ○ ◎
Example 6 ○ ◎ ◎
Example 7 ○ ◎ ◎
Example 8 ○ ○ ◎
Example 9 ○ ◎ ○
Example 10 ○ ○ ○
Example 11 ○ ◎ ◎
Comparative Example 1 ○ × ×
Comparative Example 2 × × ×
Comparative Example 3 ○ × ×
상기 표 2에서 보듯이, 본 발명에 따른 이온성 작용기 함유 아크릴계 공중합체를 포함하는 실시예 1 내지 11의 편광판은 이온화 반응이 수행되지 않은 아크릴계 공중합체를 포함하는 비교예 1 및 3의 편광판에 비해 내열성 및 내습열성이 현저히 우수하였다.As shown in Table 2, the polarizing plates of Examples 1 to 11 including the ionic functional group-containing acrylic copolymer according to the present invention are compared to the polarizing plates of Comparative Examples 1 and 3 including the acrylic copolymer in which the ionization reaction was not performed. The heat resistance and the heat and humidity resistance were remarkably excellent.
한편, 이온성 단량체를 중합하여 제조되는 이온성 작용기 함유 아크릴계 공중합체를 포함하는 비교예 2의 경우에는 내열성 및 내습열성이 낮게 나타났다. 이는 공중합체가 균일하게 제조되지 않아서 코팅이 불균일하여 기포와 박리가 생성되기 쉽기 때문으로 해석된다.On the other hand, in the case of Comparative Example 2 including the ionic functional group-containing acrylic copolymer prepared by polymerizing the ionic monomer, the heat resistance and the heat and humidity resistance was low. This is interpreted because the copolymer is not uniformly prepared, so that the coating is nonuniform and bubbles and peeling are likely to be generated.
이상으로 본 발명의 특정한 부분을 상세히 기술하였는 바, 본 발명이 속한 기술분야에서 통상의 지식을 가진 자에게 있어서 이러한 구체적인 기술은 단지 바람직한 구현예일 뿐이며, 이에 본 발명의 범위가 제한되는 것이 아님은 명백하다. 본 발명이 속한 기술분야에서 통상의 지식을 가진 자라면 상기 내용을 바탕으로 본 발명의 범주 내에서 다양한 응용 및 변형을 행하는 것이 가능할 것이다.Having described the specific part of the present invention in detail, it is apparent to those skilled in the art that this specific technology is only a preferred embodiment, which is not intended to limit the scope of the present invention. Do. Those skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above contents.
따라서, 본 발명의 실질적인 범위는 첨부된 특허청구범위와 그의 등가물에 의하여 정의된다고 할 것이다.Therefore, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.

Claims (12)

  1. 3차 아민기를 함유하는 아크릴계 공중합체와 이탈기를 함유한 화합물의 친핵성 치환반응에 의해서 제조되는 이온성 작용기 함유 아크릴계 공중합체를 포함하는 점착제 조성물.An adhesive composition comprising an ionic functional group-containing acrylic copolymer prepared by a nucleophilic substitution reaction of an acrylic copolymer containing a tertiary amine group and a compound containing a leaving group.
  2. 제1항에 있어서, 3차 아민기를 함유하는 아크릴계 공중합체는 (메타)아크릴레이트 단량체와, 불포화 이중결합과 3차 아민기를 분자 내에 동시에 함유하는 단량체의 공중합에 의하여 제조되는 점착제 조성물.The pressure-sensitive adhesive composition of claim 1, wherein the acrylic copolymer containing a tertiary amine group is prepared by copolymerization of a (meth) acrylate monomer and a monomer simultaneously containing an unsaturated double bond and a tertiary amine group in a molecule.
  3. 제2항에 있어서, 불포화 이중결합과 3차 아민기를 분자 내에 동시에 함유하는 단량체는 3차 아민기를 함유하는 (메타)아크릴레이트인 점착제 조성물.The pressure-sensitive adhesive composition of claim 2, wherein the monomer containing an unsaturated double bond and a tertiary amine group simultaneously in the molecule is a (meth) acrylate containing a tertiary amine group.
  4. 제 2항에 있어서, 불포화 이중결합과 3차 아민기를 분자 내에 동시에 함유하는 단량체는 3차 아민기를 함유하는 아크릴계 공중합체 100중량%에 대하여 1 내지 20중량% 포함되는 점착제 조성물.The pressure-sensitive adhesive composition of claim 2, wherein the monomer containing an unsaturated double bond and a tertiary amine group in the molecule is contained in an amount of 1 to 20% by weight based on 100% by weight of the acrylic copolymer containing the tertiary amine group.
  5. 제2항에 있어서, 불포화 이중결합과 3차 아민기를 분자 내에 동시에 함유하는 단량체는 하기 화학식 1 내지 6의 화합물로부터 선택된 1종 이상을 포함하는 점착제 조성물:The pressure-sensitive adhesive composition of claim 2, wherein the monomer containing an unsaturated double bond and a tertiary amine group at the same time in a molecule comprises at least one member selected from compounds of Formulas 1 to 6:
    [화학식 1][Formula 1]
    Figure PCTKR2015002435-appb-I000017
    Figure PCTKR2015002435-appb-I000017
    [화학식 2][Formula 2]
    Figure PCTKR2015002435-appb-I000018
    Figure PCTKR2015002435-appb-I000018
    [화학식 3][Formula 3]
    Figure PCTKR2015002435-appb-I000019
    Figure PCTKR2015002435-appb-I000019
    [화학식 4][Formula 4]
    Figure PCTKR2015002435-appb-I000020
    Figure PCTKR2015002435-appb-I000020
    [화학식 5][Formula 5]
    Figure PCTKR2015002435-appb-I000021
    Figure PCTKR2015002435-appb-I000021
    [화학식 6][Formula 6]
    Figure PCTKR2015002435-appb-I000022
    Figure PCTKR2015002435-appb-I000022
  6. 제1항에 있어서, 이탈기를 함유한 화합물은 하기 화학식 I의 화합물인 점착제 조성물:The pressure-sensitive adhesive composition of claim 1, wherein the compound containing a leaving group is a compound of Formula I:
    [화학식 I][Formula I]
    R-XR-X
    상기 화학식에서, In the above formula,
    R은 C1-C6의 알킬기, C2-C6의 알케닐기 또는 아랄킬기이고,R is an alkyl group of C 1 -C 6 , an alkenyl group or an aralkyl group of C 2 -C 6 ,
    X는 이탈기이다.X is a leaving group.
  7. 제6항에 있어서, The method of claim 6,
    R은 할로겐으로 치환되거나 치환되지 않은 C1-C6의 알킬기, C2-C6의 알케닐기 또는 벤질이고,R is a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group, or benzyl, optionally substituted with halogen,
    X는 할라이드, 메탄술포네이트, 트리플루오로메탄술포네이트, 벤젠술포네이트 또는 p-톨루엔술포네이트인 점착제 조성물.X is an adhesive composition wherein halide, methanesulfonate, trifluoromethanesulfonate, benzenesulfonate or p-toluenesulfonate.
  8. 제1항에 있어서, 이탈기를 함유한 화합물은 하기 화학식 7 내지 14의 화합물에서 선택되는 점착제 조성물:The pressure-sensitive adhesive composition of claim 1, wherein the compound containing a leaving group is selected from compounds of Formulas 7 to 14:
    [화학식 7][Formula 7]
    Figure PCTKR2015002435-appb-I000023
    Figure PCTKR2015002435-appb-I000023
    [화학식 8][Formula 8]
    Figure PCTKR2015002435-appb-I000024
    Figure PCTKR2015002435-appb-I000024
    [화학식 9][Formula 9]
    Figure PCTKR2015002435-appb-I000025
    Figure PCTKR2015002435-appb-I000025
    [화학식 10][Formula 10]
    Figure PCTKR2015002435-appb-I000026
    Figure PCTKR2015002435-appb-I000026
    [화학식 11][Formula 11]
    Figure PCTKR2015002435-appb-I000027
    Figure PCTKR2015002435-appb-I000027
    [화학식 12][Formula 12]
    Figure PCTKR2015002435-appb-I000028
    Figure PCTKR2015002435-appb-I000028
    [화학식 13][Formula 13]
    Figure PCTKR2015002435-appb-I000029
    Figure PCTKR2015002435-appb-I000029
    [화학식 14][Formula 14]
    Figure PCTKR2015002435-appb-I000030
    Figure PCTKR2015002435-appb-I000030
  9. 제1항에 있어서, 가교제 및 실란커플링제를 추가로 포함하는 점착제 조성물.The pressure-sensitive adhesive composition of claim 1, further comprising a crosslinking agent and a silane coupling agent.
  10. 제1항 내지 제9항 중 어느 한 항에 따른 점착제 조성물로 이루어진 점착제층이 적층된 편광판.The polarizing plate in which the adhesive layer which consists of an adhesive composition of any one of Claims 1-9 was laminated | stacked.
  11. 액정셀의 적어도 한 면에 제10항에 따른 편광판이 구비된 액정표시장치.A liquid crystal display device comprising a polarizing plate according to claim 10 on at least one side of a liquid crystal cell.
  12. 3차 아민기를 함유하는 아크릴계 공중합체와 이탈기를 함유한 화합물을 친핵성 치환반응시키는 단계를 포함하는 이온성 작용기 함유 아크릴계 공중합체의 제조방법. A method for producing an ionic functional group-containing acrylic copolymer comprising the step of nucleophilic substitution reaction of the acrylic copolymer containing a tertiary amine group and the compound containing a leaving group.
PCT/KR2015/002435 2014-03-19 2015-03-13 Adhesive composition and polarizing plate comprising same WO2015141986A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2014-0032374 2014-03-19
KR1020140032374A KR102145806B1 (en) 2014-03-19 2014-03-19 Adhesive Composition and Polarizing Plate Comprising the Same

Publications (1)

Publication Number Publication Date
WO2015141986A1 true WO2015141986A1 (en) 2015-09-24

Family

ID=54144895

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2015/002435 WO2015141986A1 (en) 2014-03-19 2015-03-13 Adhesive composition and polarizing plate comprising same

Country Status (3)

Country Link
KR (1) KR102145806B1 (en)
TW (1) TW201536883A (en)
WO (1) WO2015141986A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06322342A (en) * 1993-05-12 1994-11-22 Konishi Kk Two-pack adhesive composition
JP2005325180A (en) * 2004-05-12 2005-11-24 Denki Kagaku Kogyo Kk Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet
JP2007046018A (en) * 2005-08-12 2007-02-22 Denki Kagaku Kogyo Kk Pressure-sensitive adhesive, pressure-sensitive adhesive sheet obtained using the same, and manufacturing method of electronic component using pressure-sensitive adhesive sheet
KR20080047031A (en) * 2006-11-24 2008-05-28 동우 화인켐 주식회사 Antistatic pressure sensitive adhesive composition comprising sulfone or sulfoxide, and polarized plate comprising the same
KR20090016241A (en) * 2007-08-10 2009-02-13 동우 화인켐 주식회사 Pressure sensitive adhesive composition and polized plate comprising the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5248181B2 (en) 2007-04-20 2013-07-31 日本合成化学工業株式会社 Method for producing acrylic resin, pressure-sensitive adhesive composition using acrylic resin, and pressure-sensitive adhesive, pressure-sensitive adhesive sheet

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06322342A (en) * 1993-05-12 1994-11-22 Konishi Kk Two-pack adhesive composition
JP2005325180A (en) * 2004-05-12 2005-11-24 Denki Kagaku Kogyo Kk Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet
JP2007046018A (en) * 2005-08-12 2007-02-22 Denki Kagaku Kogyo Kk Pressure-sensitive adhesive, pressure-sensitive adhesive sheet obtained using the same, and manufacturing method of electronic component using pressure-sensitive adhesive sheet
KR20080047031A (en) * 2006-11-24 2008-05-28 동우 화인켐 주식회사 Antistatic pressure sensitive adhesive composition comprising sulfone or sulfoxide, and polarized plate comprising the same
KR20090016241A (en) * 2007-08-10 2009-02-13 동우 화인켐 주식회사 Pressure sensitive adhesive composition and polized plate comprising the same

Also Published As

Publication number Publication date
KR102145806B1 (en) 2020-08-19
TW201536883A (en) 2015-10-01
KR20150109218A (en) 2015-10-01

Similar Documents

Publication Publication Date Title
WO2016032108A1 (en) Adhesive film and display member using same
WO2013085132A1 (en) Photocurable adhesive composition, and display device comprising same
WO2012111963A2 (en) Substrate film and method for manufacturing same
WO2010120105A2 (en) Adhesive composition
WO2014204249A1 (en) Adhesive composition
WO2018159923A1 (en) Window film, window film laminate comprising same and image display device
WO2014204253A1 (en) Adhesive composition
WO2018159918A1 (en) Window substrate and image display device comprising same
WO2017010765A1 (en) Compound
WO2009131393A2 (en) Adhesive composition, and polarizing plates and lcds utilizing the adhesive composition
WO2014038810A1 (en) Adhesive composition
WO2017018672A1 (en) Adhesive composition for polarizing plate, adhesive film for polarizing plate manufactured therefrom, polarizing plate comprising the same and optical display device comprising the same
WO2017183940A1 (en) Optical adhesive composition and optical adhesive film comprising adhesive layer containing thermally cured product of optical adhesive composition
WO2015099279A1 (en) Adhesive composition containing ionic anti-static agent
WO2015147498A1 (en) Adhesive composition and polarizing plate comprising same
WO2014027766A1 (en) Acryl-based adhesive composition
WO2015141986A1 (en) Adhesive composition and polarizing plate comprising same
WO2020091450A1 (en) Adhesive composition, optical film comprising same, and organic electronic element and display device, both of which comprise same
WO2015190748A1 (en) Adhesive composition and polarizing plate comprising same
WO2015190826A1 (en) Adhesive composition having anti-static properties, and polarizing plate manufactured using same
WO2014038815A1 (en) Adhesive composition
WO2019132455A1 (en) Adhesive composition and protective film using same
WO2022050675A1 (en) Adhesive film, optical member comprising same, and optical display device comprising same
WO2023096413A1 (en) Adhesive
WO2020111821A1 (en) Coating composition

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: 15765097

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15765097

Country of ref document: EP

Kind code of ref document: A1