WO2015194805A1 - Adhesive composition and polarizing plate comprising same - Google Patents

Adhesive composition and polarizing plate comprising same Download PDF

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Publication number
WO2015194805A1
WO2015194805A1 PCT/KR2015/005985 KR2015005985W WO2015194805A1 WO 2015194805 A1 WO2015194805 A1 WO 2015194805A1 KR 2015005985 W KR2015005985 W KR 2015005985W WO 2015194805 A1 WO2015194805 A1 WO 2015194805A1
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WO
WIPO (PCT)
Prior art keywords
adhesive composition
polyester resin
polarizer
composition according
adhesive
Prior art date
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PCT/KR2015/005985
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French (fr)
Korean (ko)
Inventor
권혜림
조천희
Original Assignee
동우 화인켐 주식회사
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Publication of WO2015194805A1 publication Critical patent/WO2015194805A1/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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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

Definitions

  • the present invention relates to an adhesive composition and a polarizing plate including the same, and more particularly, to an adhesive composition for a polarizing plate having excellent adhesion with a hard-adhesive protective film, and a polarizing plate and a liquid crystal display including the same.
  • the polarizing plate usually has a structure in which a transparent protective film is laminated on both surfaces or one side of a polarizer made of a polyvinyl alcohol-based resin in which a dichroic dye is adsorbed and oriented.
  • the polarizer is produced by a method of longitudinally uniaxial stretching and dyeing with a dichroic dye on a polyvinyl alcohol-based resin film, followed by boric acid treatment to perform a crosslinking reaction, and washing with water and drying.
  • a dichroic dye iodine or a dichroic organic dye is used.
  • a polarizing plate is manufactured by stacking a protective film on both surfaces or one side of the polarizer thus manufactured, and introduces the manufactured polarizing plate into the liquid crystal display device.
  • Cellulose-based film is used a lot of protective film, the thickness is usually about 30 to 120 ⁇ m.
  • the protective film often uses an adhesive made of an aqueous solution of polyvinyl alcohol-based resin when laminated.
  • the cellulose-based protective film has a disadvantage in that it can be bonded by an adhesive only after passing through a process of saponifying (alkali treatment) the surface of the protective film when bonding the polarizer.
  • saponifying alkali treatment
  • UV adhesives and the like have been proposed as adhesives capable of bonding cellulose protective films without performing saponification processes.
  • the UV adhesive has a lower adhesive strength than the water-based adhesive, which may induce cracking of the polarizer in the thermal shock test, and has a disadvantage in that the price is very high and the economic efficiency is low.
  • the cellulose-based protective film has a disadvantage in that the polarizing plate performance is lowered or the protective film and the polarizer peel off due to low moisture and heat resistance, and the at least one protective film is composed of various resins other than cellulose-based resins (acrylic and propylene-based resins). There is an attempt to do so.
  • the conventional water-based adhesive made of an aqueous solution of polyvinyl alcohol-based resin had a problem of low adhesive strength with an acrylic protective film (see Korean Patent Publication No. 2010-0095402).
  • the present invention is to solve the above problems, one object of the present invention to provide an adhesive composition for a polarizing plate excellent in adhesion with a hard-adhesive protective film.
  • Another object of the present invention is to provide a polarizing plate comprising an adhesive layer formed from the adhesive composition for polarizing plates.
  • Still another object of the present invention is to provide a liquid crystal display device including the polarizing plate.
  • the present invention provides an adhesive composition comprising a polyester resin and a crosslinking agent.
  • the polyester resin may be a water-soluble polyester resin having a sulfonic acid, sulfonic acid salt, carboxylic acid or carboxylate functional group.
  • the polyester resin may be prepared by polymerizing an aromatic dicarboxylic acid and an aliphatic diol having a sulfonic acid, sulfonic acid salt, carboxylic acid or carboxylate functional group.
  • the polyester resin may be a polymer compound having one or more repeating units selected from repeating units of the following Chemical Formulas 1 to 2.
  • R is sulfonic acid, sulfonate, carboxylic acid or carboxylate
  • n is an integer from 1 to 10.
  • the molecular weight of the polyester resin may range from 10,000 to 40,000.
  • the crosslinking agent may be included 50 to 400 parts by weight based on 100 parts by weight of the polyester resin based on the solid content.
  • the present invention is a polarizer; An adhesive layer laminated on one or both surfaces of the polarizer and formed from the adhesive composition; And it provides a polarizing plate comprising a polarizer protective film laminated on the adhesive layer.
  • the present invention provides a liquid crystal display device comprising the polarizing plate.
  • the adhesive composition for polarizing plates according to the present invention makes it possible to bond a hard-adhesive protective film such as polymethyl methacrylate, polypropylene, and unrefined triacetyl cellulose, which are difficult to adhere with conventional water-based adhesives, with excellent adhesive strength.
  • One embodiment of the present invention relates to an adhesive composition
  • an adhesive composition comprising a polyester resin and a crosslinking agent.
  • the polyester resin may be a water-soluble polyester resin having a sulfonic acid, sulfonic acid salt, carboxylic acid or carboxylate functional group.
  • the sulfonate may be a metal salt such as sodium and potassium salts of sulfonic acid, an ammonium salt or an organic amine salt, and the like, and a sodium salt of sulfonic acid is preferable.
  • the carboxylic acid salt may be a metal salt such as sodium and potassium salts of carboxylic acid, ammonium salt or organic amine salt, and the like, and sodium salt of carboxylic acid is preferable.
  • the polyester resin may be prepared by polymerizing an aromatic dicarboxylic acid and an aliphatic diol having a sulfonic acid, a sulfonic acid salt, a carboxylic acid or a carboxylate functional group.
  • Terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, etc. may be used as the aromatic dicarboxylic acid, but is not limited thereto. These can be used individually or in combination of 2 or more types.
  • aliphatic diol ethylene glycol, 1,4-butanediol (1,4-butanediol), 1,3-propanediol (1,3-propanediol) and the like may be used, but are not limited thereto. These can be used individually or in combination of 2 or more types.
  • the polyester resin may be a polymer compound having one or more repeating units selected from repeating units of the following Chemical Formulas 1 to 2.
  • R is sulfonic acid, sulfonate, carboxylic acid or carboxylate
  • n is an integer from 1 to 10.
  • polyester resin products examples include Z-446, Z-221, Z-561, and Z-565 (formerly, GOO CHEMICAL), which are water-soluble polyester resins having sulfonate functional groups, but are not limited thereto. .
  • the said polyester resin is not specifically limited, In order to express high adhesiveness between a polarizer and a protective film, it is preferable that molecular weight exists in the range of 10,000-40,000. If the molecular weight is less than 10,000, it is difficult to express adhesiveness, and if it is more than 40,000, there is a problem of bubble mixing in the bonding process.
  • the crosslinking agent serves to improve the adhesion and durability of the polarizer and the protective film and to maintain the shape of the adhesive and the reliability at high temperatures.
  • the crosslinking agent may be an isocyanate type, an epoxy type, a peroxide type, a metal chelate type, an oxazoline type, a melamine type, a glyoxylate type, an aziridine type, or the like, or may be used alone or in combination of two or more thereof. Among them, an aziridine-based crosslinking agent is preferable in view of improving adhesion and durability.
  • the aziridine crosslinking agent is specifically described as a preferable crosslinking agent, a crosslinking agent is not limited to this.
  • the aziridine crosslinking agent may react with an aziridine functional group such as a hydrophilic group on the surface of the film, and the adhesive composition including the aziridine functional group may lower the surface energy of the film, thereby providing excellent wettability to a nonpolar film such as an acrylic film. Therefore, it is possible to have high adhesive properties even on a film having no roughness on the surface and low surface energy.
  • the aziridine crosslinking agent may form a hydrophilic group by ring opening, and the hydrophilic group may hydrogen bond with a hydroxyl group on the surface of an optical film such as a polarizer. For this reason, aziridine crosslinking agents can provide excellent adhesion compared to conventional adhesives such as polyvinyl alcohol adhesives.
  • the compound having a polyfunctional aziridine has a feature of improving the cohesive effect in the adhesive layer to prevent the mixing of bubbles and to improve the water resistance.
  • the aziridine-based crosslinking agent is pentaerythritol-tris- (beta- (N-aziridinyl) propionate, trimethylolpropane-tris (beta-N-aziridinyl) propionate, trimethylolpropane-tris (2 -Methyl-1-aziridine propionate) and the like, and trimethylolpropane-tris (2-methyl-1-aziridine propionate), which is particularly excellent in adhesion performance, is more preferable.
  • the crosslinking agent is 50 to 400 parts by weight, preferably 100 to 300 parts by weight based on 100 parts by weight of the polyester resin (based on the solid content). If the content is less than 50 parts by weight, the adhesion to the hard-adhesive protective film is hardly expressed sufficiently, and if the content exceeds 400 parts by weight, there is a problem in the stability of the preparation.
  • Adhesive composition according to an embodiment of the present invention may further include an organic solvent in order to express a high wettability between the polarizer and the protective film, the organic solvent is preferably alcohol.
  • the alcohol dissolves the surface of the hard-adhesive protective film so that the components of the adhesive composition penetrate into the hard-adhesive protective film surface, thereby causing a chemical reaction to prevent bubble mixing.
  • alcohol has an excellent wettability against the hard-adhesive protective film also has a leveling agent effect.
  • methanol, ethanol, propanol, isopropanol, butanol, t-butanol, glycerol, and the like may be used, and one or two or more thereof may be mixed.
  • the alcohol is included 3 to 30 parts by weight based on 100 parts by weight of the polyester resin (based on the solid content). If the content is less than 3 parts by weight, the peel force is lowered, and if the content exceeds 30 parts by weight, there is a problem that explosion-proof equipment is required because the critical explosion limit concentration is exceeded.
  • the adhesive composition according to one embodiment of the present invention may further include additives such as plasticizers, silane coupling agents, antistatic agents, fine particles, leveling agents, and the like, which are generally used in the art within the range of not impairing the desired effect. Can be. It is preferable to use a leveling agent etc. especially in order to improve the spreadability of an adhesive bond layer forming composition.
  • the adhesive composition which concerns on one Embodiment of this invention is liquid form in order to form a uniform adhesive bond layer on the surface of a polarizer or a protective film which is a to-be-adhered body.
  • Such liquid adhesives may be used in the form of a solution or dispersion of various solvents.
  • a solution type is preferable, and in consideration of stability, a solution or dispersion with water as a solvent is preferable. .
  • a water / alcohol mixed solvent in which the alcohol solution is easily mixed with water in the adhesive solution and has a lower boiling point than water may be used. It is preferable that the boiling point of an alcoholic solvent is 100 degrees C or less, especially 80 degrees C or less, or 70 degrees C or less.
  • One embodiment of the present invention is a polarizer; An adhesive layer laminated on one or both surfaces of the polarizer and formed from the adhesive composition; And it relates to a polarizing plate comprising a polarizer protective film laminated on the adhesive layer.
  • the polarizer is a dichroic dye adsorbed on the stretched polyvinyl alcohol-based film.
  • the polyvinyl alcohol-based resin constituting the polarizer can be obtained by saponifying a polyvinyl acetate-based resin.
  • polyvinyl acetate type resin the copolymer etc. of vinyl acetate and the other monomer copolymerizable with this besides the polyvinyl acetate which is a homopolymer of vinyl acetate are mentioned.
  • an unsaturated carboxylic acid type, an unsaturated sulfonic acid type, an olefin type, a vinyl ether type, an acrylamide type monomer which has an ammonium group, etc. are mentioned.
  • the polyvinyl alcohol-based resin may be modified, for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used.
  • Saponification degree of polyvinyl alcohol-type resin is 85-100 mol% normally, Preferably it is 98 mol% or more.
  • the degree of polymerization of the polyvinyl alcohol-based resin is usually 1,000 to 10,000, preferably 1,500 to 5,000.
  • What formed such a polyvinyl alcohol-type resin into a film is used as a raw film of a polarizer.
  • the film formation method of polyvinyl alcohol-type resin is not specifically limited, A well-known method can be used.
  • the film thickness of the raw film is not particularly limited, and may be, for example, 10 to 150 ⁇ m.
  • the polarizer of this invention is manufactured through the process of uniaxially stretching a polyvinyl alcohol-type film in aqueous solution, the process of dyeing and adsorb
  • the process of uniaxially stretching the polyvinyl alcohol-based film may be performed before dyeing, may be simultaneously performed with dyeing, or may be performed after dyeing.
  • the uniaxial stretching is performed after dyeing, it may be performed before boric acid treatment, or may be performed during boric acid treatment.
  • rolls or heat rolls with different circumferential speeds can be used.
  • uniaxial stretching may be dry stretching extending
  • the draw ratio is usually 4 to 8 times.
  • the method of immersing a polyvinyl alcohol-type film in the aqueous solution containing a dichroic dye can be used, for example.
  • a dichroic dye iodine or a dichroic dye is used.
  • the polyvinyl alcohol-based film is preferably swelled by dipping in water before dyeing.
  • the method of immersing and dyeing a polyvinyl alcohol-type film in the dyeing aqueous solution containing iodine and potassium iodide can be used normally.
  • the content of iodine in the aqueous solution for dyeing is 0.01 to 1 part by weight based on 100 parts by weight of water (distilled water), and the content of potassium iodide is 0.5 to 20 parts by weight based on 100 parts by weight of water.
  • the temperature of the aqueous solution for dyeing is usually 20 to 40 ° C.
  • the immersion time (dyeing time) is usually 20 to 1,800 seconds.
  • the method of immersing and dyeing a polyvinyl alcohol-type film in the aqueous solution containing water-soluble dichroic dye is employ
  • the content of the dichroic dye in this aqueous solution is usually 1 ⁇ 10 -4 to 10 parts by weight, preferably 1 ⁇ 10 -3 to 1 part by weight per 100 parts by weight of water.
  • This aqueous solution may contain inorganic salts, such as sodium sulfate, as a dyeing adjuvant.
  • the temperature of the dye aqueous solution used for dyeing is 20-80 degreeC normally, and the immersion time in this aqueous solution is 10-1,800 second normally.
  • Boric acid treatment of the dyed polyvinyl alcohol-based film can be carried out by immersing in a boric acid-containing aqueous solution.
  • the content of boric acid in the aqueous solution containing boric acid is 2 to 15 parts by weight, preferably 5 to 12 parts by weight, based on 100 parts by weight of water.
  • the boric acid-containing aqueous solution preferably contains potassium iodide, and the content thereof is usually 0.1 to 15 parts by weight, preferably 5 to 12 parts by weight with respect to 100 parts by weight of water.
  • the temperature of the boric acid-containing aqueous solution is usually 50 ° C or higher, preferably 50 to 85 ° C, more preferably 60 to 80 ° C, and the immersion time is usually 60 to 1,200 seconds, preferably 150 to 600 seconds, more preferably. Preferably it is 200 to 400 seconds.
  • the polyvinyl alcohol-based film is usually washed with water and dried. Washing treatment can be performed by immersing the boric acid-treated polyvinyl alcohol-based film in water.
  • cleaning process is 5-40 degreeC normally, and immersion time is 1-120 second normally.
  • a polarizer can be obtained by drying after washing with water.
  • the drying treatment can usually be carried out using a hot air dryer or a far infrared heater.
  • the drying treatment temperature is usually 30 to 100 ° C, preferably 50 to 80 ° C, and the drying time is usually 60 to 600 seconds, preferably 120 to 600 seconds.
  • the thickness of the polarizer produced as described above is 5 to 40 ⁇ m.
  • the polarizer protective film is not particularly limited as long as it is excellent in transparency, mechanical strength, thermal stability, moisture shielding, isotropy, and the like, specifically, acrylic, cellulose, polyolefin or polyester film, etc. Can be used.
  • Acrylic resin such as polymethyl (meth) acrylate and polyethyl (meth) acrylate
  • Polyester resins such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate and polybutylene terephthalate
  • Cellulose resins such as diacetyl cellulose and triacetyl cellulose
  • Polyolefin resins such as polyethylene, polypropylene, cyclo-based or norbornene-structured polyolefin-based and ethylene-propylene copolymers; A protective film containing these etc. can be mentioned.
  • the thickness of the polarizer protective film is 10 to 200 ⁇ m, preferably 10 to 150 ⁇ m.
  • the polarizer protective film when laminated on both sides of the polarizer may maintain the same or different thickness.
  • the bonding easy process can be performed to the surface joined with the polarizer of a protective film.
  • Examples of the easy-to-bond treatment include dry treatment such as primer treatment, plasma treatment, corona treatment, chemical treatment such as alkali treatment (soap treatment), coating treatment to form an easy adhesive layer, and the like.
  • the present invention is not particularly required because a protective film (eg, an ungelatinized cellulose-based protective film) that is not subjected to a chemical treatment such as an alkali treatment (saponification treatment) is easily bonded to the polarizer.
  • a protective film eg, an ungelatinized cellulose-based protective film
  • a chemical treatment such as an alkali treatment (saponification treatment) is easily bonded to the polarizer.
  • the acrylic or propylene protective film whose surface is represented by the hard adhesive protective film and the dry-treated protective film together with the uncellified cellulose protective film is also easy to bond.
  • an adhesive bond layer is 0.01-10 micrometers normally, Preferably it is 0.05-5 micrometers, More preferably, it is 0.1-1 micrometer.
  • Surfaces that are not bonded to the polarizer of the protective film may be treated for the purpose of hard coat treatment, antireflection treatment, anti-sticking, diffusion or antiglare.
  • the bonding method may be a conventional method in the art, and for example, the bonding surface of the polarizer or the protective film using a casting method, a meyer bar coating method, a gravure coating method, a die coating method, a dip coating method, a spray coating method, or the like. After apply
  • the casting method is a method in which the adhesive composition is applied to the bonding surface while the polarizer or the protective film is generally moved in the vertical direction, the horizontal direction or the inclined direction between the two. After the adhesive composition is applied, the polarizer or the protective film is sandwiched by nip roll or the like.
  • the drying treatment is carried out, for example, by spraying hot air, and the drying temperature is appropriately selected in the range of 40 to 100 ° C, preferably 60 to 100 ° C. Drying time may be about 20 to 1,200 seconds.
  • curing is preferably performed at room temperature or slightly higher, for example, at a temperature of 20 to 50 ° C. for about 12 to 600 hours.
  • the thickness of an adhesive bond layer after drying is 0.001-5 micrometers normally, Preferably it is 0.01-2 micrometers, More preferably, it is 0.01-1 micrometer. When the thickness of an adhesive bond layer exceeds 5 micrometers, it will be easy to produce the external appearance problem of a polarizing plate.
  • optical functional film may be further laminated by the pressure-sensitive adhesive layer.
  • the optical functional film include an optical compensation film in which a liquid crystalline compound or a polymer compound thereof is oriented on the surface of a substrate, a reflection type that transmits polarized light of any kind and reflects polarized light having a property opposite thereto.
  • a polarizing separation film a retardation film containing a polycarbonate resin, a retardation film containing a cyclic polyolefin resin, an antiglare function addition film having a concave-convex shape on the surface, an addition film treated with surface reflection prevention, a reflection film having a reflection function on the surface And a semi-transmissive reflective film having both a reflection function and a transmission function.
  • One embodiment of the present invention relates to a liquid crystal display device comprising the polarizing plate.
  • each component was mixed with the composition of Table 1 below to prepare an adhesive composition for a polarizing plate. At this time, each component was mixed based on the solid content.
  • Polyvinyl alcohol resin (Cosenol Z200, Nippon Synthetic Chemical Co., Ltd.)
  • a cutter blade was placed between each film (between the polarizer and the polarizer protective film) of the polarizing plate, and the method of entering the blade when pushing the blade was evaluated by the following criteria. .
  • X When pushing on a blade, a blade enters in between at least one film.
  • the bonding was performed by using a hand roller on a soda glass using a pressure-sensitive adhesive, and then subjected to autoclave treatment at a pressure of 2 atm, a temperature of 50 ° C., and a time of 20 minutes. Bubbles generated were removed.
  • soda glass / adhesive / acrylic polarizer 180 ° peel force on adhesive layer when peeling polarizer using autograph with knife between corona-treated acrylic protective film and polarizer in soda glass direction (measuring speed 300mm / min) was measured.
  • the adhesive composition of Examples 1 to 12 including the polyester resin according to the present invention is significantly superior in adhesion and peeling force than the adhesive composition of Comparative Example 1 containing a polyvinyl alcohol-based resin.

Abstract

The present invention provides an adhesive composition comprising a polyester resin and a crosslinking agent, a polarizing plate comprising the same, and a liquid crystal display. The adhesive composition for a polarizing plate according to the present invention enables poorly adhesive films such as polymethylmethacrylate, polypropylene, and triacetyl cellulose to adhere, with excellent adhesion, to a polarizer.

Description

접착제 조성물 및 이를 포함하는 편광판 Adhesive composition and polarizing plate comprising same
본 발명은 접착제 조성물 및 이를 포함하는 편광판에 관한 것으로, 보다 상세하게는 난접착성 보호필름과의 접착력이 우수한 편광판용 접착제 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 for a polarizing plate having excellent adhesion with a hard-adhesive protective film, and a polarizing plate and a liquid crystal display including the same.
편광판은 통상 2색성 색소가 흡착 배향된 폴리비닐알코올계 수지로 이루어진 편광자의 양면 또는 한쪽 면에 투명 보호필름이 적층된 구조로 되어 있다.The polarizing plate usually has a structure in which a transparent protective film is laminated on both surfaces or one side of a polarizer made of a polyvinyl alcohol-based resin in which a dichroic dye is adsorbed and oriented.
편광자는 폴리비닐알코올계 수지 필름에 세로 1축 연신과 2색성 색소에 의한 염색을 실시한 후, 붕산 처리하여 가교 반응을 수행하고, 수세, 건조시키는 방법에 의해 제조된다. 2색성 색소로는 요오드 또는 2색성 유기 염료가 사용된다. 이와 같이 제조된 편광자의 양면 또는 한쪽 면에 보호필름을 적층하여 편광판을 제조하고, 제조된 편광판을 액정표시장치에 도입한다.The polarizer is produced by a method of longitudinally uniaxial stretching and dyeing with a dichroic dye on a polyvinyl alcohol-based resin film, followed by boric acid treatment to perform a crosslinking reaction, and washing with water and drying. As the dichroic dye, iodine or a dichroic organic dye is used. A polarizing plate is manufactured by stacking a protective film on both surfaces or one side of the polarizer thus manufactured, and introduces the manufactured polarizing plate into the liquid crystal display device.
보호필름은 셀룰로스계 필름이 많이 사용되고 있으며, 두께는 통상 30 내지 120㎛ 정도이다. 또한, 보호필름은 적층 시 폴리비닐알코올계 수지의 수용액으로 이루어진 접착제를 사용하는 경우가 많다.Cellulose-based film is used a lot of protective film, the thickness is usually about 30 to 120㎛. In addition, the protective film often uses an adhesive made of an aqueous solution of polyvinyl alcohol-based resin when laminated.
그러나, 셀룰로스계 보호필름은 편광자와 접합 시 보호필름의 표면을 검화(알칼리 처리)하는 공정을 반드시 거쳐야만 접착제에 의해 접합이 가능하다는 단점이 있다. 현재 검화 공정을 수행하지 않고 셀룰로스계 보호필름을 접합할 수 있는 접착제로 UV접착제 등이 제시되어 있다. 그러나, UV접착제는 수계 접착제 보다 접착강도가 낮아 열충격 시험에서 편광자의 크랙 발생을 유도할 수 있고 가격이 매우 높아 경제성이 낮다는 단점이 있다.However, the cellulose-based protective film has a disadvantage in that it can be bonded by an adhesive only after passing through a process of saponifying (alkali treatment) the surface of the protective film when bonding the polarizer. Currently, UV adhesives and the like have been proposed as adhesives capable of bonding cellulose protective films without performing saponification processes. However, the UV adhesive has a lower adhesive strength than the water-based adhesive, which may induce cracking of the polarizer in the thermal shock test, and has a disadvantage in that the price is very high and the economic efficiency is low.
또한, 상기 셀룰로스계 보호필름은 내습열성이 낮아 편광판 성능이 저하되거나 보호필름과 편광자가 박리되는 단점이 있어, 적어도 한 쪽의 보호필름을 셀룰로스계 이외의 다양한 수지(아크릴계, 프로필렌계 수지)로 구성하려는 시도가 있다.In addition, the cellulose-based protective film has a disadvantage in that the polarizing plate performance is lowered or the protective film and the polarizer peel off due to low moisture and heat resistance, and the at least one protective film is composed of various resins other than cellulose-based resins (acrylic and propylene-based resins). There is an attempt to do so.
그러나, 종래의 폴리비닐알코올계 수지의 수용액으로 이루어진 수계 접착제는 아크릴계 보호필름과의 접착력이 낮은 문제점이 있었다[대한민국 공개특허 제2010-0095402호 참조].However, the conventional water-based adhesive made of an aqueous solution of polyvinyl alcohol-based resin had a problem of low adhesive strength with an acrylic protective film (see Korean Patent Publication No. 2010-0095402).
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로, 본 발명의 한 목적은 난접착성 보호필름과의 접착력이 우수한 편광판용 접착제 조성물을 제공하는 것이다.The present invention is to solve the above problems, one object of the present invention to provide an adhesive composition for a polarizing plate excellent in adhesion with a hard-adhesive protective film.
본 발명의 다른 목적은 상기 편광판용 접착제 조성물로부터 형성되는 접착제층을 포함하는 편광판을 제공하는 것이다.Another object of the present invention is to provide a polarizing plate comprising an adhesive layer formed from the adhesive composition for polarizing plates.
본 발명의 또 다른 목적은 상기 편광판을 포함하는 액정표시장치를 제공하는 것이다. Still another object of the present invention is to provide a liquid crystal display device including the polarizing plate.
한편으로, 본 발명은 폴리에스테르 수지 및 가교제를 포함하는 접착제 조성물을 제공한다.On the other hand, the present invention provides an adhesive composition comprising a polyester resin and a crosslinking agent.
본 발명의 일 실시형태에서, 상기 폴리에스테르 수지는 설폰산, 설폰산염, 카르복실산 또는 카르복실산염 작용기를 가지는 수용성 폴리에스테르 수지일 수 있다.In one embodiment of the present invention, the polyester resin may be a water-soluble polyester resin having a sulfonic acid, sulfonic acid salt, carboxylic acid or carboxylate functional group.
본 발명의 일 실시형태에서, 상기 폴리에스테르 수지는 설폰산, 설폰산염, 카르복실산 또는 카르복실산염 작용기를 가지는 방향족 디카르복실산과 지방족 디올을 중합반응시켜 제조될 수 있다.In one embodiment of the present invention, the polyester resin may be prepared by polymerizing an aromatic dicarboxylic acid and an aliphatic diol having a sulfonic acid, sulfonic acid salt, carboxylic acid or carboxylate functional group.
본 발명의 일 실시형태에서, 상기 폴리에스테르 수지는 하기 화학식 1 내지 2의 반복 단위 중에서 선택된 하나 이상의 반복 단위를 가지는 고분자 화합물일 수 있다. In one embodiment of the present invention, the polyester resin may be a polymer compound having one or more repeating units selected from repeating units of the following Chemical Formulas 1 to 2.
[화학식 1] [Formula 1]
Figure PCTKR2015005985-appb-I000001
Figure PCTKR2015005985-appb-I000001
[화학식 2][Formula 2]
Figure PCTKR2015005985-appb-I000002
Figure PCTKR2015005985-appb-I000002
상기 화학식에서,In the above formula,
R은 설폰산, 설폰산염, 카르복실산 또는 카르복실산염이고, R is sulfonic acid, sulfonate, carboxylic acid or carboxylate,
n은 1 내지 10의 정수이다.n is an integer from 1 to 10.
본 발명의 일 실시형태에서, 상기 폴리에스테르 수지의 분자량은 10,000 내지 40,000의 범위일 수 있다.In one embodiment of the present invention, the molecular weight of the polyester resin may range from 10,000 to 40,000.
본 발명의 일 실시형태에서, 상기 가교제가 고형분 함량을 기준으로 폴리에스테르 수지 100중량부에 대하여 50 내지 400중량부 포함될 수 있다.In one embodiment of the present invention, the crosslinking agent may be included 50 to 400 parts by weight based on 100 parts by weight of the polyester resin based on the solid content.
다른 한편으로, 본 발명은 편광자; 상기 편광자의 일면 또는 양면에 적층되고, 상기 접착제 조성물로부터 형성되는 접착제층; 및 상기 접착제층 상에 적층된 편광자 보호필름을 포함하는 편광판을 제공한다.On the other hand, the present invention is a polarizer; An adhesive layer laminated on one or both surfaces of the polarizer and formed from the adhesive composition; And it provides a polarizing plate comprising a polarizer protective film laminated on the adhesive layer.
또 다른 한편으로, 본 발명은 상기 편광판을 포함하는 액정표시장치를 제공한다.On the other hand, the present invention provides a liquid crystal display device comprising the polarizing plate.
본 발명에 따른 편광판용 접착제 조성물은 종래의 수계 접착제로는 접착하기 어려운 폴리메틸메타크릴레이트, 폴리프로필렌, 미검화 트리아세틸 셀룰로오스와 같은 난접착성 보호필름을 편광자와 우수한 접착력으로 접착 가능하게 한다. The adhesive composition for polarizing plates according to the present invention makes it possible to bond a hard-adhesive protective film such as polymethyl methacrylate, polypropylene, and unrefined triacetyl cellulose, which are difficult to adhere with conventional water-based adhesives, with excellent adhesive strength.
이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 일 실시형태는 폴리에스테르 수지 및 가교제를 포함하는 접착제 조성물에 관한 것이다. One embodiment of the present invention relates to an adhesive composition comprising a polyester resin and a crosslinking agent.
본 발명의 일 실시형태에서, 상기 폴리에스테르 수지는 설폰산, 설폰산염, 카르복실산 또는 카르복실산염 작용기를 가지는 수용성 폴리에스테르 수지일 수 있다. In one embodiment of the present invention, the polyester resin may be a water-soluble polyester resin having a sulfonic acid, sulfonic acid salt, carboxylic acid or carboxylate functional group.
상기 설폰산염은 설폰산의 나트륨염 및 칼륨염과 같은 금속염, 암모늄염 또는 유기아민염 등일 수 있으며, 설폰산의 나트륨염이 바람직하다.The sulfonate may be a metal salt such as sodium and potassium salts of sulfonic acid, an ammonium salt or an organic amine salt, and the like, and a sodium salt of sulfonic acid is preferable.
상기 카르복실산염은 카르복실산의 나트륨염 및 칼륨염과 같은 금속염, 암모늄염 또는 유기아민염 등일 수 있으며, 카르복실산의 나트륨염이 바람직하다.The carboxylic acid salt may be a metal salt such as sodium and potassium salts of carboxylic acid, ammonium salt or organic amine salt, and the like, and sodium salt of carboxylic acid is preferable.
본 발명의 일 실시형태에서, 상기 폴리에스테르 수지는 설폰산, 설폰산염, 카르복실산 또는 카르복실산염 작용기를 가지는 방향족 디카르복실산과 지방족 디올을 중합반응시켜 제조할 수 있다.In one embodiment of the present invention, the polyester resin may be prepared by polymerizing an aromatic dicarboxylic acid and an aliphatic diol having a sulfonic acid, a sulfonic acid salt, a carboxylic acid or a carboxylate functional group.
상기 방향족 디카르복실산으로는 테레프탈산, 이소프탈산, 나프탈렌 디카르복실산 등을 사용할 수 있으나, 이에 한정되는 것은 아니다. 이들은 단독 또는 2종 이상 조합하여 사용할 수 있다. Terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, etc. may be used as the aromatic dicarboxylic acid, but is not limited thereto. These can be used individually or in combination of 2 or more types.
상기 지방족 디올로는, 에틸렌글리콜, 1,4-부탄디올(1,4-butanediol), 1,3-프로판디올(1,3-propanediol) 등을 사용할 수 있으나, 이에 한정되는 것은 아니다. 이들은 단독 또는 2종 이상 조합하여 사용할 수 있다. As the aliphatic diol, ethylene glycol, 1,4-butanediol (1,4-butanediol), 1,3-propanediol (1,3-propanediol) and the like may be used, but are not limited thereto. These can be used individually or in combination of 2 or more types.
본 발명의 일 실시형태에서, 상기 폴리에스테르 수지는 하기 화학식 1 내지 2의 반복 단위 중에서 선택된 하나 이상의 반복 단위를 가지는 고분자 화합물일 수 있다. In one embodiment of the present invention, the polyester resin may be a polymer compound having one or more repeating units selected from repeating units of the following Chemical Formulas 1 to 2.
[화학식 1] [Formula 1]
Figure PCTKR2015005985-appb-I000003
Figure PCTKR2015005985-appb-I000003
[화학식 2][Formula 2]
Figure PCTKR2015005985-appb-I000004
Figure PCTKR2015005985-appb-I000004
상기 화학식에서,In the above formula,
R은 설폰산, 설폰산염, 카르복실산 또는 카르복실산염이고, R is sulfonic acid, sulfonate, carboxylic acid or carboxylate,
n은 1 내지 10의 정수이다.n is an integer from 1 to 10.
상기 폴리에스테르 수지 제품의 예로는 설폰산염 작용기를 가지는 수용성 폴리에스테르 수지인 Z-446, Z-221, Z-561 및 Z-565(구 케미컬사, GOO CHEMICAL) 등이 있으나, 이에 한정되는 것은 아니다. Examples of the polyester resin products include Z-446, Z-221, Z-561, and Z-565 (formerly, GOO CHEMICAL), which are water-soluble polyester resins having sulfonate functional groups, but are not limited thereto. .
상기 폴리에스테르 수지는 특별히 한정되지 않지만, 편광자와 보호필름 간의 높은 접착성을 발현시키기 위해서 분자량은 10,000 내지 40,000 범위에 있는 것이 바람직하다. 분자량이 10,000 미만인 경우에는 접착성을 발현하기 어렵고, 40,000 초과인 경우에는 접합공정 상에 기포 혼입의 문제점이 있다.Although the said polyester resin is not specifically limited, In order to express high adhesiveness between a polarizer and a protective film, it is preferable that molecular weight exists in the range of 10,000-40,000. If the molecular weight is less than 10,000, it is difficult to express adhesiveness, and if it is more than 40,000, there is a problem of bubble mixing in the bonding process.
본 발명의 일 실시형태에서, 상기 가교제는 편광자 및 보호필름과의 밀착성 및 내구성 향상과 고온에서의 신뢰성 및 접착제의 형상을 유지시키는 역할을 한다. In one embodiment of the present invention, the crosslinking agent serves to improve the adhesion and durability of the polarizer and the protective film and to maintain the shape of the adhesive and the reliability at high temperatures.
상기 가교제는 이소시아네이트계, 에폭시계, 과산화물계, 금속킬레이트계, 옥사졸린계, 멜라민계, 글리옥실산염계, 아지리딘계 등이 사용될 수 있으며, 단독 또는 2종 이상을 혼합 사용할 수 있다. 이 중 접착성 및 내구성 향상 면에서 아지리딘계 가교제가 바람직하다. The crosslinking agent may be an isocyanate type, an epoxy type, a peroxide type, a metal chelate type, an oxazoline type, a melamine type, a glyoxylate type, an aziridine type, or the like, or may be used alone or in combination of two or more thereof. Among them, an aziridine-based crosslinking agent is preferable in view of improving adhesion and durability.
이하, 바람직한 가교제로 아지리딘 가교제에 대하여 구체적으로 기술하나, 가교제가 이에 한정되는 것은 아니다.Hereinafter, although the aziridine crosslinking agent is specifically described as a preferable crosslinking agent, a crosslinking agent is not limited to this.
상기 아지리딘 가교제는 아지리딘 관능기가 필름 표면의 친수성기와 같은 관능기와 반응할 수 있고, 이를 포함하는 접착제 조성물은 필름의 표면에너지를 낮출 수 있어 아크릴계 필름과 같은 비극성 필름에의 젖음성이 우수하다. 따라서, 표면에 러프니스가 없고 표면에너지가 낮은 필름에도 높은 접착특성을 가질 수 있다. 또한, 상기 아지리딘 가교제는 링이 개환하여 친수성기가 형성될 수 있고, 이 친수성기는 편광자와 같은 광학 필름 표면의 히드록시기와 수소결합을 할 수 있다. 이와 같은 이유로 아지리딘 가교제는 폴리비닐알코올 접착제와 같은 기존의 접착제에 비하여 우수한 접착성을 제공할 수 있다. 또한, 다관능성 아지리딘을 갖는 화합물은 접착제층 내에서 응집효과를 높여 기포 혼입이 안되며, 내수성이 향상되는 특징을 지니고 있다. The aziridine crosslinking agent may react with an aziridine functional group such as a hydrophilic group on the surface of the film, and the adhesive composition including the aziridine functional group may lower the surface energy of the film, thereby providing excellent wettability to a nonpolar film such as an acrylic film. Therefore, it is possible to have high adhesive properties even on a film having no roughness on the surface and low surface energy. In addition, the aziridine crosslinking agent may form a hydrophilic group by ring opening, and the hydrophilic group may hydrogen bond with a hydroxyl group on the surface of an optical film such as a polarizer. For this reason, aziridine crosslinking agents can provide excellent adhesion compared to conventional adhesives such as polyvinyl alcohol adhesives. In addition, the compound having a polyfunctional aziridine has a feature of improving the cohesive effect in the adhesive layer to prevent the mixing of bubbles and to improve the water resistance.
상기 아지리딘계 가교제는 펜타에리스톨-트리스-(베타-(N-아지리디닐)프로피오네이트, 트리메틸올프로판-트리스(베타-N-아지리디닐)프로피오네이트, 트리메틸올프로판-트리스(2-메틸-1-아지리딘프로피오네이트) 등이 바람직하고, 특히 접착성능이 우수한 트리메틸올프로판-트리스(2-메틸-1-아지리딘프로피오네이트)가 보다 바람직하다. The aziridine-based crosslinking agent is pentaerythritol-tris- (beta- (N-aziridinyl) propionate, trimethylolpropane-tris (beta-N-aziridinyl) propionate, trimethylolpropane-tris (2 -Methyl-1-aziridine propionate) and the like, and trimethylolpropane-tris (2-methyl-1-aziridine propionate), which is particularly excellent in adhesion performance, is more preferable.
상기 가교제는 폴리에스테르 수지(고형분 함량 기준) 100중량부에 대하여 50 내지 400중량부, 바람직하게는 100 내지 300중량부 포함된다. 상기 함량이 50중량부 미만인 경우에는 난접착성 보호필름에 대한 접착성이 충분히 발현되기 어렵고, 함량이 400중량부를 초과하는 경우에는 조액안정성에 문제가 있다.The crosslinking agent is 50 to 400 parts by weight, preferably 100 to 300 parts by weight based on 100 parts by weight of the polyester resin (based on the solid content). If the content is less than 50 parts by weight, the adhesion to the hard-adhesive protective film is hardly expressed sufficiently, and if the content exceeds 400 parts by weight, there is a problem in the stability of the preparation.
본 발명의 일 실시형태에 따른 접착제 조성물은 편광자와 보호필름간의 높은 젖음성을 발현하기 위하여 유기용매를 추가로 포함할 수 있고, 상기 유기용매로는 알코올이 바람직하다. Adhesive composition according to an embodiment of the present invention may further include an organic solvent in order to express a high wettability between the polarizer and the protective film, the organic solvent is preferably alcohol.
상기 알코올은 난접착성 보호필름의 표면을 용해하여 접착제 조성물의 성분이 난접착성 보호필름 표면에 침투하여 화학적 반응이 일어나 기포혼입을 방지할 수 있는 역할을 한다. 또한 알코올은 난접착성 보호필름에 대해 젖음성이 우수하여 레벨링제 효과도 지니고 있다.The alcohol dissolves the surface of the hard-adhesive protective film so that the components of the adhesive composition penetrate into the hard-adhesive protective film surface, thereby causing a chemical reaction to prevent bubble mixing. In addition, alcohol has an excellent wettability against the hard-adhesive protective film also has a leveling agent effect.
상기 알코올로는 메탄올, 에탄올, 프로판올, 이소프로판올, 부탄올, t-부탄올, 글리세롤 등이 사용될 수 있으며, 1종 또는 2종 이상을 혼합 사용할 수 있다. As the alcohol, methanol, ethanol, propanol, isopropanol, butanol, t-butanol, glycerol, and the like may be used, and one or two or more thereof may be mixed.
상기 알코올은 상기 폴리에스테르 수지(고형분 함량 기준) 100 중량부에 대하여 3 내지 30중량부 포함된다. 상기 함량이 3중량부 미만이면 박리력이 저하되고, 함량이 30중량부를 초과하는 경우에는 임계 폭발 한계 농도를 넘기 때문에 방폭 설비가 필요하다는 문제점이 있다.The alcohol is included 3 to 30 parts by weight based on 100 parts by weight of the polyester resin (based on the solid content). If the content is less than 3 parts by weight, the peel force is lowered, and if the content exceeds 30 parts by weight, there is a problem that explosion-proof equipment is required because the critical explosion limit concentration is exceeded.
본 발명의 일 실시형태에 따른 접착제 조성물은 목적으로 하는 효과를 저해하지 않는 범위 내에서 당해 분야에서 일반적으로 사용되는 가소제, 실란 커플링제, 대전 방지제, 미립자, 레벨링제 등의 첨가제를 추가로 포함할 수 있다. 특히 접착제층 형성 조성물의 퍼짐성을 향상시키기 위하여 레벨링제 등을 사용하는 것이 바람직하다.The adhesive composition according to one embodiment of the present invention may further include additives such as plasticizers, silane coupling agents, antistatic agents, fine particles, leveling agents, and the like, which are generally used in the art within the range of not impairing the desired effect. Can be. It is preferable to use a leveling agent etc. especially in order to improve the spreadability of an adhesive bond layer forming composition.
본 발명의 일 실시형태에 따른 접착제 조성물은 피착체인 편광자 또는 보호필름의 표면에 균일한 접착제층을 형성하기 위해 액형인 것이 바람직하다. 이러한 액형의 접착제는 각종 용제의 용액형 또는 분산액형을 사용할 수 있으며, 기재의 도공성 면을 고려하면 용액형이 바람직하고, 안정성 면을 고려하면 물을 용매로 한 용액형 또는 분산액형이 적합하다. It is preferable that the adhesive composition which concerns on one Embodiment of this invention is liquid form in order to form a uniform adhesive bond layer on the surface of a polarizer or a protective film which is a to-be-adhered body. Such liquid adhesives may be used in the form of a solution or dispersion of various solvents. In view of the coatability of the substrate, a solution type is preferable, and in consideration of stability, a solution or dispersion with water as a solvent is preferable. .
또한, 건조 공정의 단축을 목적으로 접착제 용액 중에 물과 용이하게 혼화되고 물보다도 비점이 낮은 알코올계 용제를 배합한 물/알코올 혼합 용제를 이용할 수도 있다. 알코올계 용제의 비점은 100℃ 이하, 특히 80℃ 이하, 또는 70℃ 이하인 것이 바람직하다. In addition, for the purpose of shortening the drying step, a water / alcohol mixed solvent in which the alcohol solution is easily mixed with water in the adhesive solution and has a lower boiling point than water may be used. It is preferable that the boiling point of an alcoholic solvent is 100 degrees C or less, especially 80 degrees C or less, or 70 degrees C or less.
본 발명의 일 실시형태는 편광자; 상기 편광자의 일면 또는 양면에 적층되고, 상기 접착제 조성물로부터 형성되는 접착제층; 및 상기 접착제층 상에 적층된 편광자 보호필름을 포함하는 편광판에 관한 것이다.One embodiment of the present invention is a polarizer; An adhesive layer laminated on one or both surfaces of the polarizer and formed from the adhesive composition; And it relates to a polarizing plate comprising a polarizer protective film laminated on the adhesive layer.
본 발명의 일 실시형태에서, 상기 편광자는 연신된 폴리비닐알코올계 필름에 이색성 색소가 흡착 배향된 것이다.In one embodiment of the present invention, the polarizer is a dichroic dye adsorbed on the stretched polyvinyl alcohol-based film.
편광자를 구성하는 폴리비닐알코올계 수지는 폴리아세트산 비닐계 수지를 비누화함으로써 얻어질 수 있다. 폴리아세트산 비닐계 수지로는 아세트산 비닐의 단독 중합체인 폴리아세트산 비닐 이외에, 아세트산 비닐과 이와 공중합 가능한 다른 단량체와의 공중합체 등을 들 수 있다. 아세트산 비닐과 공중합 가능한 다른 단량체로는 불포화 카르복시산계, 불포화 술폰산계, 올레핀계, 비닐에테르계, 암모늄기를 갖는 아크릴아미드계 단량체 등을 들 수 있다. 또한 폴리비닐알코올계 수지는 변성된 것일 수도 있으며, 예를 들면 알데히드류로 변성된 폴리비닐포르말이나 폴리비닐아세탈 등도 사용할 수 있다. 폴리비닐알코올계 수지의 비누화도는 통상 85 내지 100몰%이며, 바람직하게는 98몰% 이상인 것이 좋다. 또한 폴리비닐알코올계 수지의 중합도는 통상 1,000 내지 10,000이며, 바람직하게는 1,500 내지 5,000인 것이 좋다.The polyvinyl alcohol-based resin constituting the polarizer can be obtained by saponifying a polyvinyl acetate-based resin. As polyvinyl acetate type resin, the copolymer etc. of vinyl acetate and the other monomer copolymerizable with this besides the polyvinyl acetate which is a homopolymer of vinyl acetate are mentioned. As another monomer copolymerizable with vinyl acetate, an unsaturated carboxylic acid type, an unsaturated sulfonic acid type, an olefin type, a vinyl ether type, an acrylamide type monomer which has an ammonium group, etc. are mentioned. The polyvinyl alcohol-based resin may be modified, for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used. Saponification degree of polyvinyl alcohol-type resin is 85-100 mol% normally, Preferably it is 98 mol% or more. In addition, the degree of polymerization of the polyvinyl alcohol-based resin is usually 1,000 to 10,000, preferably 1,500 to 5,000.
이러한 폴리비닐알코올계 수지를 막으로 형성한 것이 편광자의 원반 필름으로서 사용된다. 폴리비닐알코올계 수지의 막 형성 방법은 특별히 제한되는 것은 아니며, 공지된 방법을 이용할 수 있다. 원반 필름의 막 두께는 특별히 제한되지 않으며, 예를 들면 10 내지 150㎛일 수 있다.What formed such a polyvinyl alcohol-type resin into a film is used as a raw film of a polarizer. The film formation method of polyvinyl alcohol-type resin is not specifically limited, A well-known method can be used. The film thickness of the raw film is not particularly limited, and may be, for example, 10 to 150 µm.
본 발명의 편광자는 수용액 상에서 연속적으로 폴리비닐알코올계 필름을 일축 연신하는 공정, 이색성 색소로 염색하여 흡착시키는 공정, 붕산 수용액으로 처리하는 공정 및 수세, 건조하는 공정을 경유하여 제조된다.The polarizer of this invention is manufactured through the process of uniaxially stretching a polyvinyl alcohol-type film in aqueous solution, the process of dyeing and adsorb | sucking with a dichroic dye, the process of treating with an aqueous solution of boric acid, and the process of washing with water and drying.
폴리비닐알코올계 필름을 일축 연신하는 공정은 염색 전에 수행할 수 있고, 염색과 동시에 수행할 수 있으며, 염색 후에 수행할 수도 있다. 일축 연신을 염색 후에 수행하는 경우에는 붕산 처리 전에 수행할 수 있고, 붕산 처리 중에 수행할 수도 있다. 물론 이들 복수개의 단계로 일축 연신을 수행하는 것도 가능하다. 일축 연신에는 주속이 다른 롤 또는 열 롤을 이용할 수 있다. 또한 일축 연신은 대기 중에서 연신하는 건식 연신일 수도 있고, 용매로 팽윤시킨 상태에서 연신하는 습식 연신일 수도 있다. 연신비는 통상 4 내지 8배이다.The process of uniaxially stretching the polyvinyl alcohol-based film may be performed before dyeing, may be simultaneously performed with dyeing, or may be performed after dyeing. When the uniaxial stretching is performed after dyeing, it may be performed before boric acid treatment, or may be performed during boric acid treatment. Of course, it is also possible to perform uniaxial stretching in these multiple steps. For uniaxial stretching, rolls or heat rolls with different circumferential speeds can be used. In addition, uniaxial stretching may be dry stretching extending | stretching in air | atmosphere, and wet extending | stretching extending | stretching in the state swollen with a solvent may be sufficient as it. The draw ratio is usually 4 to 8 times.
연신된 폴리비닐알코올계 필름을 이색성 색소로 염색하는 공정은, 예를 들면 폴리비닐알코올계 필름을 이색성 색소를 함유하는 수용액에 침지하는 방법을 이용할 수 있다. 이색성 색소로는 요오드나 이색성 염료가 이용된다. 또한, 폴리비닐알코올계 필름은 염색 전에 물에 미리 침지하여 팽윤시키는 것이 바람직하다. As a process of dyeing a stretched polyvinyl alcohol-type film with a dichroic dye, the method of immersing a polyvinyl alcohol-type film in the aqueous solution containing a dichroic dye can be used, for example. As a dichroic dye, iodine or a dichroic dye is used. In addition, the polyvinyl alcohol-based film is preferably swelled by dipping in water before dyeing.
이색성 색소로서 요오드를 이용하는 경우에는 통상 요오드 및 요오드화칼륨을 함유하는 염색용 수용액에 폴리비닐알코올계 필름을 침지하여 염색하는 방법을 이용할 수 있다. 통상 염색용 수용액에서의 요오드의 함량은 물(증류수) 100중량부에 대하여 0.01 내지 1중량부이고, 요오드화칼륨의 함량은 물 100중량부에 대하여 0.5 내지 20중량부이다. 염색용 수용액의 온도는 통상 20 내지 40℃이고, 침지시간(염색시간)은 통상 20 내지 1,800초이다. When using iodine as a dichroic dye, the method of immersing and dyeing a polyvinyl alcohol-type film in the dyeing aqueous solution containing iodine and potassium iodide can be used normally. Usually, the content of iodine in the aqueous solution for dyeing is 0.01 to 1 part by weight based on 100 parts by weight of water (distilled water), and the content of potassium iodide is 0.5 to 20 parts by weight based on 100 parts by weight of water. The temperature of the aqueous solution for dyeing is usually 20 to 40 ° C., and the immersion time (dyeing time) is usually 20 to 1,800 seconds.
이색성 색소로서 이색성 염료를 이용하는 경우는 통상 수용성 이색성 염료를 포함하는 수용액에 폴리비닐알코올계 필름을 침지하여 염색하는 방법이 채용된다. 이 수용액에 있어서의 2색성 염료의 함유량은, 물 100 중량부 당 통상 1×10-4 내지 10중량부, 바람직하게는 1×10-3 내지 1중량부이다. 이 수용액은 황산나트륨 등의 무기염을 염색 보조제로서 함유할 수도 있다. 염색에 이용하는 염료 수용액의 온도는 통상 20 내지 80℃이고, 이 수용액에 대한 침지 시간은 통상 10 내지 1,800 초이다.When using a dichroic dye as a dichroic dye, the method of immersing and dyeing a polyvinyl alcohol-type film in the aqueous solution containing water-soluble dichroic dye is employ | adopted normally. The content of the dichroic dye in this aqueous solution is usually 1 × 10 -4 to 10 parts by weight, preferably 1 × 10 -3 to 1 part by weight per 100 parts by weight of water. This aqueous solution may contain inorganic salts, such as sodium sulfate, as a dyeing adjuvant. The temperature of the dye aqueous solution used for dyeing is 20-80 degreeC normally, and the immersion time in this aqueous solution is 10-1,800 second normally.
염색된 폴리비닐알코올계 필름을 붕산 처리하는 공정은 붕산 함유 수용액에 침지함으로써 수행할 수 있다. 통상 붕산 함유 수용액에서의 붕산의 함량은 물 100중량부에 대하여 2 내지 15중량부, 바람직하게는 5 내지 12중량부인 것이 좋다. 이색성 색소로서 요오드를 이용한 경우에는 붕산 함유 수용액은 요오드화칼륨을 함유하는 것이 바람직하며, 그 함량은 통상 물 100중량부에 대하여 0.1 내지 15중량부, 바람직하게는 5 내지 12중량부인 것이 좋다. 붕산 함유 수용액의 온도는 통상 50℃ 이상, 바람직하게는 50 내지 85℃, 보다 바람직하게는 60 내지 80℃인 것이 좋고, 침지시간은 통상 60 내지 1,200초, 바람직하게는 150 내지 600초, 보다 바람직하게는 200 내지 400초인 것이 좋다. Boric acid treatment of the dyed polyvinyl alcohol-based film can be carried out by immersing in a boric acid-containing aqueous solution. Usually, the content of boric acid in the aqueous solution containing boric acid is 2 to 15 parts by weight, preferably 5 to 12 parts by weight, based on 100 parts by weight of water. When iodine is used as the dichroic dye, the boric acid-containing aqueous solution preferably contains potassium iodide, and the content thereof is usually 0.1 to 15 parts by weight, preferably 5 to 12 parts by weight with respect to 100 parts by weight of water. The temperature of the boric acid-containing aqueous solution is usually 50 ° C or higher, preferably 50 to 85 ° C, more preferably 60 to 80 ° C, and the immersion time is usually 60 to 1,200 seconds, preferably 150 to 600 seconds, more preferably. Preferably it is 200 to 400 seconds.
붕산 처리 후 폴리비닐알코올계 필름은 통상 수세 및 건조된다. 수세처리는 붕산 처리된 폴리비닐알코올계 필름을 물에 침지함으로써 수행할 수 있다. 수세처리의 물의 온도는 통상 5 내지 40℃이고, 침지시간은 통상 1 내지 120초이다. 수세 후 건조함으로써 편광자를 얻을 수 있다. 건조처리는 통상 열풍 건조기나 원적외선 가열기를 이용하여 수행할 수 있다. 건조처리 온도는 통상 30 내지 100℃, 바람직하게는 50 내지 80℃이고, 건조시간은 통상 60 내지 600초, 바람직하게는 120 내지 600초인 것이 좋다. After the boric acid treatment, the polyvinyl alcohol-based film is usually washed with water and dried. Washing treatment can be performed by immersing the boric acid-treated polyvinyl alcohol-based film in water. The temperature of the water of a washing | cleaning process is 5-40 degreeC normally, and immersion time is 1-120 second normally. A polarizer can be obtained by drying after washing with water. The drying treatment can usually be carried out using a hot air dryer or a far infrared heater. The drying treatment temperature is usually 30 to 100 ° C, preferably 50 to 80 ° C, and the drying time is usually 60 to 600 seconds, preferably 120 to 600 seconds.
상기한 바와 같이 제조된 편광자의 두께는 5 내지 40㎛이다.The thickness of the polarizer produced as described above is 5 to 40㎛.
본 발명의 일 실시형태에서, 상기 편광자 보호필름은 투명성, 기계적 강도, 열안정성, 수분차폐성, 등방성 등이 우수한 것이라면 특별히 제한되지 않으며, 구체적으로 아크릴계, 셀룰로스계, 폴리올레핀계 또는 폴리에스테르계 필름 등이 사용될 수 있다. In one embodiment of the present invention, the polarizer protective film is not particularly limited as long as it is excellent in transparency, mechanical strength, thermal stability, moisture shielding, isotropy, and the like, specifically, acrylic, cellulose, polyolefin or polyester film, etc. Can be used.
구체적으로, 폴리메틸(메타)아크릴레이트, 폴리에틸(메타)아크릴레이트 등의 아크릴계 수지; 폴리에틸렌테레프탈레이트, 폴리에틸렌이소프탈레이트, 폴리에틸렌나프탈레이트, 폴리부틸렌테레프탈레이트 등의 폴리에스테르 수지; 디아세틸셀룰로스, 트리아세틸셀룰로스 등의 셀룰로스계 수지; 폴리에틸렌, 폴리프로필렌, 시클로계 또는 노르보넨 구조를 갖는 폴리올레핀계, 에틸렌-프로필렌 공중합체 등의 폴리올레핀계 수지; 등을 포함하는 보호필름을 들 수 있다.Specifically, Acrylic resin, such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Polyester resins such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate and polybutylene terephthalate; Cellulose resins such as diacetyl cellulose and triacetyl cellulose; Polyolefin resins such as polyethylene, polypropylene, cyclo-based or norbornene-structured polyolefin-based and ethylene-propylene copolymers; A protective film containing these etc. can be mentioned.
편광자 보호필름의 두께는 10 내지 200㎛, 바람직하게는 10 내지 150㎛인 것이 좋다. 또한, 편광자의 양면에 편광자 보호필름이 적층되는 경우 동일하거나 상이한 두께를 유지할 수 있다.The thickness of the polarizer protective film is 10 to 200㎛, preferably 10 to 150㎛. In addition, when the polarizer protective film is laminated on both sides of the polarizer may maintain the same or different thickness.
보호필름의 편광자와 접합되는 면에는 접합용이 처리를 행할 수 있다. 접합용이 처리로서는 구체적으로 프라이머 처리, 플라즈마 처리, 코로나 처리 등의 드라이 처리, 알칼리 처리(비누화 처리) 등의 화학 처리, 용이한 접착제층을 형성하는 코팅 처리 등을 들 수 있다.The bonding easy process can be performed to the surface joined with the polarizer of a protective film. Examples of the easy-to-bond treatment include dry treatment such as primer treatment, plasma treatment, corona treatment, chemical treatment such as alkali treatment (soap treatment), coating treatment to form an easy adhesive layer, and the like.
특히, 본 발명은 알칼리 처리(비누화 처리) 등의 화학처리가 수행되지 않은 보호필름(예, 미검화된 셀룰로오스계 보호필름)도 편광자와 접합이 용이하므로 특별히 이의 공정이 요구되지 않는다.In particular, the present invention is not particularly required because a protective film (eg, an ungelatinized cellulose-based protective film) that is not subjected to a chemical treatment such as an alkali treatment (saponification treatment) is easily bonded to the polarizer.
또한, 상기 미검화된 셀룰로오스계 보호필름과 함께 난접착성 보호필름으로 대표되는 표면이 드라이 처리된 아크릴계 또는 프로필렌계 보호필름도 접합이 용이하다.In addition, the acrylic or propylene protective film whose surface is represented by the hard adhesive protective film and the dry-treated protective film together with the uncellified cellulose protective film is also easy to bond.
접착제층의 두께는 통상 0.01 내지 10㎛, 바람직하게는 0.05 내지 5㎛, 보다 바람직하게는 0.1 내지 1㎛이다. 상기 보호필름의 편광자와 접합되지 않는 면에는 하드코트 처리, 반사방지 처리, 스티킹 방지, 확산 또는 안티글레어를 목적으로 한 처리를 행할 수도 있다.The thickness of an adhesive bond layer is 0.01-10 micrometers normally, Preferably it is 0.05-5 micrometers, More preferably, it is 0.1-1 micrometer. Surfaces that are not bonded to the polarizer of the protective film may be treated for the purpose of hard coat treatment, antireflection treatment, anti-sticking, diffusion or antiglare.
접합방법은 당해 분야에서 통상적인 방법일 수 있으며, 예를 들면 유연법, 마이어 바 코팅법, 그라비아 코팅법, 다이 코팅법, 딥 코팅법, 스프레이 코팅법 등을 이용하여 편광자 또는 보호필름의 접합 면에 접착제 조성물을 도포한 후 이들을 접합하는 방법을 들 수 있다. 유연법은 편광자 또는 보호필름을 대체로 수직방향, 수평방향 또는 이 둘 사이의 경사방향으로 이동시키면서 접합 면에 접착제 조성물을 유하하여 도포하는 방법이다. 접착제 조성물을 도포한 후 편광자 또는 보호필름을 닙롤 등에 끼워서 접합시킨다.The bonding method may be a conventional method in the art, and for example, the bonding surface of the polarizer or the protective film using a casting method, a meyer bar coating method, a gravure coating method, a die coating method, a dip coating method, a spray coating method, or the like. After apply | coating an adhesive composition to this, the method of joining these is mentioned. The casting method is a method in which the adhesive composition is applied to the bonding surface while the polarizer or the protective film is generally moved in the vertical direction, the horizontal direction or the inclined direction between the two. After the adhesive composition is applied, the polarizer or the protective film is sandwiched by nip roll or the like.
편광자와 보호필름을 접합한 후에는 건조처리가 수행될 수 있다. 건조처리는 예를 들면 열풍을 분무함으로써 수행되는데, 건조온도는 40 내지 100℃, 바람직하게는 60 내지 100℃의 범위에서 적절하게 선택된다. 건조시간은 20 내지 1,200초 정도일 수 있다. 건조 후에는 상온 또는 그보다 약간 높은 온도, 예를 들면 20 내지 50℃의 온도에서 12 내지 600시간 정도 양생시키는 것이 바람직하다. 건조 후 접착제층의 두께는 통상 0.001 내지 5㎛이고, 바람직하게는 0.01 내지 2㎛, 보다 바람직하게는 0.01 내지 1㎛인 것이 좋다. 접착제층의 두께가 5㎛를 초과하는 경우에는 편광판의 외관 불량 문제를 일으키기 쉽다.After bonding the polarizer and the protective film may be a drying treatment. The drying treatment is carried out, for example, by spraying hot air, and the drying temperature is appropriately selected in the range of 40 to 100 ° C, preferably 60 to 100 ° C. Drying time may be about 20 to 1,200 seconds. After drying, curing is preferably performed at room temperature or slightly higher, for example, at a temperature of 20 to 50 ° C. for about 12 to 600 hours. The thickness of an adhesive bond layer after drying is 0.001-5 micrometers normally, Preferably it is 0.01-2 micrometers, More preferably, it is 0.01-1 micrometer. When the thickness of an adhesive bond layer exceeds 5 micrometers, it will be easy to produce the external appearance problem of a polarizing plate.
일면에 편광자 보호필름이 접합된 편광자의 다른 면 상에는 필요에 따라 하드코팅층, 반사방지층, 방현층, 대전방지층 등의 표면처리층이 더 적층될 수 있다. 또한 점착제층에 의해 광학 기능성 필름이 더 적층될 수도 있다. 상기 광학 기능성 필름으로는, 예를 들면 기재 표면에 액정성 화합물 또는 이의 고분자 화합물 등이 배향되어 있는 광학보상 필름, 어떠한 종류의 편광광을 투과시키고 그것과 반대되는 성질의 편광광을 반사시키는 반사형 편광분리 필름, 폴리카보네이트 수지를 포함하는 위상차 필름, 환상 폴리올레핀계 수지를 포함하는 위상차 필름, 표면에 요철 형상을 갖는 방현기능 부가 필름, 표면 반사 방지 처리된 부가 필름, 표면에 반사 기능을 갖는 반사 필름, 반사 기능과 투과 기능을 함께 갖는 반투과 반사 필름 등을 들 수 있다.Surface treatment layers such as a hard coating layer, an antireflection layer, an antiglare layer, an antistatic layer and the like may be further laminated on the other side of the polarizer having the polarizer protective film bonded to one surface thereof. In addition, the optical functional film may be further laminated by the pressure-sensitive adhesive layer. Examples of the optical functional film include an optical compensation film in which a liquid crystalline compound or a polymer compound thereof is oriented on the surface of a substrate, a reflection type that transmits polarized light of any kind and reflects polarized light having a property opposite thereto. A polarizing separation film, a retardation film containing a polycarbonate resin, a retardation film containing a cyclic polyolefin resin, an antiglare function addition film having a concave-convex shape on the surface, an addition film treated with surface reflection prevention, a reflection film having a reflection function on the surface And a semi-transmissive reflective film having both a reflection function and a transmission function.
본 발명의 일 실시형태는 상기 편광판을 포함하는 액정표시장치에 관한 것이다. One embodiment of the present invention relates to a liquid crystal display device comprising the polarizing plate.
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: 편광자의 제조Preparation Example 1 Preparation of Polarizer
평균 중합도가 2,400이고 비누화도가 99.9몰% 이상인 75㎛ 두께의 폴리비닐알코올 필름을 건식으로 약 5배로 일축 연신하고, 연신 상태를 유지한 채로 60℃의 물(증류수)에 1분 동안 침지한 후, 요오드/요오드화칼륨/증류수의 중량비가 0.05/5/100인 28℃의 수용액에서 60초 동안 침지하였다. 그 후, 요오드화칼륨/붕산/증류수의 중량비가 8.5/8.5/100인 72℃ 수용액에 300초 동안 침지하고, 26℃의 증류수로 20초 동안 세척한 후, 65℃에서 건조하여 PVA계 필름에 요오드가 흡착 배향된 편광자를 제조하였다. After uniaxially stretching a polyvinyl alcohol film having a thickness of 2,400 with an average degree of polymerization of 2,400 and a saponification degree of 99.9 mol% to about 5 times by dry, immersing in 60 ° C water (distilled water) for 1 minute while maintaining the stretched state. And immersed for 60 seconds in an aqueous solution at 28 ° C. having a weight ratio of iodine / potassium iodide / distilled water of 0.05 / 5/100. Thereafter, the weight ratio of potassium iodide / boric acid / distilled water was immersed in an aqueous solution of 72 ° C. having 8.5 / 8.5 / 100 for 300 seconds, washed with distilled water at 26 ° C. for 20 seconds, and then dried at 65 ° C. to iodine on a PVA film. The adsorbed oriented polarizer was prepared.
실시예 1 내지 12 및 비교예 1: Examples 1-12 and Comparative Example 1:
(1) 편광판용 접착제 조성물의 제조(1) Preparation of Adhesive Composition for Polarizing Plates
하기 표 1의 조성으로 각 성분을 혼합하여 편광판용 접착제 조성물을 제조하였다. 이때, 각 성분은 고형분 함량을 기준으로 혼합하였다.Each component was mixed with the composition of Table 1 below to prepare an adhesive composition for a polarizing plate. At this time, each component was mixed based on the solid content.
(2) 편광판의 제조(2) Preparation of Polarizing Plate
제조예 1에서 수득한 요오드가 흡착 배향된 편광자의 양면에, 상기 접착제 조성물을 건조막 두께가 0.1㎛가 되도록 도포한 후, 닙롤을 이용하여 코로나 처리된 폴리메틸(메타)아크릴레이트 보호필름을 접합시켰다. 이후에 80℃의 열풍 건조기에서 5분 동안 건조하여 편광판을 제조하였다.After applying the adhesive composition to a dry film thickness of 0.1 μm on both surfaces of the polarizer with the iodine adsorption-oriented orientation obtained in Preparation Example 1, using a nip roll to bond the polymethyl (meth) acrylate protective film I was. After drying for 5 minutes in a hot air dryer of 80 ℃ to prepare a polarizing plate.
표 1
Figure PCTKR2015005985-appb-T000001
 Table 1
Figure PCTKR2015005985-appb-T000001
Z-446 및 Z-221(구 케미컬사): 폴리에스테르 수지Z-446 and Z-221 (formerly chemical company): polyester resin
CL-427(메나디오나사): 펜타에리스톨-트리스-(베타-N-아지리디닐)프로피오네이트CL-427 (menadiona thread): pentaerythritol-tris- (beta-N-aziridinyl) propionate
CX-100(DSM사): 트리메틸올프로판-트리스(2-메틸-1-아지리딘프로피오네이트)CX-100 (DSM company): trimethylolpropane-tris (2-methyl-1-aziridinepropionate)
에탄올(알드리치사)Ethanol (Aldrich)
폴리비닐알코올계 수지(코세놀 Z200, 일본합성화학공업㈜)Polyvinyl alcohol resin (Cosenol Z200, Nippon Synthetic Chemical Co., Ltd.)
실험예 1: 접착성 및 박리력 평가Experimental Example 1 Evaluation of Adhesiveness and Peeling Force
상기 실시예 및 비교예에서 제조된 편광판의 물성을 하기와 같은 방법으로 측정하여, 그 결과를 하기 표 2에 나타내었다.The physical properties of the polarizing plates prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Table 2 below.
(1) 접착성(커터) 평가(1) Adhesiveness (Cutter) Evaluation
제조된 편광판을 1시간 상온에서 방치한 후, 편광판의 각 필름 사이(편광자와 편광자 보호필름 사이)에 커터의 날을 넣고, 날을 밀고 나아갔을 때의 날이 들어가는 방식을 하기의 기준으로 평가하였다.After leaving the prepared polarizing plate at room temperature for 1 hour, a cutter blade was placed between each film (between the polarizer and the polarizer protective film) of the polarizing plate, and the method of entering the blade when pushing the blade was evaluated by the following criteria. .
<평가 기준><Evaluation Criteria>
◎: 커터의 날이 어느 필름 사이에도 들어가지 않는다.(Double-circle): The cutter blade does not enter between any films.
○: 날을 밀고 나아갔을 때, 적어도 어느 한 쪽의 필름 사이에 날이 1 내지 2 mm 들어갔을 때 멈춘다.(Circle): When pushing on a blade, it stops when a blade enters 1-2 mm between at least one film.
△: 날을 밀고 나아갔을 때, 적어도 어느 한 쪽의 필름 사이에 날이 3 내지 5 mm 들어갔을 때 멈춘다.(Triangle | delta): When pushing on a blade, it stops when a blade enters 3-5 mm between at least one film.
×: 날을 밀고 나아갔을 때, 적어도 어느 한 쪽의 필름 사이에 날이 무리 없이 들어간다.X: When pushing on a blade, a blade enters in between at least one film.
(2) 박리력(2) peeling force
제조된 편광판을 1시간 상온에서 방치한 후, 점착제를 이용해 소다 글래스 위에 핸드롤러를 이용해서 접합을 진행한 후, 압력 2atm, 온도 50℃, 시간 20분의 조건에서 오토클레이브 처리를 진행하여 접합 시 발생된 기포를 제거하였다. 소다 글래스/점착제/아크릴계 편광판에서, 소다 글래스 방향에 코로나 처리된 아크릴계 보호필름과 편광자 사이에 칼을 넣고 오토 그라프를 이용하여 편광자 박리 시 접착제층 면에서의 180o 박리력(측정속도 300mm/min)을 측정하였다.After leaving the prepared polarizing plate at room temperature for 1 hour, the bonding was performed by using a hand roller on a soda glass using a pressure-sensitive adhesive, and then subjected to autoclave treatment at a pressure of 2 atm, a temperature of 50 ° C., and a time of 20 minutes. Bubbles generated were removed. In soda glass / adhesive / acrylic polarizer, 180 ° peel force on adhesive layer when peeling polarizer using autograph with knife between corona-treated acrylic protective film and polarizer in soda glass direction (measuring speed 300mm / min) Was measured.
표 2
Figure PCTKR2015005985-appb-T000002
 TABLE 2
Figure PCTKR2015005985-appb-T000002
상기 표 2에서 보듯이, 본 발명에 따른 폴리에스테르 수지를 포함하는 실시예 1 내지 12의 접착제 조성물은 폴리비닐알코올계 수지를 포함하는 비교예 1의 접착제 조성물에 비해 접착성 및 박리력이 현저히 우수함을 확인할 수 있었다. As shown in Table 2, the adhesive composition of Examples 1 to 12 including the polyester resin according to the present invention is significantly superior in adhesion and peeling force than the adhesive composition of Comparative Example 1 containing a polyvinyl alcohol-based resin. Could confirm.
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 (14)

  1. 폴리에스테르 수지 및 가교제를 포함하는 접착제 조성물.Adhesive composition containing a polyester resin and a crosslinking agent.
  2. 제1항에 있어서, 폴리에스테르 수지는 설폰산, 설폰산염, 카르복실산 또는 카르복실산염 작용기를 가지는 수용성 폴리에스테르 수지인 접착제 조성물. The adhesive composition according to claim 1, wherein the polyester resin is a water-soluble polyester resin having sulfonic acid, sulfonic acid salt, carboxylic acid or carboxylate functional group.
  3. 제2항에 있어서, 설폰산염은 설폰산의 나트륨염인 접착제 조성물. The adhesive composition of claim 2, wherein the sulfonate is a sodium salt of sulfonic acid.
  4. 제1항에 있어서, 폴리에스테르 수지는 설폰산, 설폰산염, 카르복실산 또는 카르복실산염 작용기를 가지는 방향족 디카르복실산과 지방족 디올을 중합반응시켜 제조되는 접착제 조성물. The adhesive composition according to claim 1, wherein the polyester resin is prepared by polymerizing an aromatic dicarboxylic acid and an aliphatic diol having sulfonic acid, sulfonic acid salt, carboxylic acid or carboxylate functional group.
  5. 제4항에 있어서, 방향족 디카르복실산은 테레프탈산, 이소프탈산 및 나프탈렌 디카르복실산으로 이루어진 군에서 1종 이상 선택되는 접착제 조성물.The adhesive composition according to claim 4, wherein the aromatic dicarboxylic acid is at least one selected from the group consisting of terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid.
  6. 제4항에 있어서, 지방족 디올은 에틸렌글리콜, 1,4-부탄디올 및 1,3-프로판디올로 이루어진 군에서 1종 이상 선택되는 접착제 조성물.The adhesive composition according to claim 4, wherein the aliphatic diol is selected from the group consisting of ethylene glycol, 1,4-butanediol and 1,3-propanediol.
  7. 제1항에 있어서, 폴리에스테르 수지는 하기 화학식 1 내지 2의 반복 단위 중에서 선택된 하나 이상의 반복 단위를 가지는 고분자 화합물인 접착제 조성물:The adhesive composition according to claim 1, wherein the polyester resin is a high molecular compound having at least one repeating unit selected from repeating units of the following Chemical Formulas 1-2.
    [화학식 1] [Formula 1]
    Figure PCTKR2015005985-appb-I000005
    Figure PCTKR2015005985-appb-I000005
    [화학식 2][Formula 2]
    Figure PCTKR2015005985-appb-I000006
    Figure PCTKR2015005985-appb-I000006
    상기 화학식에서,In the above formula,
    R은 설폰산, 설폰산염, 카르복실산 또는 카르복실산염이고, R is sulfonic acid, sulfonate, carboxylic acid or carboxylate,
    n은 1 내지 10의 정수이다.n is an integer from 1 to 10.
  8. 제1항에 있어서, 폴리에스테르 수지의 분자량은 10,000 내지 40,000의 범위인 접착제 조성물.The adhesive composition of claim 1 wherein the molecular weight of the polyester resin is in the range of 10,000 to 40,000.
  9. 제1항에 있어서, 가교제가 고형분 함량을 기준으로 폴리에스테르 수지 100중량부에 대하여 50 내지 400중량부 포함되는 접착제 조성물.The adhesive composition according to claim 1, wherein the crosslinking agent is included in an amount of 50 to 400 parts by weight based on 100 parts by weight of the polyester resin based on the solid content.
  10. 제1항에 있어서, 알코올을 추가로 포함하는 접착제 조성물.The adhesive composition of claim 1 further comprising an alcohol.
  11. 제10항에 있어서, 알코올이 고형분 함량을 기준으로 폴리에스테르 수지 100중량부에 대하여 3 내지 30중량부 포함되는 접착제 조성물.The adhesive composition according to claim 10, wherein the alcohol is included in an amount of 3 to 30 parts by weight based on 100 parts by weight of the polyester resin based on the solid content.
  12. 편광자; 상기 편광자의 일면 또는 양면에 적층되고, 제1항 내지 제11항 중 어느 한 항에 따른 접착제 조성물로부터 형성되는 접착제층; 및 상기 접착제층 상에 적층된 편광자 보호필름을 포함하는 편광판.Polarizer; An adhesive layer laminated on one or both surfaces of the polarizer and formed from the adhesive composition according to any one of claims 1 to 11; And a polarizer protective film laminated on the adhesive layer.
  13. 제12항에 있어서, 편광자 보호필름이 아크릴계, 셀룰로스계, 폴리올레핀계 또는 폴리에스테르계 필름인 편광판.The polarizing plate according to claim 12, wherein the polarizer protective film is an acrylic, cellulose, polyolefin, or polyester film.
  14. 제12항에 따른 편광판을 포함하는 액정표시장치.A liquid crystal display device comprising the polarizing plate of claim 12.
PCT/KR2015/005985 2014-06-20 2015-06-15 Adhesive composition and polarizing plate comprising same WO2015194805A1 (en)

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Publication number Priority date Publication date Assignee Title
JPH08271733A (en) * 1995-04-03 1996-10-18 Fujimori Kogyo Kk Front side protective sheet for front side polarizing plate, its production and sticking method of front side protective sheet to polarizing base film
KR20100011179A (en) * 2008-07-24 2010-02-03 주식회사 엘지화학 Pressure-sensitive adhesive composition, polarizers and liquid crystal display comprising the same
KR20130019001A (en) * 2007-12-06 2013-02-25 닛토덴코 가부시키가이샤 Polarizing plate and image display device
KR20130103290A (en) * 2012-03-09 2013-09-23 제일모직주식회사 Adhesive composition for polarizing plate and polarizing plate using the same
KR20140015346A (en) * 2011-02-02 2014-02-06 도요보 가부시키가이샤 Highly adhesive polyester film for protection of polarizers

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Publication number Priority date Publication date Assignee Title
KR101197164B1 (en) 2009-02-20 2012-11-02 주식회사 엘지화학 Modified Poly Vinyl Alcohol Resin, Adhesive, Polarizing Plate and Display Apparatus Comprising the Same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08271733A (en) * 1995-04-03 1996-10-18 Fujimori Kogyo Kk Front side protective sheet for front side polarizing plate, its production and sticking method of front side protective sheet to polarizing base film
KR20130019001A (en) * 2007-12-06 2013-02-25 닛토덴코 가부시키가이샤 Polarizing plate and image display device
KR20100011179A (en) * 2008-07-24 2010-02-03 주식회사 엘지화학 Pressure-sensitive adhesive composition, polarizers and liquid crystal display comprising the same
KR20140015346A (en) * 2011-02-02 2014-02-06 도요보 가부시키가이샤 Highly adhesive polyester film for protection of polarizers
KR20130103290A (en) * 2012-03-09 2013-09-23 제일모직주식회사 Adhesive composition for polarizing plate and polarizing plate using the same

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