WO2015099285A1 - Adhesive composition - Google Patents

Adhesive composition Download PDF

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Publication number
WO2015099285A1
WO2015099285A1 PCT/KR2014/010650 KR2014010650W WO2015099285A1 WO 2015099285 A1 WO2015099285 A1 WO 2015099285A1 KR 2014010650 W KR2014010650 W KR 2014010650W WO 2015099285 A1 WO2015099285 A1 WO 2015099285A1
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WO
WIPO (PCT)
Prior art keywords
formula
adhesive composition
pressure
sensitive adhesive
meth
Prior art date
Application number
PCT/KR2014/010650
Other languages
French (fr)
Korean (ko)
Inventor
최한영
유민근
허지혜
Original Assignee
동우화인켐 주식회사
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Application filed by 동우화인켐 주식회사 filed Critical 동우화인켐 주식회사
Publication of WO2015099285A1 publication Critical patent/WO2015099285A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition excellent in durability.
  • the liquid crystal display device is composed of a liquid crystal cell containing a liquid crystal and a polarizing plate, which is mainly bonded by forming an adhesive layer on one surface of the polarizing plate.
  • a retardation plate, a wide viewing angle compensation plate, or a brightness enhancement film is additionally attached to the polarizing plate through an adhesive or the like.
  • a polarizing plate is a structure containing an iodine compound or a dichroic polarizing material arranged in a predetermined direction in a stretched polyvinyl alcohol (PVA) molecular chain or a dehydration reaction of a polyvinyl alcohol film or polyvinyl chloride (polyvinyl chloride).
  • chloride, PVC) film polarizer having a polyene (Polyene) formed by the dehydrochlorination reaction, and a transparent protective film for protecting the polarizer on at least one side of the polarizer, for example triacetyl cellulose (Triacetyl cellulose,
  • TAC triacetyl cellulose
  • the pressure-sensitive adhesive layer and the release film for attaching to the liquid crystal cell are sequentially stacked, and the other side of the polarizer or the transparent protective film has a multilayer structure in which a surface protective film is laminated.
  • the polarizing plate and the liquid crystal cell may be exposed to a high temperature and high humidity environment during the manufacturing process, transportation, or handling after bonding, and thus may cause problems such as bubbles or peeling between the bonding sites, thus maintaining excellent adhesion in harsh environments.
  • a pressure-sensitive adhesive composition There is a need for a pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive composition having such excellent durability has not yet been established.
  • Korean Laid-Open Patent Publication No. 2008-73883 discloses an acrylic pressure-sensitive adhesive composition for a polarizing plate.
  • Patent Document 1 Korean Patent Publication No. 2008-73883
  • An object of the present invention is to provide an adhesive composition with remarkably improved durability.
  • a pressure-sensitive adhesive composition comprising an acrylic copolymer and a crosslinking agent of the following general formula (1):
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms).
  • the crosslinking agent of Formula 1 is at least one selected from the group consisting of Formula 2 to 6, the pressure-sensitive adhesive composition:
  • Pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition of any one of 1 to 3.
  • Polarizing plate comprising a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition of any one of 1 to 3 on at least one side.
  • Image display device including the polarizing plate of the above five.
  • the pressure-sensitive adhesive composition of the present invention has markedly improved durability. Thereby, excellent adhesive force can be maintained even in severe conditions, such as high temperature, high humidity.
  • the present invention relates to a pressure-sensitive adhesive composition
  • a pressure-sensitive adhesive composition comprising an acrylic copolymer and a crosslinking agent of the formula (1), which has a markedly improved durability and can maintain excellent adhesion even under severe conditions such as high temperature and high humidity.
  • the adhesive composition of this invention contains an acryl-type copolymer.
  • the acrylic copolymer is not particularly limited and may be one known in the art, and may be, for example, a polymerized product including a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and a polymerizable monomer having a crosslinkable functional group.
  • (meth) acrylate means acrylate and methacrylate.
  • Examples of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms include n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth).
  • the polymerizable monomer having a crosslinkable functional group is a component for reinforcing the cohesive force or adhesive strength of the pressure-sensitive adhesive composition by chemical bonding and imparting durability and cutting property.
  • the monomer etc. which have a tertiary amine group are mentioned, These can be used individually or in mixture of 2 or more types. In view of excellent reactivity with the crosslinking agent to be described later may be preferably a monomer having a hydroxy 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; Succinic anhydride ring-opening adduct of 2-hydroxyalkyl (meth) acrylate with 2-3 carbon atoms of an alkyl group, Succinic anhydride ring opening adduct of hydroxyalkylene glycol (meth) acrylate with 2-4 carbon atoms of an alkylene group And a compound obtained by ring-opening addition of succinic anhydride to a caprolactone adduct of 2-hydroxyalkyl (meth) acrylate having 2 or 3 carbon atoms of an alkyl group, and among these, (meth) acrylic acid is preferable.
  • (meth) acrylic acid is preferable.
  • Examples of the monomer having an amide group include (meth) acrylamide, N-isopropylacrylamide, N-tert-butylacrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (meth) acrylamide, 6 -Hydroxyhexyl (meth) acrylamide, 8-hydroxyoctyl (meth) acrylamide, 2-hydroxyethylhexyl (meth) acrylamide, etc. are mentioned, Among these, (meth) acrylamide is preferable.
  • Monomers having a tertiary amine group include N, N- (dimethylamino) ethyl (meth) acrylate, N, N- (diethylamino) ethyl (meth) acrylate, and N, N- (dimethylamino) propyl ( Meth) acrylate, etc. are mentioned.
  • the content and the mixing ratio of the monomer are not particularly limited, and for example, the polymerizable monomer having a crosslinkable functional group may be included in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms. Preferably, it is 0.1-8 weight part. If the content is less than 0.05 parts by weight, the cohesive force of the pressure-sensitive adhesive may be reduced, the durability may be lowered. If the content is more than 10 parts by weight, the adhesive strength is lowered and durability may be lowered by a high gel fraction.
  • the acrylic copolymer may further include a polymerizable monomer known in the art in addition to the above monomers in a range that does not lower the adhesive strength, such as 10 wt% or less of the total weight of the monomers.
  • 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 preferably has a weight average molecular weight (polystyrene equivalent, Mw) measured by gel permeation chromatography (GPC) of 50,000 to 2 million, more preferably 400,000 to 2 million. If the weight average molecular weight is less than 50,000, there is a lack of cohesion between the copolymers may cause problems in adhesion durability, if the weight average molecular weight is more than 2 million may require a large amount of dilution solvent to ensure fairness during coating.
  • Mw polystyrene equivalent
  • the pressure-sensitive adhesive composition of the present invention further includes a crosslinking agent of the following Chemical Formula 1:
  • R 1 and R 2 are independently alkoxy giim a hydrogen atom, a halogen atom, a C 1 -C 5 alkyl group or a group having 1 to 5 carbon atoms of each other).
  • the crosslinking agent of the formula (1) is very excellent in crosslinking efficiency, it is possible to improve the cohesive force of the pressure-sensitive adhesive composition of the present invention.
  • the reactivity to the crosslinking reaction is improved can exhibit a more excellent crosslinking efficiency. This significantly improves the durability of the pressure-sensitive adhesive composition.
  • the crosslinking efficiency is excellent, even if only a small amount is added as compared to the conventional crosslinking agent, the durability improvement effect is more excellent.
  • the compound of Formula 1 is not particularly limited and may be, for example, at least one compound selected from the group consisting of Formulas 2-6:
  • the compound of formula 1 is not particularly limited in the preparation method, and may be prepared via, for example, a compound of formula 8 using the compound of formula 7 as a starting material:
  • R is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms).
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms).
  • the method for obtaining the compound of formula 8 from the compound of formula 7 is not particularly limited, and can be prepared, for example, by reacting the compound of formula 7 with formaldehyde in the presence of an acid.
  • the reaction may be carried out under a solvent conventionally used in the art, for example, may be used a polar solvent such as water, alcohol having an alkyl group having 1 to 6 carbon atoms, ether.
  • a solvent conventionally used in the art for example, may be used a polar solvent such as water, alcohol having an alkyl group having 1 to 6 carbon atoms, ether.
  • the acid which can be used is not specifically limited, For example, hydrochloric acid, a sulfuric acid, phosphoric acid, etc. are mentioned.
  • the compound of formula 1 may be prepared from the compound of formula 8 obtained.
  • the method is not particularly limited and can be prepared, for example, by dissolving the compound of formula 8 in an organic solvent and reacting with an isocyanate in the presence of an acid.
  • the organic solvent which can be used is not specifically limited, For example, a non-hydrolyzable organic solvent like chlorobenzene, toluene, xylene, etc. are mentioned.
  • an isocyanate agent is a compound which makes an amino group an isocyanate group
  • an isocyanate agent known in the art may be used, for example, a compound represented by the following formula (9):
  • R 1 and R 2 are each independently a halogen atom or OR 3 ;
  • R 3 is an alkyl group having 1 to 5 carbon atoms substituted with at least one halogen atom).
  • R 3 is an alkyl group having 1 to 5 carbon atoms substituted with at least one halogen atom, for example, one carbon is substituted with 1 to 3 halogens, or a plurality of carbons are substituted with 1 to 3 halogens It may be a structure, which is not particularly limited.
  • the content of the crosslinking agent of Formula 1 is not particularly limited, and may be included, for example, in an amount of 0.1 to 1 part by weight based on 100 parts by weight of the acrylic copolymer. If the content is less than 0.1 part by weight, the effect of improving the cohesion may be insufficient, so that the effect of improving the durability may be insignificant. If the content is more than 1 part by weight, the adhesive force may be lowered due to a decrease in the initial wettability due to excessive increase of the cohesion, which may result in poor peeling. Preferably 0.1 to 0.5 parts by weight may be included.
  • the pressure-sensitive adhesive composition of the present invention may further include a silane coupling agent.
  • the silane coupling agent covalently bonds to the adherend surface polar group, thereby improving adhesion.
  • silane coupling agent is not particularly limited and silane coupling agents known in the art can be used, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltri Methoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethoxysildimethoxysilane, 3-chloropropyltrimethoxysilane , 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri
  • the content of the silane coupling agent is not particularly limited, and may be included, for example, in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the acrylic copolymer. If the content is less than 0.01 parts by weight, the effect of improving the adhesive strength may be insignificant, and if it exceeds 10 parts by weight, the cohesion may be excessively increased and the durability of the adhesive properties, such as adhesive strength, may be lowered.
  • the pressure-sensitive adhesive composition of the present invention may further include additives such as antioxidants, corrosion inhibitors, antifoaming agents, fillers, antistatic agents, and the like, which are commonly used in the art, without departing from the object of the present invention.
  • additives such as antioxidants, corrosion inhibitors, antifoaming agents, fillers, antistatic agents, and the like, which are commonly used in the art, without departing from the object of the present invention.
  • the present invention provides a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition.
  • the thickness of the adhesive layer is not particularly limited, and may be, for example, 0.5 to 50 ⁇ m.
  • the adhesive sheet of the present invention includes an adhesive layer formed on at least one surface of the release film.
  • the pressure-sensitive adhesive layer can be formed by coating the pressure-sensitive adhesive composition on at least one surface of the release film.
  • the coating method is not particularly limited, and methods known in the art may be used. For example, methods such as a bar coater, air knife, gravure, reverse roll, kiss roll, spray, blade, die coater, casting, and spin coating may be used. It is available.
  • the release film is not particularly limited, and a release film commonly used in an adhesive sheet may be used, for example, polyester resins such as polyethylene terephthalate, polybutyrene terephthalate, polyethylene naphthalate, and polybutylene naphthalate; Polyimide resins; Acrylic resins; Styrene resins such as polystyrene and acrylonitrile-styrene; Polycarbonate resins; Polylactic acid resins; Polyurethane resins; Polyolefin resins such as polyethylene, polypropylene, ethylene-propylene copolymers; Vinyl resins such as polyvinyl chloride and polyvinylidene chloride; Polyamide resins; Sulfone resins; Polyether ether ketone resins; Allyl resins; Or it may be formed of a mixture of the resin.
  • polyester resins such as polyethylene terephthalate, polybutyrene terephthalate, polyethylene naphthalate, and polybutylene
  • the thickness of the release film is not particularly limited, and may be, for example, 5 to 500 ⁇ m, and preferably 10 to 100 ⁇ m.
  • the present invention provides a polarizing plate including a pressure-sensitive adhesive layer formed on at least one surface of the pressure-sensitive adhesive composition.
  • the polarizing plate of the present invention includes a polarizer, a protective film bonded to at least one surface of the polarizer, and an adhesive layer formed of the pressure-sensitive adhesive composition on the protective film.
  • the polarizer may be a polarizer known in the art, and for example, may be manufactured by swelling, dyeing, crosslinking, stretching, washing, drying, and the like of a polyvinyl alcohol-based film.
  • the protective film is not particularly limited as long as the film is excellent in transparency, mechanical strength, thermal stability, moisture shielding, and isotropy.
  • polyester film such as polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate; Cellulose films such as diacetyl cellulose and triacetyl cellulose; Polycarbonate film; Acrylic films such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene films such as polystyrene and acrylonitrile-styrene copolymers; Polyolefin-based film; Vinyl chloride film; Polyamide films such as nylon and aromatic polyamides; Imide film; Sulfone film; Polyether ketone film; Sulfided polyphenylene-based films; Vinyl alcohol film; Vinylidene chloride-based film; Vinyl butyral film; Allylate film; Polyoxymethylene film; Urethane film; Epoxy film; Silicone film etc. are mentioned.
  • the adhesive layer may be directly coated on the protective film, or may be formed by attaching the adhesive sheet to the protective film.
  • the present invention provides an image display device including the polarizing plate.
  • the image display apparatus of the present invention may further include a configuration known in the art in addition to the polarizing plate.
  • Nitrogen gas is refluxed, 85 parts by weight of n-butyl acrylate, 7 parts by weight of methacrylate, 5 parts by weight of 2-hydroxyethyl acrylate, 3 parts of acrylic acid in a 1 L reactor equipped with a cooling device for easy temperature control. After adding a monomer mixture consisting of parts, 100 parts by weight of ethyl acetate was added as a solvent. Nitrogen gas was then purged for 1 hour to remove oxygen and then held at 62 ° C. After the mixture was uniformly mixed, 0.07 parts by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator, and reacted for 8 hours to prepare an acrylic copolymer (a weight average molecular weight of about 1 million).
  • AIBN azobisisobutyronitrile
  • Nitrogen gas is refluxed, 90 parts by weight of n-butyl acrylate, 5 parts by weight of methacrylate, 4 parts by weight of 2-hydroxyethyl acrylate, 1 weight of acrylic acid in a 1 L reactor equipped with a cooling device for easy temperature control. After adding a monomer mixture consisting of parts, 100 parts by weight of ethyl acetate was added as a solvent. Nitrogen gas was then purged for 1 hour to remove oxygen and then held at 62 ° C. After the mixture was uniformly mixed, 0.07 parts by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator, and reacted for 8 hours to prepare an acrylic copolymer (a weight average molecular weight of about 1 million).
  • AIBN azobisisobutyronitrile
  • the pressure-sensitive adhesive compositions of Examples and Comparative Examples were applied on a release film coated with a silicone release agent so as to have a thickness of 25 ⁇ m, and dried at 100 ° C. for 1 minute to form an adhesive layer.
  • the adhesive film was prepared by laminating a release film on the adhesive layer.
  • the release film of the prepared pressure-sensitive adhesive sheet was laminated on the adhesive layer iodine-based polarizing film (total thickness 185 ⁇ m) bonded to the triacetyl cellulose-based protective film on both sides by adhesive processing to prepare a polarizing plate.
  • the prepared polarizing plate was stored under curing conditions at 23 ° C. and 60% RH.
  • Each polarizing plate was cut to a size of 90 mm x 170 mm and the release film was peeled off, and then attached to both surfaces of the glass substrate (110 mm x 190 mm x 0.7 mm) so that the absorption axes of the polarizing plates were perpendicular to each other.
  • the attachment was applied at a pressure of 5 kg / cm 2 and was performed in a clean room to prevent bubbles or foreign substances from being formed.
  • the heat resistance of the laminate was evaluated by observing the occurrence of bubbles or peeling after leaving for 500 hours at a temperature of 80 °C.
  • the heat and humidity evaluation was evaluated by observing the occurrence of bubbles or peeling after 500 hours left at 60 °C 90% humidity conditions.
  • the pressure-sensitive adhesive composition of Examples 1 to 9 was very excellent in heat resistance and heat and moisture resistance.

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

Abstract

The present invention related to an adhesive composition, and more specifically, to an adhesive composition comprising an acrylic copolymer and a cross-linking agent represented by chemical formula 1, thereby having significantly improved durability which enables the adhesive composition to maintain excellent adhesive force even under extreme conditions such as high temperature and high humidity.

Description

점착제 조성물Pressure-sensitive adhesive composition
본 발명은 내구성이 우수한 점착제 조성물에 관한 것이다.The present invention relates to a pressure-sensitive adhesive composition excellent in durability.
액정표시장치는 액정을 포함하고 있는 액정셀과 편광판으로 구성되며, 이는 주로 편광판의 일면에 점착층을 형성하여 접합된다. 이외에도 액정표시장치의 기능을 향상시키기 위하여 위상차판, 광시야각 보상판, 또는 휘도향상 필름 등을 부가적으로 편광판에 접착제 등을 통해 부착하여 사용한다.The liquid crystal display device is composed of a liquid crystal cell containing a liquid crystal and a polarizing plate, which is mainly bonded by forming an adhesive layer on one surface of the polarizing plate. In addition, in order to improve the function of the liquid crystal display, a retardation plate, a wide viewing angle compensation plate, or a brightness enhancement film is additionally attached to the polarizing plate through an adhesive or the like.
일반적으로 편광판은 연신된 폴리비닐알콜계(polyvinyl alcohol, PVA) 분자사슬에 일정한 방향으로 배열된 요오드계 화합물 또는 이색성 편광물질을 포함하는 구조 또는 폴리비닐알콜 필름의 탈수반응 또는 폴리비닐클로라이드(polyvinyl chloride, PVC) 필름의 탈염산 반응에 의해 폴리엔(Polyene)을 형성한 구조의 편광자와, 상기 편광자의 적어도 한 면에 편광자를 보호하기 위한 투명보호필름, 예를 들어 트리아세틸셀룰로오스(Triacetyl cellulose, TAC)로 대표되는 필름이 적층된 구조를 갖는다. 상기, 편광자 또는 투명보호필름의 한 면에는 액정셀에 부착하기 위한 점착제층과 이형필름이 순서대로 적층되며, 상기 편광자 또는 투명보호필름의 다른 한 면에는 표면보호필름이 적층되는 다층 구조를 갖는다.In general, a polarizing plate is a structure containing an iodine compound or a dichroic polarizing material arranged in a predetermined direction in a stretched polyvinyl alcohol (PVA) molecular chain or a dehydration reaction of a polyvinyl alcohol film or polyvinyl chloride (polyvinyl chloride). chloride, PVC) film polarizer having a polyene (Polyene) formed by the dehydrochlorination reaction, and a transparent protective film for protecting the polarizer on at least one side of the polarizer, for example triacetyl cellulose (Triacetyl cellulose, The film represented by TAC) has a laminated structure. On one side of the polarizer or the transparent protective film, the pressure-sensitive adhesive layer and the release film for attaching to the liquid crystal cell are sequentially stacked, and the other side of the polarizer or the transparent protective film has a multilayer structure in which a surface protective film is laminated.
이러한 편광판과 액정셀은 접합 이후의 제조 공정, 운송 또는 취급 중에 고온 다습한 환경에 노출되어 접합 부위 사이에 기포가 발생하거나 박리되는 등의 문제가 발생할 수 있으므로, 가혹 환경에서도 점착력을 유지할 수 있도록 우수한 내구성을 갖는 점착제 조성물이 요구된다. 그러나, 이러한 우수한 내구성을 갖는 점착제 조성물은 아직 확립되지 않은 실정이다.The polarizing plate and the liquid crystal cell may be exposed to a high temperature and high humidity environment during the manufacturing process, transportation, or handling after bonding, and thus may cause problems such as bubbles or peeling between the bonding sites, thus maintaining excellent adhesion in harsh environments. There is a need for a pressure-sensitive adhesive composition. However, the pressure-sensitive adhesive composition having such excellent durability has not yet been established.
한국공개특허 제2008-73883호에는 편광판용 아크릴계 점착제 조성물이 개시되어 있다.Korean Laid-Open Patent Publication No. 2008-73883 discloses an acrylic pressure-sensitive adhesive composition for a polarizing plate.
[선행기술문헌][Preceding technical literature]
[특허문헌][Patent Documents]
(특허문헌 1) 한국공개특허 제2008-73883호(Patent Document 1) Korean Patent Publication No. 2008-73883
본 발명은 내구성이 현저히 개선된 점착제 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide an adhesive composition with remarkably improved durability.
1. 아크릴계 공중합체 및 하기 화학식 1의 가교제를 포함하는, 점착제 조성물:1.A pressure-sensitive adhesive composition comprising an acrylic copolymer and a crosslinking agent of the following general formula (1):
[화학식 1][Formula 1]
Figure PCTKR2014010650-appb-I000001
Figure PCTKR2014010650-appb-I000001
(식 중, R1 및 R2는 서로 독립적으로 수소 원자, 할로겐 원자, 탄소수 1 내지 5의 알킬기 또는 탄소수 1 내지 5의 알콕시기임).(Wherein R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms).
2. 위 1에 있어서, 상기 화학식 1의 가교제는 하기 화학식 2 내지 6으로 이루어진 군에서 선택된 적어도 하나인, 점착제 조성물:2. In the above 1, wherein the crosslinking agent of Formula 1 is at least one selected from the group consisting of Formula 2 to 6, the pressure-sensitive adhesive composition:
[화학식 2][Formula 2]
Figure PCTKR2014010650-appb-I000002
Figure PCTKR2014010650-appb-I000002
[화학식 3][Formula 3]
Figure PCTKR2014010650-appb-I000003
Figure PCTKR2014010650-appb-I000003
[화학식 4][Formula 4]
Figure PCTKR2014010650-appb-I000004
Figure PCTKR2014010650-appb-I000004
[화학식 5][Formula 5]
Figure PCTKR2014010650-appb-I000005
Figure PCTKR2014010650-appb-I000005
[화학식 6][Formula 6]
Figure PCTKR2014010650-appb-I000006
Figure PCTKR2014010650-appb-I000006
3. 위 1에 있어서, 상기 화학식 1의 가교제는 아크릴계 공중합체 100중량부에 대하여 0.1 내지 1중량부로 포함되는, 점착제 조성물.3. In the above 1, wherein the crosslinking agent of Formula 1 is included in 0.1 to 1 parts by weight based on 100 parts by weight of the acrylic copolymer, pressure-sensitive adhesive composition.
4. 위 1 내지 3 중 어느 한 항의 점착제 조성물로 형성된 점착층을 포함하는 점착 시트.4. Pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition of any one of 1 to 3.
5. 적어도 일면에 위 1 내지 3 중 어느 한 항의 점착제 조성물로 형성된 점착층을 포함하는 편광판.5. Polarizing plate comprising a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition of any one of 1 to 3 on at least one side.
6. 위 5의 편광판을 포함하는 화상 표시 장치.6. Image display device including the polarizing plate of the above five.
본 발명의 점착제 조성물은 현저히 개선된 내구성을 갖는다. 이에 따라 고온 고습 등의 가혹 조건에서도 우수한 점착력을 유지할 수 있다.The pressure-sensitive adhesive composition of the present invention has markedly improved durability. Thereby, excellent adhesive force can be maintained even in severe conditions, such as high temperature, high humidity.
본 발명은 아크릴계 공중합체 및 화학식 1의 가교제를 포함함으로써, 현저히 개선된 내구성을 가져 고온 고습 등의 가혹 조건에서도 우수한 점착력을 유지할 수 있는 점착제 조성물에 관한 것이다.The present invention relates to a pressure-sensitive adhesive composition comprising an acrylic copolymer and a crosslinking agent of the formula (1), which has a markedly improved durability and can maintain excellent adhesion even under severe conditions such as high temperature and high humidity.
이하 본 발명을 상세히 설명하기로 한다.Hereinafter, the present invention will be described in detail.
<점착제 조성물><Adhesive Composition>
본 발명의 점착제 조성물은 아크릴계 공중합체를 포함한다.The adhesive composition of this invention contains an acryl-type copolymer.
아크릴계 공중합체는 특별히 한정되지 않고 당 분야에 공지된 것이 사용될 수 있으며, 예를 들면 탄소수 1 내지 12의 알킬기를 갖는 (메타)아크릴레이트 단량체 및 가교 가능한 관능기를 갖는 중합성 단량체를 포함하여 중합된 것일 수 있다. 여기서, (메타)아크릴레이트는 아크릴레이트 및 메타크릴레이트를 의미한다.The acrylic copolymer is not particularly limited and may be one known in the art, and may be, for example, a polymerized product including a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and a polymerizable monomer having a crosslinkable functional group. Can be. Here, (meth) acrylate means acrylate and methacrylate.
상기 탄소수 1 내지 12의 알킬기를 갖는 (메타)아크릴레이트 단량체로는 n-부틸(메타)아크릴레이트, 2-부틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트, 2-에틸헥실(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, 노닐(메타)아크릴레이트, 데실(메타)아크릴레이트, 라우릴(메타)아크릴레이트 등을 들 수 있으며, 이들 중에서 n-부틸아크릴레이트, 2-에틸헥실아크릴레이트 또는 이들의 혼합물이 바람직하다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.Examples of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms include n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (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, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, and the like, among which n-butyl acrylate and 2-ethylhexyl acrylate Or mixtures thereof. These can be used individually or in mixture of 2 or more types.
가교 가능한 관능기를 갖는 중합성 단량체는 화학 결합에 의해 점착제 조성물의 응집력 또는 점착 강도를 보강하여 내구성과 절단성을 부여하기 위한 성분으로서, 예컨대 히드록시기를 갖는 단량체, 카르복시기를 갖는 단량체, 아미드기를 갖는 단량체, 3차 아민기를 갖는 단량체 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다. 후술할 가교제와의 우수한 반응성의 측면에서 바람직하게는 히드록시기를 갖는 단량체일 수 있다.The polymerizable monomer having a crosslinkable functional group is a component for reinforcing the cohesive force or adhesive strength of the pressure-sensitive adhesive composition by chemical bonding and imparting durability and cutting property. The monomer etc. which have a tertiary amine group are mentioned, These can be used individually or in mixture of 2 or more types. In view of excellent reactivity with the crosslinking agent to be described later may be preferably a monomer having a hydroxy group.
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, 4-히드록시부틸비닐에테르, 5-히드록시펜틸비닐에테르, 6-히드록시헥실비닐에테르, 7-히드록시헵틸비닐에테르, 8-히드록시옥틸비닐에테르, 9-히드록시노닐비닐에테르, 및 10-히드록시데실비닐에테르 등을 들 수 있으며, 이들 중에서 4-히드록시부틸비닐에테르가 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 ( Meta) acrylate, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 7-hydroxyheptyl vinyl ether, 8-hydroxyoctyl vinyl ether, 9-hydroxynonyl Vinyl ether, 10-hydroxydecyl vinyl ether, etc. are mentioned, Among these, 4-hydroxybutyl vinyl ether 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 무수 호박산 개환 부가체, 및 알킬기의 탄소수가 2 또는 3인 2-히드록시알킬(메타)아크릴레이트의 카프로락톤 부가체에 무수 호박산을 개환 부가시킨 화합물 등을 들 수 있으며, 이들 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; Succinic anhydride ring-opening adduct of 2-hydroxyalkyl (meth) acrylate with 2-3 carbon atoms of an alkyl group, Succinic anhydride ring opening adduct of hydroxyalkylene glycol (meth) acrylate with 2-4 carbon atoms of an alkylene group And a compound obtained by ring-opening addition of succinic anhydride to a caprolactone adduct of 2-hydroxyalkyl (meth) acrylate having 2 or 3 carbon atoms of an alkyl group, and among these, (meth) acrylic acid is preferable.
아미드기를 갖는 단량체로는 (메타)아크릴아미드, N-이소프로필아크릴아미드, N-3차부틸아크릴아미드, 3-히드록시프로필(메타)아크릴아미드, 4-히드록시부틸(메타)아크릴아미드, 6-히드록시헥실(메타)아크릴아미드, 8-히드록시옥틸(메타)아크릴아미드, 및 2-히드록시에틸헥실(메타)아크릴아미드 등을 들 수 있으며, 이들중에서 (메타)아크릴아미드가 바람직하다. Examples of the monomer having an amide group include (meth) acrylamide, N-isopropylacrylamide, N-tert-butylacrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (meth) acrylamide, 6 -Hydroxyhexyl (meth) acrylamide, 8-hydroxyoctyl (meth) acrylamide, 2-hydroxyethylhexyl (meth) acrylamide, etc. are mentioned, Among these, (meth) acrylamide is preferable.
3차 아민기를 갖는 단량체로는 N,N-(디메틸아미노)에틸(메타)아크릴레이트, N,N-(디에틸아미노)에틸(메타)아크릴레이트, 및 N,N-(디메틸아미노)프로필(메타)아크릴레이트 등을 들 수 있다. Monomers having a tertiary amine group include N, N- (dimethylamino) ethyl (meth) acrylate, N, N- (diethylamino) ethyl (meth) acrylate, and N, N- (dimethylamino) propyl ( Meth) acrylate, etc. are mentioned.
단량체의 함량 및 혼합비는 특별히 한정되지 않으며, 예를 들면 가교 가능한 관능기를 갖는 중합성 단량체가 탄소수 1 내지 12의 알킬기를 갖는 (메타)아크릴레이트 단량체 100중량부에 대하여 0.05 내지 10중량부로 포함될 수 있으며, 바람직하게는 0.1 내지 8중량부인 것이 좋다. 함량이 0.05중량부 미만인 경우 점착제의 응집력이 작아지게 되어 내구성이 저하될 수 있으며, 10중량부 초과인 경우 높은 겔분율에 의해 점착력이 떨어지고 내구성이 저하될 수 있다.The content and the mixing ratio of the monomer are not particularly limited, and for example, the polymerizable monomer having a crosslinkable functional group may be included in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms. Preferably, it is 0.1-8 weight part. If the content is less than 0.05 parts by weight, the cohesive force of the pressure-sensitive adhesive may be reduced, the durability may be lowered. If the content is more than 10 parts by weight, the adhesive strength is lowered and durability may be lowered by a high gel fraction.
아크릴계 공중합체는 상기 단량체들 이외에 당 분야에 공지된 중합성 단량체를 점착력을 저하시키지 않는 범위, 예컨대 전체 단량체 총 중량 중 10중량% 이하로 더 포함할 수 있다.The acrylic copolymer may further include a polymerizable monomer known in the art in addition to the above monomers in a range that does not lower the adhesive strength, such as 10 wt% or less of the total weight of the monomers.
공중합체의 제조방법은 특별히 한정되지 않으며, 당 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.
아크릴계 공중합체는 겔투과크로마토그래피(Gel permeation chromatography, GPC)에 의해 측정된 중량평균분자량(폴리스티렌 환산, Mw)이 5만 내지 200만인 것이 바람직하며, 보다 바람직하기로는 40만 내지 200만인 것이 좋다. 중량평균분자량이 5만 미만인 경우 공중합체 간의 응집력이 부족하여 점착 내구성에 문제를 야기할 수 있고, 200만 초과인 경우 도공 시 공정성을 확보하기 위하여 다량의 희석 용매를 필요로 할 수 있다. The acrylic copolymer preferably has a weight average molecular weight (polystyrene equivalent, Mw) measured by gel permeation chromatography (GPC) of 50,000 to 2 million, more preferably 400,000 to 2 million. If the weight average molecular weight is less than 50,000, there is a lack of cohesion between the copolymers may cause problems in adhesion durability, if the weight average molecular weight is more than 2 million may require a large amount of dilution solvent to ensure fairness during coating.
또한, 본 발명의 점착제 조성물은 하기 하기 화학식 1의 가교제를 더 포함한다:In addition, the pressure-sensitive adhesive composition of the present invention further includes a crosslinking agent of the following Chemical Formula 1:
[화학식 1][Formula 1]
Figure PCTKR2014010650-appb-I000007
Figure PCTKR2014010650-appb-I000007
(식 중, R1 및 R2는 서로 독립적으로 수소 원자, 할로겐 원자, 탄소수 1 내지 5의 알킬기 또는 탄소수 1 내지 5의 알콕시기임).(Wherein, R 1 and R 2 are independently alkoxy giim a hydrogen atom, a halogen atom, a C 1 -C 5 alkyl group or a group having 1 to 5 carbon atoms of each other).
화학식 1의 가교제는 가교 효율이 매우 우수하여, 본 발명의 점착제 조성물의 응집력을 개선할 수 있다. 특히, 히드록시기를 갖는 단량체를 포함하여 중합된 아크릴계 공중합체와 조합하여 사용하는 경우 가교 반응에 대한 반응성이 개선되어 더욱 우수한 가교 효율을 나타낼 수 있다. 이에 따라 점착제 조성물의 내구성이 현저히 개선된다.The crosslinking agent of the formula (1) is very excellent in crosslinking efficiency, it is possible to improve the cohesive force of the pressure-sensitive adhesive composition of the present invention. In particular, when used in combination with a polymerized acrylic copolymer including a monomer having a hydroxy group, the reactivity to the crosslinking reaction is improved can exhibit a more excellent crosslinking efficiency. This significantly improves the durability of the pressure-sensitive adhesive composition.
그리고, 가교 효율이 우수하므로 종래 가교제에 비해 소량만 첨가하여도 내구성 개선 효과가 더 우수하다.In addition, since the crosslinking efficiency is excellent, even if only a small amount is added as compared to the conventional crosslinking agent, the durability improvement effect is more excellent.
화학식 1의 화합물은 특별히 한정되지 않으며, 예를 들면 하기 화학식 2 내지 6으로 이루어진 군에서 선택된 적어도 하나의 화합물일 수 있다:The compound of Formula 1 is not particularly limited and may be, for example, at least one compound selected from the group consisting of Formulas 2-6:
[화학식 2][Formula 2]
Figure PCTKR2014010650-appb-I000008
Figure PCTKR2014010650-appb-I000008
[화학식 3][Formula 3]
Figure PCTKR2014010650-appb-I000009
Figure PCTKR2014010650-appb-I000009
[화학식 4][Formula 4]
Figure PCTKR2014010650-appb-I000010
Figure PCTKR2014010650-appb-I000010
[화학식 5][Formula 5]
Figure PCTKR2014010650-appb-I000011
Figure PCTKR2014010650-appb-I000011
[화학식 6][Formula 6]
Figure PCTKR2014010650-appb-I000012
Figure PCTKR2014010650-appb-I000012
화학식 1의 화합물은 제조 방법은 특별히 한정되지 않으며, 예를 들면 하기 화학식 7의 화합물을 시작 물질로 하여, 화학식 8의 화합물을 거쳐 제조될 수 있다:The compound of formula 1 is not particularly limited in the preparation method, and may be prepared via, for example, a compound of formula 8 using the compound of formula 7 as a starting material:
[화학식 7][Formula 7]
Figure PCTKR2014010650-appb-I000013
Figure PCTKR2014010650-appb-I000013
(식 중, R은 수소 원자, 할로겐 원자, 탄소수 1 내지 5의 알킬기 또는 탄소수 1 내지 5의 알콕시기임).(Wherein R is a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms).
[화학식 8][Formula 8]
Figure PCTKR2014010650-appb-I000014
Figure PCTKR2014010650-appb-I000014
(식 중, R1 및 R2는 서로 독립적으로 수소 원자, 할로겐 원자, 탄소수 1 내지 5의 알킬기 또는 탄소수 1 내지 5의 알콕시기임).(Wherein R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms).
화학식 7의 화합물로부터 화학식 8의 화합물을 얻는 방법은 특별히 한정되지 않으며, 예를 들면 산 존재 하에 화학식 7의 화합물을 포름알데히드와 반응시킴으로써 제조할 수 있다.The method for obtaining the compound of formula 8 from the compound of formula 7 is not particularly limited, and can be prepared, for example, by reacting the compound of formula 7 with formaldehyde in the presence of an acid.
상기 반응은 당 분야에 통상적으로 사용되는 용매 하에 수행될 수 있으며, 예를 들면 물, 탄소수 1 내지 6의 알킬기를 갖는 알코올, 에테르 등의 극성 용매를 사용할 수 있다.The reaction may be carried out under a solvent conventionally used in the art, for example, may be used a polar solvent such as water, alcohol having an alkyl group having 1 to 6 carbon atoms, ether.
사용 가능한 산은 특별히 한정되지 않으며, 예를 들면 염산, 황산, 인산 등을 들 수 있다.The acid which can be used is not specifically limited, For example, hydrochloric acid, a sulfuric acid, phosphoric acid, etc. are mentioned.
이후에, 얻어진 화학식 8의 화합물로부터 화학식 1의 화합물을 제조할 수 있다. 그 방법은 특별히 한정되지 않으며, 예를 들면 화학식 8의 화합물을 유기 용매에 용해시키고 산 존재 하에 이소시아네이트화제와 반응시킴으로써 제조할 수 있다.Thereafter, the compound of formula 1 may be prepared from the compound of formula 8 obtained. The method is not particularly limited and can be prepared, for example, by dissolving the compound of formula 8 in an organic solvent and reacting with an isocyanate in the presence of an acid.
사용 가능한 유기 용매는 특별히 한정되지 않으며, 예를 들면 클로로벤젠, 톨루엔, 자일렌 등과 같이 비가수분해성 유기 용제를 들 수 있다.The organic solvent which can be used is not specifically limited, For example, a non-hydrolyzable organic solvent like chlorobenzene, toluene, xylene, etc. are mentioned.
본 명세서에서 이소시아네이트화제는 아미노기를 이소시아네이트기로 만드는 화합물로서, 당 분야에 공지된 이소시아네이트화제가 사용될 수 있으며, 예를 들면 하기 화학식 9의 화합물을 들 수 있다:In the present specification, an isocyanate agent is a compound which makes an amino group an isocyanate group, and an isocyanate agent known in the art may be used, for example, a compound represented by the following formula (9):
[화학식 9][Formula 9]
Figure PCTKR2014010650-appb-I000015
Figure PCTKR2014010650-appb-I000015
(식 중, R1 및 R2는 서로 독립적으로 할로겐 원자 또는 OR3이고; R3는 적어도 하나의 할로겐 원자로 치환된 탄소수 1 내지 5의 알킬기임).(Wherein R 1 and R 2 are each independently a halogen atom or OR 3 ; R 3 is an alkyl group having 1 to 5 carbon atoms substituted with at least one halogen atom).
상기 식 중, R3는 적어도 하나의 할로겐 원자로 치환된 탄소수 1 내지 5의 알킬기로서, 예를 들면 1개의 탄소가 1 내지 3개의 할로겐으로 치환되거나, 다수의 탄소가 1 내지 3개의 할로겐으로 치환된 구조일 수 있고, 이는 특별히 한정되지 않는다.In the above formula, R 3 is an alkyl group having 1 to 5 carbon atoms substituted with at least one halogen atom, for example, one carbon is substituted with 1 to 3 halogens, or a plurality of carbons are substituted with 1 to 3 halogens It may be a structure, which is not particularly limited.
화학식 1의 가교제의 함량은 특별히 한정되지 않으며, 예를 들면 아크릴계 공중합체 100중량부에 대하여 0.1 내지 1중량부로 포함될 수 있다. 함량이 0.1중량부 미만이면 응집력의 향상 효과가 부족하여 내구성 개선 효과가 미미할 수 있고, 1중량부 초과이면 응집력의 지나친 상승에 의한 초기 젖음성의 저하로 점착력이 저하되어 박리불량이 발생할 수 있다. 바람직하게는 0.1 내지 0.5중량부로 포함될 수 있다.The content of the crosslinking agent of Formula 1 is not particularly limited, and may be included, for example, in an amount of 0.1 to 1 part by weight based on 100 parts by weight of the acrylic copolymer. If the content is less than 0.1 part by weight, the effect of improving the cohesion may be insufficient, so that the effect of improving the durability may be insignificant. If the content is more than 1 part by weight, the adhesive force may be lowered due to a decrease in the initial wettability due to excessive increase of the cohesion, which may result in poor peeling. Preferably 0.1 to 0.5 parts by weight may be included.
본 발명의 점착제 조성물은 실란 커플링제를 더 포함할 수 있다.The pressure-sensitive adhesive composition of the present invention may further include a silane coupling agent.
실란 커플링제는 피착체 표면 극성기와 공유 결합하여, 점착력을 개선한다.The silane coupling agent covalently bonds to the adherend surface polar group, thereby improving adhesion.
실란 커플링제는 특별히 한정되지 않고 당 분야에 공지된 실란커플링제가 사용될 수 있으며, 예를 들면 비닐트리메톡시실란, 비닐트리에톡시실란, 비닐트리스(2-메톡시에톡시)실란, N-(2-아미노에틸)-3-아미노프로필메틸디메톡시실란, N-(2-아미노에틸)-3-아미노프로필트리메톡시실란, 3-아미노프로필트리에톡시실란, 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필메틸디메톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, 3-클로로프로필메톡실디메톡시실란, 3-클로로프로필트리메톡시실란, 3-메타크릴록시프로필트리메톡시실란, 3-메르캅토프로필트리메톡시실란, 3-글리시독시프로필트리에톡시실란, 3-글리시독시프로필디메톡시메틸실란, 3-글리시독시프로필에톡시디메틸실란 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The silane coupling agent is not particularly limited and silane coupling agents known in the art can be used, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltri Methoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethoxysildimethoxysilane, 3-chloropropyltrimethoxysilane , 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyl Ethoxy dimethylsilane etc. are mentioned. These can be used individually or in mixture of 2 or more types.
실란 커플링제의 함량은 특별히 한정되지 않으며, 예를 들면 아크릴계 공중합체 100중량부에 대하여 0.01 내지 10중량부, 바람직하게는 0.1 내지 5중량부로 포함될 수 있다. 함량이 0.01중량부 미만이면 점착력 개선 효과가 미미할 수 있고, 10중량부 초과이면 응집력이 지나치게 증가하여 점착력 등의 점착 물성이 저하됨에 따라 마찬가지로 내구성이 저하될 수 있다.The content of the silane coupling agent is not particularly limited, and may be included, for example, in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the acrylic copolymer. If the content is less than 0.01 parts by weight, the effect of improving the adhesive strength may be insignificant, and if it exceeds 10 parts by weight, the cohesion may be excessively increased and the durability of the adhesive properties, such as adhesive strength, may be lowered.
또한, 본 발명의 점착제 조성물은 본 발명의 목적을 벗어나지 않는 범위 내에서, 당 분야에서 통상적으로 사용되는, 산화 방지제, 부식 방지제, 소포제, 충전제, 대전 방지제 등의 첨가제를 더 포함할 수 있다.In addition, the pressure-sensitive adhesive composition of the present invention may further include additives such as antioxidants, corrosion inhibitors, antifoaming agents, fillers, antistatic agents, and the like, which are commonly used in the art, without departing from the object of the present invention.
<점착 시트><Adhesive sheet>
또한, 본 발명은 상기 점착제 조성물로 형성된 점착층을 포함하는 점착 시트를 제공한다.In addition, the present invention provides a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition.
점착층의 두께는 특별히 한정되지 않으며, 예를 들면 0.5 내지 50㎛일 수 있다.The thickness of the adhesive layer is not particularly limited, and may be, for example, 0.5 to 50 μm.
본 발명의 점착 시트는 이형필름의 적어도 일면에 형성된 점착층을 포함한다.The adhesive sheet of the present invention includes an adhesive layer formed on at least one surface of the release film.
점착층은 상기 점착제 조성물을 이형필름의 적어도 일면에 도공함으로써 형성할 수 있다. 도공 방법은 특별히 한정되지 않고 당 분야에 공지된 방법이 사용될 수 있으며, 예를 들면 바 코터, 에어 나이프, 그라비아, 리버스 롤, 키스 롤, 스프레이, 블레이드, 다이 코터, 캐스팅, 스핀 코팅 등의 방법을 이용할 수 있다.The pressure-sensitive adhesive layer can be formed by coating the pressure-sensitive adhesive composition on at least one surface of the release film. The coating method is not particularly limited, and methods known in the art may be used. For example, methods such as a bar coater, air knife, gravure, reverse roll, kiss roll, spray, blade, die coater, casting, and spin coating may be used. It is available.
이형필름은 특별히 한정되지 않고 점착 시트에 통상적으로 사용되는 이형필름이 사용될 수 있으며, 예를 들면 폴리에틸렌테레프탈레이트, 폴리부티렌테레프탈레이드, 폴리에틸렌나프탈레이트, 폴리부티렌나프탈레이트 등의 폴리에스터 수지; 폴리이미드 수지; 아크릴 수지; 폴리스타이렌 및 아크릴로니트릴-스타이렌 등의 스타이렌계 수지; 폴리카보네이트 수지; 폴리락틱에시드 수지; 폴리우레탄 수지; 폴리에틸렌, 폴리프로필렌, 에틸렌-프로필렌 공중합체와 같은 폴리올레핀 수지; 폴리비닐클로라이드, 폴리비닐리덴클로라이드 등의 비닐 수지; 폴리아미드 수지; 설폰계 수지; 폴리에테르-에테르케톤계 수지; 알릴레이트계 수지; 또는 상기 수지들의 혼합물로 형성된 것일 수 있다.The release film is not particularly limited, and a release film commonly used in an adhesive sheet may be used, for example, polyester resins such as polyethylene terephthalate, polybutyrene terephthalate, polyethylene naphthalate, and polybutylene naphthalate; Polyimide resins; Acrylic resins; Styrene resins such as polystyrene and acrylonitrile-styrene; Polycarbonate resins; Polylactic acid resins; Polyurethane resins; Polyolefin resins such as polyethylene, polypropylene, ethylene-propylene copolymers; Vinyl resins such as polyvinyl chloride and polyvinylidene chloride; Polyamide resins; Sulfone resins; Polyether ether ketone resins; Allyl resins; Or it may be formed of a mixture of the resin.
이형필름의 두께는 특별히 한정되지 않으며, 예를 들면 5 내지 500㎛일 수 있고, 바람직하게는 10 내지 100㎛일 수 있다.The thickness of the release film is not particularly limited, and may be, for example, 5 to 500 μm, and preferably 10 to 100 μm.
<편광판><Polarizing plate>
또한, 본 발명은 적어도 일면에 상기 점착제 조성물로 형성된 점착층을 포함하는 편광판을 제공한다.In addition, the present invention provides a polarizing plate including a pressure-sensitive adhesive layer formed on at least one surface of the pressure-sensitive adhesive composition.
본 발명의 편광판은 편광자, 상기 편광자의 적어도 일면에 접합된 보호필름 및 상기 보호필름 상에 상기 점착제 조성물로 형성된 점착층을 포함한다.The polarizing plate of the present invention includes a polarizer, a protective film bonded to at least one surface of the polarizer, and an adhesive layer formed of the pressure-sensitive adhesive composition on the protective film.
편광자는 당 분야에 공지된 편광자일 수 있으며, 예를 들면 폴리비닐알콜계 필름을 팽윤, 염색, 가교, 연신, 수세, 건조하는 등의 과정을 거쳐 제조된 것일 수 있다.The polarizer may be a polarizer known in the art, and for example, may be manufactured by swelling, dyeing, crosslinking, stretching, washing, drying, and the like of a polyvinyl alcohol-based film.
보호필름으로는 투명성, 기계적 강도, 열안정성, 수분차폐성, 등방성 등이 우수한 필름이라면 특별히 제한되지 않는다. 구체적으로, 폴리에틸렌테레프탈레이트, 폴리에틸렌이소프탈레이트, 폴리부틸렌테레프탈레이트 등의 폴리에스테르계 필름; 디아세틸셀룰로오스, 트리아세틸셀룰로오스 등의 셀룰로오스계 필름; 폴리카보네이트계 필름; 폴리메틸(메타)아크릴레이트, 폴리에틸(메타)아크릴레이트 등의 아크릴계 필름; 폴리스티렌, 아크릴로니트릴-스티렌 공중합체 등의 스티렌계 필름; 폴리올레핀계 필름; 염화비닐계 필름; 나일론, 방향족 폴리아미드 등의 폴리아미드계 필름; 이미드계 필름; 술폰계 필름; 폴리에테르케톤계 필름; 황화 폴리페닐렌계 필름; 비닐알코올계 필름; 염화비닐리덴계 필름; 비닐부티랄계 필름; 알릴레이트계 필름; 폴리옥시메틸렌계 필름; 우레탄계 필름; 에폭시계 필름; 실리콘계 필름 등을 들 수 있다. 이들 중에서도 특히 알칼리 등에 의해 비누화(검화)된 표면을 가진 셀룰로오스계 필름이 편광특성 또는 내구성을 고려하면 바람직하다. 또한, 보호필름은 광학층의 기능을 겸비한 것일 수도 있다.The protective film is not particularly limited as long as the film is excellent in transparency, mechanical strength, thermal stability, moisture shielding, and isotropy. Specifically, polyester film, such as polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate; Cellulose films such as diacetyl cellulose and triacetyl cellulose; Polycarbonate film; Acrylic films such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene films such as polystyrene and acrylonitrile-styrene copolymers; Polyolefin-based film; Vinyl chloride film; Polyamide films such as nylon and aromatic polyamides; Imide film; Sulfone film; Polyether ketone film; Sulfided polyphenylene-based films; Vinyl alcohol film; Vinylidene chloride-based film; Vinyl butyral film; Allylate film; Polyoxymethylene film; Urethane film; Epoxy film; Silicone film etc. are mentioned. Among these, especially the cellulose type film which has the surface saponified by saponification by alkali etc. is preferable in consideration of polarization characteristic or durability. In addition, the protective film may have a function of the optical layer.
점착층은 보호필름에 직접 도공된 것이거나, 보호필름에 점착 시트를 부착하여 형성된 것일 수 있다.The adhesive layer may be directly coated on the protective film, or may be formed by attaching the adhesive sheet to the protective film.
<화상표시장치><Image display device>
또한, 본 발명은 상기 편광판을 포함하는 화상표시장치를 제공한다.In addition, the present invention provides an image display device including the polarizing plate.
본 발명의 화상표시장치는 상기 편광판 외에 당 분야에 공지된 구성을 더 포함할 수 있다.The image display apparatus of the present invention may further include a configuration known in the art in addition to the polarizing plate.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 이들 실시예는 본 발명을 예시하는 것일 뿐 첨부된 특허청구범위를 제한하는 것이 아니며, 본 발명의 범주 및 기술사상 범위 내에서 실시예에 대한 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.
제조예 1Preparation Example 1
1-1. 아크릴계 공중합체의 제조1-1. Preparation of Acrylic Copolymer
질소 가스가 환류되며, 온도 조절이 용이하도록 냉각장치를 설치한 1L의 반응기에 n-부틸아크릴레이트 85중량부, 메타아크릴레이트 7중량부, 2-히드록시에틸아크릴레이트 5중량부, 아크릴산 3중량부로 이루어진 단량체 혼합물을 투입한 후, 용제로 에틸아세테이트 100중량부를 투입하였다. 그 다음 산소를 제거하기 위하여 질소 가스를 1시간 동안 퍼징한 후, 62℃로 유지하였다. 상기 혼합물을 균일하게 혼합한 후, 반응 개시제로 아조비스이소부티로니트릴(AIBN) 0.07중량부를 투입하고, 8시간 동안 반응시켜 아크릴계 공중합체(중량평균분자량 약 100만)를 제조하였다. Nitrogen gas is refluxed, 85 parts by weight of n-butyl acrylate, 7 parts by weight of methacrylate, 5 parts by weight of 2-hydroxyethyl acrylate, 3 parts of acrylic acid in a 1 L reactor equipped with a cooling device for easy temperature control. After adding a monomer mixture consisting of parts, 100 parts by weight of ethyl acetate was added as a solvent. Nitrogen gas was then purged for 1 hour to remove oxygen and then held at 62 ° C. After the mixture was uniformly mixed, 0.07 parts by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator, and reacted for 8 hours to prepare an acrylic copolymer (a weight average molecular weight of about 1 million).
1-2. 아크릴계 공중합체의 제조1-2. Preparation of Acrylic Copolymer
질소 가스가 환류되며, 온도조절이 용이하도록 냉각장치를 설치한 1L의 반응기에 n-부틸아크릴레이트 90중량부, 메타아크릴레이트 5중량부, 2-히드록시에틸아크릴레이트 4중량부, 아크릴산 1중량부로 이루어진 단량체 혼합물을 투입한 후, 용제로 에틸아세테이트 100중량부를 투입하였다. 그 다음 산소를 제거하기 위하여 질소 가스를 1시간 동안 퍼징한 후, 62℃로 유지하였다. 상기 혼합물을 균일하게 혼합한 후, 반응 개시제로 아조비스이소부티로니트릴(AIBN) 0.07중량부를 투입하고, 8시간 동안 반응시켜 아크릴계 공중합체(중량평균분자량 약 100만)를 제조하였다.Nitrogen gas is refluxed, 90 parts by weight of n-butyl acrylate, 5 parts by weight of methacrylate, 4 parts by weight of 2-hydroxyethyl acrylate, 1 weight of acrylic acid in a 1 L reactor equipped with a cooling device for easy temperature control. After adding a monomer mixture consisting of parts, 100 parts by weight of ethyl acetate was added as a solvent. Nitrogen gas was then purged for 1 hour to remove oxygen and then held at 62 ° C. After the mixture was uniformly mixed, 0.07 parts by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator, and reacted for 8 hours to prepare an acrylic copolymer (a weight average molecular weight of about 1 million).
제조예 2Preparation Example 2
2-1. 화학식 2의 화합물의 합성2-1. Synthesis of Compound of Formula 2
[반응식 1]Scheme 1
Figure PCTKR2014010650-appb-I000016
Figure PCTKR2014010650-appb-I000016
4-메틸벤젠-1,3-디아민 35.8g(293mmol)를 물 1400ml에 교반 용해하고, c-HCl 10ml를 반응기에 투입하고, 5℃로 냉각한다. 이어서, 35% 포름알데히드 수용액 12.6ml(147mmol)을 10℃ 이하에서 30분간 천천히 적가하고, 상온으로 승온 후 3시간 교반하였다. 전개용매로 에틸아세테이트를 사용한 박층 크로마토그래피로 반응 종결을 확인한 뒤, 상온에서 여과하고 물로 세척하고 감압 건조하여, 중간체 12.3g을 수득하였다.35.8 g (293 mmol) of 4-methylbenzene-1,3-diamine was dissolved in 1400 ml of water with stirring, 10 ml of c-HCl was added to the reactor, and cooled to 5 ° C. Subsequently, 12.6 ml (147 mmol) of 35% aqueous formaldehyde solution was slowly added dropwise at 10 占 폚 or lower for 30 minutes, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction by thin layer chromatography using ethyl acetate as a developing solvent, the mixture was filtered at room temperature, washed with water, and dried under reduced pressure to obtain an intermediate 12.3 g.
얻어진 중간체는 NMR 분석하여 상기 반응식의 중간체임을 확인하였다.The obtained intermediate was analyzed by NMR to confirm that it was an intermediate of the above scheme.
CDCl3/300MHz : 6.71 (2H), 6.08 (2H) 3.58 (2H), 3.50 (8H), 2.07(6H).CDCl 3/300 MHz: 6.71 (2H), 6.08 (2H) 3.58 (2H), 3.50 (8H), 2.07 (6H).
얻어진 중간체 12.3g(47.98mmol)에 클로로벤젠 490ml를 가하고, 질소 flow하에서 교반하였다. 이후에 4N HCl in dioxane 61.9ml(239.9mmol)를 반응기에 투입하고, 반응기 온도를 5℃로 냉각한 후에, 트리클로로메틸 클로로포메이트(ClCOOCCl3) 29ml(240mmol)를 5℃ 이하에서 30분간 적가하였다. 상온으로 승온 후 24시간 교반하고, 추가적으로 110℃로 승온 후 7시간 교반하였다. 상온에서 냉각하고 1시간 방치한 후에, 상층액만 질소 하에서 플라스크에 이송시켜 90℃에서 감압 농축하여, 화합물 14.5g을 수득하였다. 수득된 화합물의 NMR 스펙트럼을 분석하여 상기 화학식 2의 화합물임을 확인하였다.490 ml of chlorobenzene was added to 12.3 g (47.98 mmol) of the obtained intermediate, and the mixture was stirred under a nitrogen flow. Thereafter, 61.9 ml (239.9 mmol) of 4N HCl in dioxane was added to the reactor, and after cooling the reactor temperature to 5 ° C., 29 ml (240 mmol) of trichloromethyl chloroformate (ClCOOCCl 3) was added dropwise at 5 ° C. or lower for 30 minutes. . After the temperature was raised to room temperature, the mixture was stirred for 24 hours, and further heated to 110 ° C, and then stirred for 7 hours. After cooling to room temperature and standing for 1 hour, only the supernatant was transferred to a flask under nitrogen, and concentrated under reduced pressure at 90 ° C. to obtain 14.5 g of a compound. The NMR spectrum of the obtained compound was analyzed to confirm that it is a compound of Chemical Formula 2.
CDCl3/300MHz : 6.88 (2H), 6.81 (2H) 3.88 (2H), 2.25(6H).CDCl 3/300 MHz: 6.88 (2H), 6.81 (2H) 3.88 (2H), 2.25 (6H).
2-2. 화학식 3의 화합물의 합성2-2. Synthesis of Compound of Formula 3
[반응식 2]Scheme 2
Figure PCTKR2014010650-appb-I000017
Figure PCTKR2014010650-appb-I000017
4-메틸벤젠-1,3-디아민 대신에 2-메틸벤젠-1,3-디아민을 시작물질로 사용한 것을 제외하고는 제조예 2-1과 동일한 반응을 수행하여 화합물을 수득하였고, 이의 NMR 스펙트럼을 분석하여 화학식 3의 화합물임을 확인하였다.Except for using 2-methylbenzene-1,3-diamine instead of 4-methylbenzene-1,3-diamine as a starting material, the reaction was carried out in the same manner as in Preparation Example 2-1 to obtain a compound, NMR spectrum thereof It was confirmed that the compound of formula 3 by analyzing.
CDCl3/300MHz : 7.00 (2H), 6.89 (2H) 3.81 (2H), 2.35(6H).CDCl 3/300 MHz: 7.00 (2H), 6.89 (2H) 3.81 (2H), 2.35 (6H).
2-3. 화학식 4의 화합물의 합성2-3. Synthesis of Compound of Formula 4
[반응식 3]Scheme 3
Figure PCTKR2014010650-appb-I000018
Figure PCTKR2014010650-appb-I000018
4-메틸벤젠-1,3-디아민 대신에 4-메톡시벤젠-1,3-디아민을 시작물질로 사용한 것을 제외하고는 제조예 2-1과 동일한 반응을 수행하여 화합물을 수득하였고, 이의 NMR 스펙트럼을 분석하여 화학식 4의 화합물임을 확인하였다.Except for using 4-methoxybenzene-1,3-diamine instead of 4-methylbenzene-1,3-diamine as a starting material to carry out the same reaction as in Preparation Example 2-1 to give a compound, NMR thereof Spectrum analysis confirmed that the compound of Formula 4.
CDCl3/300MHz : 7.00 (2H), 6.60 (2H) 3.81 (2H), 3.73(6H).CDCl 3/300 MHz: 7.00 (2H), 6.60 (2H) 3.81 (2H), 3.73 (6H).
2-4. 화학식 5의 화합물의 합성2-4. Synthesis of Compound of Formula 5
[반응식 4]Scheme 4
Figure PCTKR2014010650-appb-I000019
Figure PCTKR2014010650-appb-I000019
4-메틸벤젠-1,3-디아민 대신에 4-클로로벤젠-1,3-디아민을 시작물질로 사용한 것을 제외하고는 제조예 2-1과 동일한 반응을 수행하여 화합물을 수득하였고, 이의 NMR 스펙트럼을 분석하여 화학식 5의 화합물임을 확인하였다.Except for using 4-chlorobenzene-1,3-diamine instead of 4-methylbenzene-1,3-diamine as a starting material to carry out the same reaction as in Preparation Example 2-1 to give a compound, its NMR spectrum It was confirmed that the compound of formula 5 by analyzing.
CDCl3/300MHz : 7.10 (4H), 3.81 (2H)CDCl3 / 300MHz: 7.10 (4H), 3.81 (2H)
2-5. 화학식 6의 화합물의 합성2-5. Synthesis of Compound of Formula 6
[반응식 5]Scheme 5
Figure PCTKR2014010650-appb-I000020
Figure PCTKR2014010650-appb-I000020
4-메틸벤젠-1,3-디아민 대신에 1,3-디아미노벤젠을 시작물질로 사용한 것을 제외하고는 제조예 2-1과 동일한 반응을 수행하여 화합물을 수득하였고, 이의 NMR 스펙트럼을 분석하여 화학식 6의 화합물임을 확인하였다.A compound was obtained in the same manner as in Preparation Example 2-1, except that 1,3-diaminobenzene was used as a starting material instead of 4-methylbenzene-1,3-diamine, and the NMR spectrum thereof was analyzed. It was confirmed that the compound of the formula (6).
CDCl3/300MHz : 7.10 (4H), 6.92 (2H) 3.81 (2H).CDCl 3/300 MHz: 7.10 (4H), 6.92 (2H) 3.81 (2H).
실시예 및 비교예Examples and Comparative Examples
하기 표 1에 기재된 조성 및 함량을 갖는 점착제 조성물을 제조하였다.To prepare a pressure-sensitive adhesive composition having the composition and content shown in Table 1.
표 1
Figure PCTKR2014010650-appb-T000001
 Table 1
Figure PCTKR2014010650-appb-T000001
실험예. 내구성(내열성, 내습열성) 평가Experimental Example Evaluation of durability (heat resistance, heat and humidity resistance)
실시예 및 비교예의 점착제 조성물을 실리콘 이형제가 코팅된 이형필름 상에 경화 후 두께가 25㎛가 되도록 도포하고 100℃에서 1분 동안 건조시켜 점착층을 형성하였다. 상기 점착층 위에 이형필름을 라미네이션하여 점착 시트를 제조하였다.The pressure-sensitive adhesive compositions of Examples and Comparative Examples were applied on a release film coated with a silicone release agent so as to have a thickness of 25 μm, and dried at 100 ° C. for 1 minute to form an adhesive layer. The adhesive film was prepared by laminating a release film on the adhesive layer.
상기 제조된 점착시트의 이형필름을 박리한 후 양면에 트리아세틸셀룰로오스계 보호필름이 접합된 요오드계 편광필름(총 두께 185㎛) 에 상기 제조된 점착층을 점착 가공으로 적층하여 편광판을 제조하였다. 제조된 편광판을 23℃, 60% RH의 조건 하에서 양생 기간 동안 보관하였다. After peeling the release film of the prepared pressure-sensitive adhesive sheet was laminated on the adhesive layer iodine-based polarizing film (total thickness 185㎛) bonded to the triacetyl cellulose-based protective film on both sides by adhesive processing to prepare a polarizing plate. The prepared polarizing plate was stored under curing conditions at 23 ° C. and 60% RH.
상기 각각의 편광판을 90㎜×170㎜ 크기로 절단하고 이형필름을 박리한 후, 유리기판(110㎜×190㎜×0.7㎜)의 양면으로 각 편광판의 흡수축이 직교가 되도록 부착하였다. 상기 부착은 5kg/cm2의 압력을 가하며, 기포나 이물이 생기지 않도록 크린룸에서 수행되었다.Each polarizing plate was cut to a size of 90 mm x 170 mm and the release film was peeled off, and then attached to both surfaces of the glass substrate (110 mm x 190 mm x 0.7 mm) so that the absorption axes of the polarizing plates were perpendicular to each other. The attachment was applied at a pressure of 5 kg / cm 2 and was performed in a clean room to prevent bubbles or foreign substances from being formed.
상기 적층체의 내열 특성은 80℃의 온도에서 500시간 동안 방치한 후에 기포나 박리의 발생 여부를 관찰하여 평가하였다. 또한 내습열 평가는 60℃ 90%습도 조건에서 500시간 방치 후 기포나 박리의 발생 여부를 관찰하여 평가하였다.The heat resistance of the laminate was evaluated by observing the occurrence of bubbles or peeling after leaving for 500 hours at a temperature of 80 ℃. In addition, the heat and humidity evaluation was evaluated by observing the occurrence of bubbles or peeling after 500 hours left at 60 ℃ 90% humidity conditions.
<평가 기준><Evaluation Criteria>
ⓞ: 기포나 박리 없음Ⓞ: no bubbles or peeling
○: 기포나 박리 3개 미만○: less than 3 bubbles or peeling
△: 기포나 박리 3개 이상 5개 미만△: less than five or more bubbles or peeling
×: 기포나 박리 5개 이상×: 5 or more bubbles or peelings
표 2
Figure PCTKR2014010650-appb-T000002
 TABLE 2
Figure PCTKR2014010650-appb-T000002
상기 표 2를 참조하면, 실시예 1 내지 9의 점착제 조성물은 내열성 및 내습열성이 매우 우수하였다.Referring to Table 2, the pressure-sensitive adhesive composition of Examples 1 to 9 was very excellent in heat resistance and heat and moisture resistance.
그러나, 비교예 1 및 2의 점착제 조성물은 내열성 및 내습열성이 떨어졌다.However, the adhesive compositions of Comparative Examples 1 and 2 were inferior in heat resistance and heat and humidity resistance.

Claims (6)

  1. 아크릴계 공중합체 및 하기 화학식 1의 가교제를 포함하는, 점착제 조성물:Pressure-sensitive adhesive composition comprising an acrylic copolymer and a crosslinking agent of the formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2014010650-appb-I000021
    Figure PCTKR2014010650-appb-I000021
    (식 중, R1 및 R2는 서로 독립적으로 수소 원자, 할로겐 원자, 탄소수 1 내지 5의 알킬기 또는 탄소수 1 내지 5의 알콕시기임).(Wherein R 1 and R 2 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms).
  2. 청구항 1에 있어서, 상기 화학식 1의 가교제는 하기 화학식 2 내지 6으로 이루어진 군에서 선택된 적어도 하나인, 점착제 조성물:The pressure-sensitive adhesive composition of claim 1, wherein the crosslinking agent of Chemical Formula 1 is at least one selected from the group consisting of Chemical Formulas 2 to 6:
    [화학식 2][Formula 2]
    Figure PCTKR2014010650-appb-I000022
    Figure PCTKR2014010650-appb-I000022
    [화학식 3][Formula 3]
    Figure PCTKR2014010650-appb-I000023
    Figure PCTKR2014010650-appb-I000023
    [화학식 4][Formula 4]
    Figure PCTKR2014010650-appb-I000024
    Figure PCTKR2014010650-appb-I000024
    [화학식 5][Formula 5]
    Figure PCTKR2014010650-appb-I000025
    Figure PCTKR2014010650-appb-I000025
    [화학식 6][Formula 6]
    Figure PCTKR2014010650-appb-I000026
    Figure PCTKR2014010650-appb-I000026
  3. 청구항 1에 있어서, 상기 화학식 1의 가교제는 아크릴계 공중합체 100중량부에 대하여 0.1 내지 1중량부로 포함되는, 점착제 조성물.The pressure-sensitive adhesive composition of claim 1, wherein the crosslinking agent of Chemical Formula 1 is included in an amount of 0.1 to 1 parts by weight based on 100 parts by weight of the acrylic copolymer.
  4. 청구항 1 내지 3 중 어느 한 항의 점착제 조성물로 형성된 점착층을 포함하는 점착 시트.The adhesive sheet containing the adhesion layer formed from the adhesive composition of any one of Claims 1-3.
  5. 적어도 일면에 청구항 1 내지 3 중 어느 한 항의 점착제 조성물로 형성된 점착층을 포함하는 편광판.Polarizing plate comprising a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition of any one of claims 1 to 3 on at least one side.
  6. 청구항 5의 편광판을 포함하는 화상 표시 장치.An image display device comprising the polarizing plate of claim 5.
PCT/KR2014/010650 2013-12-23 2014-11-07 Adhesive composition WO2015099285A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020056447A (en) * 2000-12-29 2002-07-10 성재갑 Acrylic pressure sensitive adhesive for the polarizing firm
US20060217472A1 (en) * 2005-03-11 2006-09-28 Staunton Thomas J Scratch resistant curable coating composition
KR20120110032A (en) * 2011-03-23 2012-10-09 주식회사 엘지화학 Pressure sensitive adhesive composition
KR20130023183A (en) * 2011-08-25 2013-03-07 주식회사 엘지화학 Pressure sensitive adhesive
KR20130040725A (en) * 2011-10-14 2013-04-24 주식회사 엘지화학 Adhesive for polarizing plate and polarizing plate comprising the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020056447A (en) * 2000-12-29 2002-07-10 성재갑 Acrylic pressure sensitive adhesive for the polarizing firm
US20060217472A1 (en) * 2005-03-11 2006-09-28 Staunton Thomas J Scratch resistant curable coating composition
KR20120110032A (en) * 2011-03-23 2012-10-09 주식회사 엘지화학 Pressure sensitive adhesive composition
KR20130023183A (en) * 2011-08-25 2013-03-07 주식회사 엘지화학 Pressure sensitive adhesive
KR20130040725A (en) * 2011-10-14 2013-04-24 주식회사 엘지화학 Adhesive for polarizing plate and polarizing plate comprising the same

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