KR20170069818A - Adhesive film for polarizing plate, polarizing plate comprising the same and optical display apparatus comprising the same - Google Patents

Adhesive film for polarizing plate, polarizing plate comprising the same and optical display apparatus comprising the same Download PDF

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KR20170069818A
KR20170069818A KR1020150177495A KR20150177495A KR20170069818A KR 20170069818 A KR20170069818 A KR 20170069818A KR 1020150177495 A KR1020150177495 A KR 1020150177495A KR 20150177495 A KR20150177495 A KR 20150177495A KR 20170069818 A KR20170069818 A KR 20170069818A
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polarizing plate
meth
adhesive film
mol
group
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KR1020150177495A
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Korean (ko)
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KR101943694B1 (en
Inventor
남이리나
김대윤
김영종
김원
한인천
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삼성에스디아이 주식회사
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Priority to KR1020150177495A priority Critical patent/KR101943694B1/en
Priority to TW105137997A priority patent/TWI642742B/en
Priority to CN201611048768.1A priority patent/CN106978111B/en
Priority to US15/360,557 priority patent/US10358581B2/en
Publication of KR20170069818A publication Critical patent/KR20170069818A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • C09J7/02—
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • 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
    • C09J2205/114—
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)

Abstract

A pressure-sensitive adhesive film for a polarizing plate formed from a pressure-sensitive adhesive composition for a polarizing plate comprising a (meth) acrylic copolymer and a cellulose ester binder having an alkyl group, a hydroxyl group, an alicyclic group and a heterocyclic group and having a modulus of 100,000 Pa or higher at 30 ° C, And an optical display device including the same.

Description

TECHNICAL FIELD [0001] The present invention relates to an adhesive film for a polarizing plate, a polarizing plate including the same, and an optical display device including the polarizing plate.

The present invention relates to a pressure-sensitive adhesive film for a polarizing plate, a polarizing plate including the same, and an optical display device including the same.

The liquid crystal display device includes a liquid crystal panel and a polarizing plate attached to both sides of the liquid crystal panel. The polarizing plate includes a polarizer and a protective film formed on one or both surfaces of the polarizer to protect the polarizer. The polarizing plate is attached to the liquid crystal panel by an adhesive film for a polarizing plate. The pressure sensitive adhesive film for a polarizing plate is formed of a pressure sensitive adhesive composition for a polarizing plate.

When the polarizing plate is placed on a glass plate such as a liquid crystal panel, the pencil hardness of the polarizing plate on the glass plate is high. However, when the polarizing plate is adhered to a glass plate such as a liquid crystal panel with an adhesive film for a polarizing plate and the pencil hardness is measured, the pencil hardness of the polarizing plate on the adhesive film becomes lower than the pencil hardness of the polarizing plate on the glass plate. When the polarizing plate is adhered to the liquid crystal panel by the adhesive film, if the pencil hardness of the polarizing plate on the adhesive film is lowered, it may be difficult to use in an optical display device.

The adhesive film for a polarizing plate having a high modulus can increase the pencil hardness of the polarizing plate on the adhesive film. However, an adhesive film having a high modulus even at a high temperature may cause durability deterioration such as light leakage, lifting of a polarizing plate, attraction or bubble generation. Light leakage, durability and the like are caused by contraction due to heat and / or moisture of the polarizer. Therefore, a pressure-sensitive adhesive film for a polarizing plate which is high in modulus as a hard-type pressure-sensitive adhesive film at room temperature and high in pencil hardness of a polarizing plate on a pressure-sensitive adhesive film and soft in low temperature to suppress light leakage and enhance durability is required. In a conventional hard type adhesive film having a high modulus, the modulus is lowered at a high temperature. However, since the degree of reduction of modulus is extremely low, light leakage may occur at high temperatures or durability may be poor.

The background art of the present invention is described in Japanese Laid-Open Patent Application No. 2015-010192.

An object of the present invention is to provide an adhesive film for a polarizing plate capable of increasing the pencil hardness of a polarizing plate on a pressure-sensitive adhesive film.

Another object of the present invention is to provide a pressure sensitive adhesive film for a polarizing plate capable of increasing the pencil hardness of a polarizing plate on a pressure sensitive adhesive film at room temperature and modulating the light leakage at a high temperature and / will be.

Another object of the present invention is to provide a pressure-sensitive adhesive film for a polarizing plate capable of improving durability even from a low temperature to a high temperature.

It is still another object of the present invention to provide a polarizing plate comprising the above-mentioned pressure sensitive adhesive film for a polarizing plate.

It is still another object of the present invention to provide an optical display device comprising the polarizing plate or the polarizing plate.

The pressure-sensitive adhesive film for a polarizing plate of the present invention is formed of a pressure-sensitive adhesive composition for a polarizing plate comprising a (meth) acrylic copolymer having an alkyl group, a hydroxyl group, an alicyclic group and a heterocyclic group and a cellulose ester binder, and has a modulus of 100,000 Pa or more .

The adhesive film for a polarizing plate of the present invention has a creep of 200 占 퐉 or less at 25 占 폚, a modulus ratio of 1.5 or more and a modulus of 100,000 Pa or more at 30 占 폚.

<Formula 1>

Modulus ratio = A / B

(In the above formula 1, A and B are as defined in the detailed description of the present invention).

In the polarizing plate of the present invention, the adhesive film for a polarizing plate, the polarizer, and the optical film are sequentially laminated, the polarizing plate has a pencil hardness of 2H or more, the polarizing plate adhesive film has a creep of 250 탆 or more at 85 캜, The film may be 200 占 퐉 or less at 25 占 폚.

The optical display device of the present invention may include the polarizing plate or the polarizing plate.

The present invention provides a pressure-sensitive adhesive film for a polarizing plate capable of increasing pencil hardness of a polarizing plate on a pressure-sensitive adhesive film.

The present invention provides a pressure sensitive adhesive film for a polarizing plate capable of increasing the pencil hardness of a polarizing plate on a pressure sensitive adhesive film at room temperature and having a modulus at a high temperature and / or high temperature and high humidity, thereby suppressing light leakage and enhancing durability.

The present invention provides a pressure-sensitive adhesive film for a polarizing plate capable of improving durability even under heat shock from a low temperature to a high temperature.

The present invention provides a polarizing plate comprising the above-mentioned pressure sensitive adhesive film for a polarizing plate.

The present invention provides an optical display device comprising the polarizing plate or the polarizing plate.

1 is a conceptual diagram of measurement of a creep in this specification.
2 is a cross-sectional view of a polarizing plate of one embodiment of the present invention.
3 is a cross-sectional view of a polarizing plate of another embodiment of the present invention.
4 is a sectional view of a liquid crystal display device according to an embodiment of the present invention.
5 is a plan view of a light leakage measurement specimen.

The present invention is not limited to the above embodiments and various changes and modifications may be made by those skilled in the art without departing from the scope of the present invention. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and the same or similar components are denoted by the same reference numerals throughout the specification.

It should be noted that the terms "upper" and "lower" in the present specification are based on the drawings and are not necessarily fixed to the upper and lower portions, .

In the present specification, "adhesive film for polarizing plate" and "pressure-sensitive adhesive composition for polarizing plate" may be referred to as "adhesive film" and "pressure-sensitive adhesive composition", respectively.

As used herein, "(meth) acrylic" means acrylic and / or methacrylic.

In the present specification, the "modulus" of the pressure-sensitive adhesive film is a storage modulus, and a plurality of pressure-sensitive adhesive films having a thickness of 20 μm are laminated and cut to produce circular specimens having a thickness of 500 μm and a diameter of 8 mm. The strain 5%, the angular frequency (ω) of 10 rad / s and the normal force (normal force) were measured with a Physica MCR501 (Anton parr) at a heating rate of 10 ° C./min from 0 ° C. to 150 ° C. on a disk having a diameter of 8 mm. Quot; means values at 30 ° C and 120 ° C when evaluated at 1.5N. At this time, the pressure-sensitive adhesive film was prepared by coating a pressure-sensitive adhesive composition on a polyethylene terephthalate film coated with a silicone material as a releasing agent, drying it at 105 ° C for 4 minutes and aging it at 35 ° C and 45% RH for 48 hours to produce a pressure- And releasing from the release film. However, the present invention is not limited thereto.

1, a creep test specimen 23 is laminated on the end of an alkali-free glass plate 20 with an area of axb (for example, 15 mm x 15 mm) and a load W is applied for 1000 seconds The distance measured from the alkali-free glass plate 20 was measured when the specimen 23 for creep measurement was pulled out. The specimen 23 for creep measurement includes a pressure-sensitive adhesive film 21 (thickness: 20 占 퐉) and a polarizing plate 22 formed on the pressure-sensitive adhesive film 21. The polarizing plate 22 includes a triacetylcellulose film, a polarizer, and a triacetylcellulose film which are sequentially laminated. The load W was 2250 g at a creep measurement temperature of 25 ° C and 1500 g at a creep measurement temperature of 85 ° C. The creep can be measured using TEXTURE ANALYZER TA.XT PLUS (5 kg load cell, EKO Instruments). At this time, the adhesive film may be the same as the adhesive film in the measurement of the modulus.

In the present specification, "pencil hardness of the polarizing plate on the pressure-sensitive adhesive film" in the present specification means a pressure-sensitive adhesive film is usually placed on a glass plate for measuring pencil hardness and a polarizing plate is placed on the adhesive film. Then, pencil hardness (Heidon) . The pencil hardness of the polarizing plate on the pressure-sensitive adhesive film was measured for a specimen in which an adhesive film / triacetylcellulose film 1 (thickness: 40 m) / polarizer (thickness: 8 m) / triacetylcellulose film 2 Respectively. The pressure-sensitive adhesive film of the specimen was attached to a glass plate, and the specimen was fixed to a glass plate and treated in an autoclave at 5 atm, 50 ° C, and 1000 seconds. Prior to pencil hardness measurements, they were held for 24 hours at 23 &lt; 0 &gt; C and 55% relative humidity. Pencil hardness was measured on the surface of the triacetyl cellulose film 2 in the specimen using a COASTEK pencil hardness tester (COA TECH KOREA). The pencil hardness was measured at a speed of 48 mm / min and the pencil load of the triacetylcellulose film 2 was 500 g. When measured with the same pencil hardness, it is the maximum pencil hardness value when there is no scratch at all five times in the evaluation of 5 times.

Hereinafter, a pressure-sensitive adhesive film for a polarizing plate and a pressure-sensitive adhesive composition for a polarizing plate according to an embodiment of the present invention will be described.

The adhesive film for a polarizing plate according to this embodiment may include a (meth) acrylic copolymer having an alkyl group, a hydroxyl group, an alicyclic group, and a heteroalicyclic group, and a cellulose ester binder.

The pressure-sensitive adhesive film for a polarizing plate may have a high modulus at 30 DEG C due to hydrogen bonding between the hetero-alicyclic group of the (meth) acrylic copolymer and the cellulose ester binder. Specifically, the pressure-sensitive adhesive film for a polarizing plate may have a modulus of 100,000 Pa or more, more specifically 100,000 Pa to 450,000 Pa at 30 占 폚. Within the above-mentioned range, excellent workability and processability at room temperature, excellent reliability, high pencil hardness of the polarizing plate on the pressure-sensitive adhesive film, and improvement of warping and light leakage can be obtained.

The pressure-sensitive adhesive film for a polarizing plate can contain a (meth) acrylic copolymer and a cellulose ester binder, so that the modulus can be low at 120 캜, creep can be lowered at room temperature, and creep can be made higher at high temperature. Specifically, the pressure-sensitive adhesive film for a polarizing plate may have a modulus of 80,000 Pa or less, specifically 20,000 Pa to 80,000 Pa at 120 ° C. In the above range, light leakage can be suppressed at a high temperature, and durability can be improved. Specifically, the adhesive film for a polarizing plate may have a creep of 200 占 퐉 or less at 25 占 폚 and a creep of 250 占 퐉 or more at 85 占 폚. In the above range, the hard adhesive film is low in creep at room temperature, so that the pencil hardness of the polarizing plate on the adhesive film is high and the creep is high at high temperature, so that the soft adhesive film can suppress light leakage and improve adhesion and durability. Specifically, the adhesive film for a polarizing plate may have a creep at 25 占 폚 of 50 占 퐉 to 200 占 퐉 and a crease at 85 占 폚 of 250 占 퐉 to 800 占 퐉, specifically 250 占 퐉 to 500 占 퐉.

Therefore, the pressure-sensitive adhesive film for a polarizing plate has a high modulus at room temperature (for example, 30 ° C) and a modulus at low temperature and / or high temperature and high humidity (for example, 120 ° C) The hardness is increased, the light leakage is suppressed at high temperature, and the durability can be increased. The pressure-sensitive adhesive film for a polarizing plate may have a modulus ratio of 1.5 or more, specifically 1.5 to 50, more specifically 1.8 to 30, and even more specifically 4 to 20 in the following formula 1:

<Formula 1>

Modulus ratio = A / B

(Wherein A is the modulus of the polarizing plate adhesive film at 30 DEG C and B is the modulus of the polarizing plate adhesive film at 120 DEG C)

The adhesive film for a polarizing plate is optically transparent and can be used in an optical display device. Specifically, the adhesive film may have a light transmittance of 85% or more, more specifically 85% to 99.9% in a visible light region (e.g., a wavelength of 380 nm to 780 nm).

The thickness of the pressure sensitive adhesive film for a polarizing plate may be 40 占 퐉 or less, specifically 5 占 퐉 to 30 占 퐉. In the above range, it can be used in an optical display device.

The pressure-sensitive adhesive film for a polarizing plate can be produced by coating the pressure-sensitive adhesive composition for a polarizing plate to a predetermined thickness, drying it, and then aging at a constant temperature and humidity of 25 to 35 DEG C and a relative humidity of 30 to 60%.

Hereinafter, the pressure-sensitive adhesive composition for a polarizing plate will be described in detail.

The pressure-sensitive adhesive composition for a polarizing plate may include a (meth) acrylic copolymer having an alkyl group, a hydroxyl group, an alicyclic group and a hetero-alicyclic group, a curing agent, and a cellulose ester binder.

The (meth) acrylic copolymer having an alkyl group, a hydroxyl group, an alicyclic group and a hetero-alicyclic group may form a matrix of a pressure-sensitive adhesive film for a polarizing plate. The (meth) acrylic copolymer having an alkyl group, a hydroxyl group, an alicyclic group and a hetero-alicyclic group can increase the modulus of the pressure-sensitive adhesive film at 30 ° C through bonding of a heteroalicyclic group and a cellulose ester binder. The (meth) acrylic copolymer having an alkyl group, a hydroxyl group, an alicyclic group and a heteroalicyclic group is preferably a (meth) acrylic monomer having an alkyl group, a (meth) acrylic monomer having a hydroxyl group, a (meth) acrylic monomer having an alicyclic group and a heteroalicyclic (Meth) acryl-based monomer having a (meth) acryl-based monomer.

The (meth) acrylic monomer having an alkyl group is contained in the (meth) acrylic copolymer to form a matrix of the adhesive film, thereby increasing the mechanical strength of the adhesive film and providing stickiness and stickiness. The (meth) acrylic monomer having an alkyl group may be contained in the monomer mixture in an amount of 40 mol% to 95 mol%, specifically 45 mol% to 90 mol% and 55 mol% to 85 mol%. Within the above range, the mechanical strength of the pressure-sensitive adhesive film can be increased.

The (meth) acrylic monomer having an alkyl group may include a (meth) acrylic acid ester having an unsubstituted C4 to C12 alkyl group. Specifically, the (meth) acrylic monomer having an alkyl group is selected from the group consisting of n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (Meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, But are not limited to, one or more of dodecyl (meth) acrylate. These may be included singly or in combination of two or more.

The (meth) acrylic monomer having a hydroxyl group can provide a hydroxyl group to the (meth) acrylic copolymer to react with the curing agent and / or increase the adhesive strength of the adhesive film and enhance the durability of the adhesive film. The (meth) acrylic monomer having a hydroxyl group may be contained in an amount of 0.1 mol% to 20 mol%, specifically 0.5 mol% to 10 mol% and 1 mol% to 7.5 mol% in the monomer mixture. Within the above range, the adhesive strength and durability of the adhesive film are improved, and peelability and cohesive force can be improved.

The (meth) acrylic monomer having a hydroxyl group is a (meth) acrylic monomer having a C1 to C20 alkyl group having at least one hydroxyl group, a (meth) acrylic monomer having a C3 to C20 cycloalkyl group having at least one hydroxyl group, (Meth) acryl-based monomers having C6 to C20 aromatic groups. Specifically, the (meth) acrylic monomer having a hydroxyl group is preferably selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl Cyclohexanedimethanol mono (meth) acrylate, 1-chloro-2-hydroxypropyl (meth) acrylate, diethylene glycol (meth) acrylate, At least one of mono (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4-hydroxycyclopentyl (meth) acrylate and 4-hydroxycyclohexyl (meth) . These may be included singly or in combination of two or more.

The (meth) acrylic monomer having an alicyclic group is included in the (meth) acrylic copolymer, and the pencil hardness of the polarizing plate on the pressure-sensitive adhesive film of the polarizing plate to which the pressure-sensitive adhesive film for polarizing plate is adhered can be increased. Specifically, in the polarizing plate to which the polarizing plate adhesive film is adhered, the pencil hardness of the polarizing plate on the adhesive film may be 2H or more, more specifically 2H to 3H. When a general adhesive film is measured for the same polarizing plate, the pencil hardness of the polarizing plate on the pressure-sensitive adhesive film can be from 4B to H. In the above range, even when the polarizing plate is adhered to a liquid crystal panel such as a glass material with an adhesive film for a polarizing plate, the polarizing plate can be used for an optical display device because the contrast pencil hardness is not significantly reduced when the polarizing plate is adhered to the liquid crystal panel without an adhesive film.

Further, the (meth) acrylic monomer having an alicyclic group is included in the (meth) acrylic copolymer together with the (meth) acrylic monomer having the following hetero-alicyclic group to reduce the creep at 25 ° C of the polarizing plate adhesive film, Can be increased. Particularly, when the (meth) acrylic monomer having a cycloaliphatic group and the (meth) acrylic monomer having a heteroalicyclic group each have a glass transition temperature of not less than 5 ° C and specifically 10 ° C to 200 ° C at the homopolymer, the creep is lowered at 25 ° C The creep can be increased at 85 ° C. The (meth) acrylic monomer having the alicyclic group and the (meth) acrylic monomer having the heteroalicyclic group in the monomer mixture may be contained in a molar ratio of 1: 0.5 to 1:40, specifically 1: 0.5 to 1:20. Within this range, there may be an effect of increasing the pencil hardness.

The (meth) acrylic monomer having an alicyclic group may be contained in an amount of from 1 mol% to 30 mol%, specifically from 5 mol% to 25 mol%, of the monomer mixture. In the above range, the pencil hardness of the polarizing plate on the pressure-sensitive adhesive film can be increased, and reliability can be improved.

The (meth) acrylic monomer having an alicyclic group may include a (meth) acrylic acid ester having a substituted or unsubstituted C5 to C20 monocyclic or heterocyclic alicyclic group. Means that at least one hydrogen is substituted with a C1 to C10 alkyl group, a C3 to C10 alicyclic group, a C6 to C20 aromatic group, a halogen, or a nitro group. The term " substituted or unsubstituted " The "cycloaliphatic group" means a non-heteroalicyclic group containing no hetero atom of nitrogen, oxygen or sulfur. The "heterocycle" means that two or more alicyclic groups share one or more carbon atoms and are linked. Specifically, the (meth) acrylic acid ester having a substituted or unsubstituted C5 to C20 alicyclic or alicyclic alicyclic group is preferably selected from cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl ) Acrylate, methylcyclohexyl (meth) acrylate, and dicyclopentenyl (meth) acrylate. These may be included singly or in combination of two or more.

The (meth) acrylic monomer having a hetero-alicyclic group is included in the (meth) acrylic copolymer and can be bonded to the cellulose ester binder to increase the modulus of the adhesive film. Further, the (meth) acrylic monomer having a hetero-alicyclic group can lower the creep at 25 ° C and the creep at 85 ° C together with the (meth) acrylic monomer having an alicyclic group.

The (meth) acrylic monomer having a hetero-alicyclic group may be contained in an amount of 1 mol% to 20 mol%, specifically 5 mol% to 10 mol% in the monomer mixture. Within this range, the modulus of the pressure-sensitive adhesive film at 30 占 폚 may be increased and the reliability may be improved.

(Meth) acrylic monomers having a hetero-alicyclic group may include (meth) acrylic acid esters having C4 to C9 hetero-alicyclic groups containing at least one of nitrogen, oxygen or sulfur. Specifically, the (meth) acrylic monomer having a heteroalicyclic group may include (meth) acryloylmorpholine, but is not limited thereto.

The monomer mixture may further comprise at least one other monomer selected from (meth) acrylic acid esters having C1 to C3 alkyl groups, monomers having an amide group, and monomers having an aromatic group. Specifically, other monomers may include, but are not limited to, methyl (meth) acrylate, (meth) acrylamide, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, styrene and the like.

The (meth) acrylic copolymer may be prepared by polymerizing a monomer mixture by a conventional polymerization method. The polymerization method may include conventional methods known to those skilled in the art. For example, the (meth) acrylic copolymer can be prepared by adding an initiator to a monomer mixture, followed by conventional copolymerization, such as suspension polymerization, emulsion polymerization, solution polymerization and the like. The polymerization temperature may be 65 占 폚 to 70 占 폚, and the polymerization time may be 6 hours to 8 hours. The initiator may be an azo-based polymerization initiator; And / or peroxides such as benzoyl peroxide or acetyl peroxide, and the like.

(Meth) acrylic copolymer has a weight average molecular weight (Mw) of 2,000,000 g / mol or less, specifically 200,000 g / mol to 1,500,000 g / mol, more specifically 200,000 g / mol to 1,300,000 g / mol . Within the above range, high durability can be ensured. The weight average molecular weight may be a value obtained by converting the polystyrene in the gel permeation chromatography method. (Meth) acrylic copolymer may have a glass transition temperature of -100 ° C to 0 ° C, specifically, -80 ° C to -5 ° C. Within the above range, it has fluidity as a pressure-sensitive adhesive and high durability can be ensured. The (meth) acrylic copolymer may have a polydispersity of 2.5 to 9.0, specifically 3 to 6. Within the above range, the polymerization is stable and the decrease in durability can be excluded. The (meth) acrylic copolymer may have an acid value of 5 mg KOH / g or less, more specifically 0.01 mg KOH / g to 3 mg KOH / g. Within this range, it is possible to realize a corrosion inhibiting effect directly or indirectly on the adherend.

The curing agent may react with the (meth) acrylic copolymer to form an adhesive film and provide adhesion. The curing agent may include at least one of an isocyanate curing agent, a metal chelating curing agent, an epoxy curing agent, an aziridine curing agent, and a carbodiimide curing agent. Specifically, the curing agent includes at least one of an isocyanate-based curing agent, a metal chelate-based curing agent, and an aziridine curing agent, thereby further improving the reliability and the aging-shortening effect at room temperature.

The isocyanate-based curing agent may include an isocyanate-based curing agent having two or more functional groups, for example, bifunctional or hexafunctional. Specifically, the isocyanate-based curing agent is a trifunctional isocyanate curing agent including trifunctional trimethylolpropane-modified toluene diisocyanate adduct, trifunctional toluene diisocyanate trimer, trimethylolpropane-modified xylene diisocyanate adduct, etc., 6 Functionalized trimethylolpropane-modified toluene diisocyanate, and hexafunctional isocyanurate-modified toluene diisocyanate. These may be included singly or in combination of two or more.

The metal chelate-based curing agent may include a coordination compound of a polyvalent metal such as aluminum. For example, the metal chelate-based curing agent may include an aluminum chelate-based compound such as trisethylacetoacetate aluminum, ethylacetoacetate aluminum diisopropylate, and trisacetylacetonate aluminum.

The aziridine curing agent may be at least one selected from the group consisting of N, N'-hexane-1,6-diylbis (2-methyl aziridine-1-carboxamide), N, N'- Dipentaerythritol dicarboxamide), and the like.

The mixture of at least one of a curing agent, that is, an isocyanate curing agent, a metal chelating curing agent, and an aziridine curing agent is 0.01 to 10 parts by weight, for example, 0.01 to 5 parts by weight per 100 parts by weight of the (meth) 0.05 part by weight to 5 parts by weight, and 0.1 part by weight to 0.7 part by weight. Within this range, there may be an effect of improving the reliability and lowering the creep at room temperature.

In one embodiment, the curing agent may be an isocyanate curing agent alone, or a mixture of an isocyanate curing agent and a metal chelating curing agent, or a mixture of an isocyanate curing agent and an aziridine curing agent. The above mixture may further have a synergistic effect of modulus at room temperature. The isocyanate-based curing agent: metal chelate-based curing agent in the mixture is contained in a weight ratio of 1: 0.1 to 1:10, specifically 1: 0.1 to 1: 5, and 1: 1.5 to 1: 5, . The isocyanate-based curing agent: the aziridine-based curing agent is contained at a weight ratio of 1: 0.1 to 1:10, specifically 1: 0.1 to 1: 5, and 1: 1.5 to 1: 5.

The cellulose ester binder can bond with the heteroalicyclic group of the (meth) acrylic copolymer to increase the modulus of the pressure-sensitive adhesive film at 30 ° C. Further, the cellulose ester binder may have an effect of lowering the creep at 25 占 폚 and improving durability (thermal shock, heat resistance and humidity resistance).

Cellulose ester binder may include a binder, a modified cellulose or a portion of -OH is one or more -O- (C = O) -R a -OH group of the -CH 2 -OH. In this case, R may be an alkyl group of C1 to C10, for example, a methyl group, an ethyl group, or a butyl group. The cellulose ester binder may comprise the same or different -O- (C = O) -R. Specifically, the cellulose ester binder may include one or more of cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate, and cellulose propionate.

The cellulose ester binder may be contained in an amount of 0.1 to 30 parts by weight, specifically 5 to 20 parts by weight, based on 100 parts by weight of the (meth) acrylic copolymer. Within the above range, it is possible to increase the modulus of the pressure-sensitive adhesive film at 30 캜, lower the creep at 25 캜, and have an excellent durability (thermal shock, heat and humidity resistant condition).

The pressure-sensitive adhesive composition for a polarizing plate may further comprise a silane coupling agent. The silane coupling agent can increase the adhesion of the polarizing plate adhesive film to an adherend such as glass.

The silane coupling agent may comprise conventional silane coupling agents known to those skilled in the art. For example, the silane coupling agent may have an epoxy structure such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. ; A polymerizable unsaturated group-containing silicon compound such as vinyltrimethoxysilane, vinyltriethoxysilane and (meth) acryloxypropyltrimethoxysilane; Containing silicon compounds such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane. ; And 3-chloropropyltrimethoxysilane, and the like, but are not limited thereto.

The silane coupling agent may be contained in an amount of 0.01 to 5 parts by weight, specifically 0.01 to 1 part by weight based on 100 parts by weight of the (meth) acrylic copolymer. Within the above range, endurance reliability is excellent, and changes in components and physical properties with time can be small.

The pressure sensitive adhesive composition for a polarizing plate may further comprise a curing catalyst. The curing catalyst catalyzes the curing reaction between the (meth) acrylic copolymer and the curing agent, and can shorten the curing rate. The curing catalyst comprises at least one of an organometallic catalyst, specifically a tin containing catalyst, for example, dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin diacetyl acetonate, tetrabutyl tin, trimethyl tin hydroxide . The curing catalyst may comprise at least one of a tertiary amine catalyst, specifically triethanolamine, trialkylamine.

The curing catalyst may be contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the (meth) acrylic copolymer. Within the above range, there is an effect of increasing the curing rate, and it is possible to prevent the transparency of the adhesive film from deteriorating due to the residual of the curing catalyst.

The pressure-sensitive adhesive composition for a polarizing plate may further contain usual additives. The additives may include antistatic agents, ultraviolet absorbers, antioxidants, tackifying resins, plasticizers, reworking agents, and the like. Specifically, the reworking agent may comprise a polysiloxane oligomer or a mixture comprising it. The additive may be included in an amount of 0.001 to 5 parts by weight, specifically 0.01 to 1 part by weight based on 100 parts by weight of the (meth) acrylic copolymer. Within the above range, the additive effect can be obtained without affecting the physical properties of the polarizing plate adhesive film.

The pressure-sensitive adhesive composition for a polarizing plate may have a viscosity of 1,000 cPs to 4,000 cPs at 25 占 폚. Within the above range, the thickness of the adhesive film can be easily adjusted, there is no unevenness in the adhesive film, and the coated surface can have a uniform effect.

Hereinafter, a pressure-sensitive adhesive film for a polarizing plate and a pressure-sensitive adhesive composition for a polarizing plate according to another embodiment of the present invention will be described.

The adhesive film for a polarizing plate according to this embodiment may include a (meth) acrylic copolymer and a cellulose ester binder having an alkyl group, a hydroxyl group, an alicyclic group, a heterocyclic group, and a tertiary amine group. Is substantially the same as the adhesive film for a polarizing plate according to an embodiment of the present invention, except that the (meth) acrylic copolymer further has a tertiary amine group. (Meth) acrylic copolymer has a tertiary amine group, the speed of aging of the pressure-sensitive adhesive composition for a polarizing plate or the dried product thereof can be increased. Hereinafter, only (meth) acrylic copolymers having an alkyl group, a hydroxyl group, an alicyclic group, a hetero-alicyclic group and a tertiary amine group will be described.

The (meth) acrylic copolymer having an alkyl group, a hydroxyl group, an alicyclic group, a heteroalicyclic group and a tertiary amine group may be a (meth) acrylic monomer having an alkyl group, a (meth) acrylic monomer having a hydroxyl group, , (Meth) acrylic monomers having a hetero-alicyclic group, and (meth) acrylic monomers having a tertiary amine group.

(Meth) acrylic monomers having an alkyl group, (meth) acrylic monomers having a hydroxyl group, (meth) acrylic monomers having an alicyclic group, and (meth) acrylic monomers having a heterocyclic group are respectively as described above.

The (meth) acrylic monomer having a tertiary amine group may include a dialkylaminoalkyl (meth) acrylate ester. Specifically, the dialkylaminoalkyl (meth) acrylate is selected from the group consisting of dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, diethylaminoethyl (Meth) acrylate, diethylaminopropyl (meth) acrylate, diethylaminobutyl (meth) acrylate, and dibutylaminoethyl (meth) acrylate.

The (meth) acrylic monomer having a tertiary amine group may include 0.001 to 15 mol%, specifically 0.01 to 10 mol%, of the monomer mixture. In the above range, the aging speed of the pressure-sensitive adhesive composition for a polarizing plate or the dried product thereof at room temperature may be increased, and the curing reaction speed may be increased.

In one embodiment, the monomer mixture comprises 40 mol% to 95 mol% of a (meth) acrylic monomer having an alkyl group, 0.1 mol% to 20 mol% of a (meth) acrylic monomer having a hydroxyl group, 1 mol% to 30 mol % Of a (meth) acrylic monomer having a tertiary amine group and 1 mol% to 20 mol% of a (meth) acrylic monomer having a tertiary amine group, and 0.001 to 15 mol% of a (meth) acrylic monomer having a tertiary amine group.

Hereinafter, a pressure-sensitive adhesive film for a polarizing plate and a pressure-sensitive adhesive composition for a polarizing plate according to another embodiment of the present invention will be described. The adhesive film for a polarizing plate according to this embodiment may include a (meth) acrylic copolymer and a cellulose ester binder having an alkyl group, a hydroxyl group, an alicyclic group, a heterocyclic group, a tertiary amine group, and a carboxylic acid group. Is similar to the pressure-sensitive adhesive film for a polarizing plate and the pressure-sensitive adhesive composition of the embodiment, except that a tertiary amine group and a carboxylic acid group are further added. The monomer having a carboxylic acid group may be (meth) acrylic acid or the like and may be contained in an amount of 0.001 mol% to 10 mol%, specifically 0.001 mol% to 5 mol%, specifically 0.01 mol% to 3 mol% in the monomer mixture. It may not be corrosive to metals while increasing the modulus of the metal. In one embodiment, the monomer mixture comprises 40 mol% to 95 mol% of a (meth) acrylic monomer having an alkyl group, 0.1 mol% to 20 mol% of a (meth) acrylic monomer having a hydroxyl group, 1 mol% to 30 mol (Meth) acrylic monomer having a carboxylic acid group in an amount of from 0.001 mol% to 10 mol% based on the total amount of the (meth) acrylic monomer having a tertiary amine group and the (meth) acrylic monomer having a tertiary amine group .

Hereinafter, the polarizing plate of the present invention will be described.

The polarizing plate of the present invention may include a pressure-sensitive adhesive film for a polarizing plate according to embodiments of the present invention. The polarizing plate of the present invention can be manufactured by adhering a pressure sensitive adhesive film for a polarizing plate according to embodiments of the present invention to one side of a polarizing plate or by coating the pressure sensitive adhesive composition for a polarizing plate on a side of a polarizing plate to a predetermined thickness and then aging.

The polarizing plate of the present invention includes the above-mentioned pressure-sensitive adhesive film, so that the pencil hardness of the polarizing plate on the pressure-sensitive adhesive film is 2H More specifically 2H to 3H. In the above range, even when the polarizing plate is adhered to a liquid crystal panel such as a glass material with an adhesive film for a polarizing plate, the polarizing plate can be used for an optical display device because the contrast pencil hardness is not significantly reduced when the polarizing plate is adhered to the liquid crystal panel without an adhesive film.

The polarizing plate may include a polarizer and an optical film formed on at least one side of the polarizer. The polarizer and the optical film are based on conventional contents known to those skilled in the art.

The thickness of the polarizing plate may be 30 탆 to 200 탆, specifically 50 탆 to 100 탆. In the above range, it can be used in an optical display device.

2 is a cross-sectional view of a polarizing plate of one embodiment of the present invention. 2, the polarizer 100 of the present invention includes a polarizer 110, a first optical film 120 formed on the upper surface of the polarizer 110, an adhesive film (not shown) formed on the lower surface of the polarizer 110 130, and the adhesive film 130 may include the adhesive film for a polarizing plate of the present invention. Although not shown in Fig. 2, the adhesive film 130 may be adhered to the liquid crystal display panel.

The polarizer 110 is made of a polyvinyl alcohol-based film and is not particularly limited as long as it is a polyvinyl alcohol-based film regardless of the manufacturing method. For example, a polarizer may be a modified polyvinyl alcohol film such as a partially-formalized polyvinyl alcohol film or an acetoacetyl-modified polyvinyl alcohol film. Specifically, a polyvinyl alcohol film is prepared by dyeing iodine or a dichroic dye and stretching it in a predetermined direction. Specifically, it is produced through a swelling process, a dyeing process, and a stretching process. Methods of performing each step are commonly known to those skilled in the art. The polarizer 110 may have a thickness of 5 占 퐉 to 50 占 퐉. And can be used in an optical display device in the above range.

The first optical film 120 may be formed of an optically transparent resin, specifically, a cyclic olefin polymer including a cyclic olefin polymer (COP), a poly (meth) acrylate, a polycarbonate, a polyethylene terephthalate Based, polyamide-based, polyimide-based, polyolefin-based, polyarylate-based, poly (ethylene terephthalate), and poly A polyvinyl chloride-based resin, a polyvinyl alcohol-based resin, a polyvinyl chloride-based resin, and a polyvinylidene chloride-based resin. The first optical film 120 may have a thickness of 10 占 퐉 to 200 占 퐉, for example, 20 占 퐉 to 120 占 퐉, and may be used in an optical display device in the above range.

3 is a cross-sectional view of a polarizing plate of another embodiment of the present invention. 3, the polarizing plate 200 of another embodiment of the present invention includes a polarizer 110, a first optical film 120 formed on the upper surface of the polarizer 110, a second optical film 120 formed on the lower surface of the polarizer 110, And the adhesive film 130 formed on the lower surface of the film 140 and the second optical film 140. The adhesive film 130 may include the adhesive film for a polarizing plate of the present invention. Except that a second optical film 140 is further formed between the polarizer 110 and the adhesive film 130. The polarizing plate 110 of the present invention is the same as the polarizing plate of the first embodiment. The second optical film 140 may be formed of the same or different resin as the first optical film 120. The thickness of the second optical film 140 may be the same as or different from that of the first optical film 120.

Although not shown in Figs. 2 and 3, an adhesive layer formed of an adhesive for a polarizing plate may be included between the polarizer and the first optical film, and between the polarizer and the second optical film. The adhesive for the polarizing plate may be an aqueous adhesive, a pressure sensitive adhesive, . &Lt; / RTI &gt;

The optical display device of one embodiment of the present invention may include the polarizing plate of the present invention. For example, the optical display device may include a liquid crystal display device, an organic light emitting display device, but is not limited thereto.

4 is a sectional view of a liquid crystal display device according to an embodiment of the present invention. 4, a liquid crystal display 300 according to an exemplary embodiment of the present invention includes a liquid crystal display panel 310, a first polarizer 320 formed on the upper surface of the liquid crystal display panel 310, A second polarizer 330 formed on the lower surface and a backlight unit 340 formed on the lower portion of the second polarizer 330. One or more of the first polarizer 320 and the second polarizer 330 may be used in the present invention A polarizing plate may be included.

The liquid crystal display panel can be used in an IPS (In-Plain Switching) mode, a PLS (Plane to Line Switching) mode, a TN (twisted nematic) mode, a VA (vertical alignment) mode, a PVA patterned vertical alignment) mode. Particularly, the PLS mode liquid crystal display panel can exhibit a superior light leakage improving effect.

Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

The specifications of the components used in the following examples and comparative examples are as follows.

(A) (Meth) Acrylic Copolymer: A (meth) acrylic copolymer

(B) Curing agent

(B1) isocyanate curing agent: trimethylol propane (TMP) modified toluene diisocyanate adduct (L-45, Soken, solid content 45 wt% in Toluene)

(B2) Metal chelating curing agent: aluminum chelate (BXX 4805, Toyo Ink, solid content: about 3 wt%)

(B3) aziridine curing agent: N, N'-hexane-1,6-diylbis (PZH-100, Menadina, Spain, 6.5 wt% in Methyl Ethyl Ketone)

(C) Cellulose ester binder: Cellulose acetate butyrate (CAB-381-0.5, Eastman)

(D) Silane coupling agent: (A-50, Soken)

(E) Crosslinking catalyst: tin catalyst (S promoter, Soken)

Manufacturing example 1: (meth) acrylic  Preparation of Copolymer

Methyl-ethyl ketone was added to a 1 L reactor equipped with a cooling device for reflux of nitrogen gas and easy temperature control. acryloylmorpholine, 10 mol% of acryloylmorpholine, 5 mol% of isobornyl acrylate, 5 mol% of 4-hydroxybutyl acrylate, 0.05 mol% of dimethylaminoethyl acrylate and 0.5 mol% of acrylic acid Of the monomer mixture was added to the reactor. In order to remove oxygen from the monomer mixture, nitrogen gas was introduced for 30 minutes to replace the reactor, and the internal temperature of the reactor was maintained at 65 ° C. After uniformly stirring the monomer mixture, V601 (Wako) was added as an initiator at a rate of 0.5 g per 1000 g of the monomer mixture and reacted for 4 hours. Initiator V601 (Wako) was further added so that the internal temperature of the reactor was raised to 70 캜 and the total amount of the initiator was the amount shown in Table 1. Followed by further reaction at 71 ° C for 2 hours and cooling to obtain a (meth) acrylic copolymer.

Manufacturing example  2 to Manufacturing example 10: (meth) acrylic  Preparation of Copolymer

(Meth) acrylic copolymer was prepared in the same manner as in Production Example 1, except that the kind and content of the monomers in the monomer mixture and the content of the initiator were changed as shown in Table 1 below.

BA
(mol%) ACMO
(mol%) IBXA
(mol%) 4-HBA
(mol%) DMAEA
(mol%) AAc
(mol%) Initiator, g per 1000 g total monomer Mw
(g / mol) Tg (占 폚) Production Example 1 79.45 10 5 5 0.05 0.5 0.6 489,900 -26.2 Production Example 2 74.45 10 10 5 0.05 0.5 0.6 465,500 -19.7 Production Example 3 69.45 10 15 5 0.05 0.5 0.6 453,000 -15.2 Production Example 4 64.45 10 20 5 0.05 0.5 0.6 441,200 -8.4 Production Example 5 70 10 15 5 - - 0.5 520,800 -15.7 Production Example 6 70 10 15 5 - - 0.4 865,500 -16.0 Production Example 7 69.45 10 15 5 0.05 0.5 0.2 1,299,500 -15.6 Production Example 8 69.95 10 15 5 0.05 - 0.4 864,200 -15.9 Production Example 9 80 - 15 5 - - 0.3 1,057,300 -28.6 Production Example 10 94.95 - - 5 0.05 - 0.3 1,002,500 -41.0

In Table 1, BA: n-butyl acrylate, ACMO: acryloylmorpholine, IBXA: isobornyl acrylate, 4-HBA: 4-hydroxybutyl acrylate, DMAEA: dimethylaminoethyl acrylate, AAc : Acrylic acid, Mw: weight average molecular weight of the (meth) acrylic copolymer, Tg: glass transition temperature of the (meth) acrylic copolymer.

Example  One

(B1) isocyanate curing agent 0.2 part by weight, (B2) metal chelating curing agent 0.5 part by weight, (C) cellulose ester binder 10 parts by weight, (D) ) Silane coupling agent, and (E) 0.2 part by weight of a crosslinking catalyst were mixed to prepare a pressure-sensitive adhesive composition for a polarizing plate.

The pressure-sensitive adhesive composition for a polarizing plate was coated on a polyethylene terephthalate film as a release film and dried at 105 DEG C for 4 minutes to prepare a pressure-sensitive adhesive sheet having a thickness of 20 mu m.

The polyvinyl alcohol film was stretched three times at 60 DEG C, adsorbed iodine, and then stretched 2.5 times in an aqueous boric acid solution at 40 DEG C to prepare a polarizer. A triacetyl cellulose film was adhered to both sides of the polarizer with an adhesive (Z-200, Nippon Goshei) to prepare a polarizing plate.

The pressure sensitive adhesive sheet was attached to one side of one triacetyl cellulose film and aged for 24 hours at constant temperature and humidity (35 캜, 45% relative humidity) for aging time to produce a polarizing plate including the pressure sensitive adhesive film.

Example  2 to Example  9

A pressure-sensitive adhesive composition for a polarizing plate was prepared in the same manner as in Example 1, except that the kind of the (meth) acrylic copolymer, the curing agent, and the content of the cellulose ester binder were changed as shown in Table 2 below.

A pressure-sensitive adhesive sheet and a pressure-sensitive adhesive film for a polarizing plate were prepared in the same manner as in Example 1 with the pressure-sensitive adhesive composition for a polarizing plate.

Comparative Example  1 to Comparative Example  3

A pressure-sensitive adhesive composition for a polarizing plate was prepared in the same manner as in Example 1, except that the kind of the (meth) acrylic copolymer, the curing agent, and the content of the cellulose ester binder were changed as shown in Table 2 below. A pressure-sensitive adhesive sheet and a pressure-sensitive adhesive film for a polarizing plate were prepared in the same manner as in Example 1 with the pressure-sensitive adhesive composition for a polarizing plate.

The compositions of the pressure-sensitive adhesive compositions of Examples and Comparative Examples are shown in Table 2 below.

(A)
rescue (A)
(Parts by weight) (B1)
(Parts by weight) (B2)
(Parts by weight) (B3)
(Parts by weight) (C)
(Parts by weight) Example 1 Production Example 1 100 0.2 0.5 - 10 Example 2 Production Example 2 100 0.2 0.5 - 10 Example 3 Production Example 3 100 0.2 0.5 - 10 Example 4 Production Example 4 100 0.2 0.5 - 10 Example 5 Production Example 5 100 0.2 - - 10 Example 6 Production Example 6 100 0.2 - - 10 Example 7 Production Example 7 100 0.2 0.5 - 10 Example 8 Production Example 8 100 0.2 0.5 - 10 Example 9 Production Example 3 100 0.2 - 0.5 10 Comparative Example 1 Production Example 3 100 0.2 - - - Comparative Example 2 Production Example 9 100 0.2 - - - Comparative Example 3 Production Example 10 100 0.2 0.5 - 10

The properties of the pressure-sensitive adhesive films and polarizing plates for the polarizing plate of Examples and Comparative Examples were evaluated in Table 3 below.

(1) Creep: Referring to FIG. 1, the creep was measured on the adhesive film using TEXTURE ANALYZER TA.XT PLUS (5 kg of load cell, EKO Instruments). The pressure-sensitive adhesive films were obtained by aging the pressure-sensitive adhesive sheets of Examples and Comparative Examples at 35 DEG C and 45% relative humidity for 48 hours.

A specimen 23 for creep measurement including the adhesive film 21 (thickness: 20 m) and the polarizing plate 22 formed on the adhesive film 21 was produced. The polarizing plate 22 includes a sequentially stacked triacetyl cellulose film (thickness: 40 占 퐉), a polarizer (thickness: 8 占 퐉), and a triacetyl cellulose film (thickness: 40 占 퐉). When the specimen 23 for creep measurement was pulled out for 1000 seconds under the load W by lapping the specimen 23 for creep measurement with the area of axb (for example, 15 mm x 15 mm) at the end of the alkali-free glass plate 20, And the distance of the specimen 23 for creep measurement from the alkali-free glass plate 20 was measured. The load W was 2250 g at 25 ° C for creep measurement and 1500 g at 85 ° C for creep measurement.

(2) Storage Modulus: The pressure-sensitive adhesive sheets of Examples and Comparative Examples were aged at 35 占 폚 and 45% RH for 48 hours to prepare an adhesive film (thickness: 20 占 퐉), releasing the adhesive film from the release film, A plurality of films were laminated and cut to prepare circular specimens having a thickness of 500 탆 and a diameter of 8 mm. The prepared specimens were thermally treated on a disc having a diameter of 8 mm with a Physica MCR501 (Anton parr) at 0 캜 to 150 캜 at 10 캜 Min at a temperature rise rate of 30 ° C and 120 ° C when the strain is evaluated at 5%, angular frequency (ω) of 10 rad / s and normal force of 1.5 N.

(3) Pencil hardness of the polarizing plate on the pressure-sensitive adhesive film: The pressure-sensitive adhesive film is placed on a glass plate for measuring the pencil hardness, and the polarizing plate is placed on the pressure-sensitive adhesive film. The polarizing plate is measured by the JIS K5400 method using pencil hardness It is.

The pencil hardness of the polarizing plate on the pressure-sensitive adhesive film was measured using a pressure-sensitive adhesive film / triacetylcellulose film 1 (thickness: 40 탆, N-TAC, KONICA MINOLTA) / polarizer (thickness: 8 탆) / triacetylcellulose film 2 -TAC, KONICA MINOLTA) were measured for sequentially stacked specimens. The pressure-sensitive adhesive film of the specimen was attached to a glass plate, and the specimen was fixed to a glass plate and treated in an autoclave at 5 atm, 50 ° C, and 1000 seconds. Prior to pencil hardness measurements, they were held for 24 hours at 23 &lt; 0 &gt; C and 55% relative humidity. Pencil hardness was measured on the surface of the triacetyl cellulose film 2 in the specimen using a COASTEK pencil hardness tester (COA TECH KOREA). The pencil hardness was measured at a speed of 48 mm / min and the pencil load on the triacetylcellulose film 2 was 500 g. When measured with the same pencil hardness, it is the maximum pencil hardness value when there is no scratch at all five times in the evaluation of 5 times.

(4) Durability: The pressure-sensitive adhesive sheets of Examples and Comparative Examples were aged at constant temperature and humidity of 35 ° C and 45% relative humidity for 24 hours to produce an adhesive film. The polyvinyl alcohol film was stretched three times at 60 DEG C, adsorbed iodine, and then stretched 2.5 times in an aqueous boric acid solution at 40 DEG C to prepare a polarizer. A triacetyl cellulose film was adhered to both sides of the polarizer to prepare a polarizing plate. An adhesive film was laminated on the polarizing plate and cut into a rectangle having a size of length x length (150 mm x 100 mm) to prepare a polarizing plate for durability evaluation. The polarizer for durability evaluation was laminated on an alkali glass plate of the same size and subjected to autoclave treatment at 50 占 폚 for 1000 seconds to prepare a specimen in which a durability evaluation polarizing plate was laminated on a glass plate. The specimens were allowed to stand at 85 ° C for 500 hours, or the specimens were subjected to thermal shock with a cycle of 200 cycles at -40 ° C for 30 minutes and then at 85 ° C for 30 minutes, or 60 ° C and 95% relative Humidity for 500 hours and evaluated for the polarizing plate.

○: No lift, drag, and bubble formation

Δ: At least one of lifting, dragging, and bubbling occurred finely

X: There is a lot of lifting, attracting and bubbling.

(5) Light leakage: A sample having a polarizing plate attached to a polarizing plate adhesive film was prepared in the same manner as in (1), and light leakage was measured. Both sides of the glass plate were laminated so that the absorption axes of the polarizers were perpendicular to each other. Then, it was left at 85 캜 for 500 hours and left at 25 캜 for 2 hours. After driving the liquid crystal display for the PLS mode, the luminance of the entire display panel was measured at a height of 1 m by using a luminance measuring device (RISA, Hiland). Specifically, the luminance (c) at the center of the panel and the luminance (a), (b), (d), and (e) of the corner where the light leakage appears are measured. As shown in Fig. 5, the luminance measurement point was set such that the measurement radius in the vicinity of each vertex of the panel was 0.5 cm. In FIG. 5, a, b, c, d, and e indicate luminance measurement points. The degree of light leakage (L) was quantified according to the following equation (2). The lower the L, the better the light leakage. And evaluated according to the following evaluation criteria.

<Formula 2>

? L = | [(a + b + d + e) / 4] / c - 1 |

(Where a, b, d and e are the luminance measured at the luminance measurement points a, b, d and e (high luminance area) in FIG. 5 and c Is the brightness of point c.

○ - Luminous glands with L greater than or equal to 0 and less than or equal to 0.1,

△ - Low light with a L less than 0.3 but less than 0.3.

× - L is over 0.3, light leakage is severe.

Creep
(25 캜, 탆) Creep
(85 캜, 탆)
Modulus
(30 ° C, Pa) Modulus
(120 ° C, Pa) Pencil hardness of polarizer on adhesive film durability
Light beam 85 ℃ Thermal shock at -40 ° C / 85 ° C 60 ° C and 95% relative humidity Example 1 75 426 346,000 70,300 2H ○ ○ ○ ○ Example 2 86 395 334,000 59,000 2H ○ ○ ○ ○ Example 3 88 365 312,000 30,500 3H ○ ○ ○ ○ Example 4 90 402 302,000 28,300 3H ○ ○ ○ ○ Example 5 88 329 357,000 51,600 3H ○ ○ ○ ○ Example 6 94 285 368,000 20,500 3H ○ ○ ○ ○ Example 7 75 355 408,000 26,300 3H ○ ○ ○ ○ Example 8 161 346 351,000 45,700 3H ○ ○ ○ ○ Example 9 85 351 365,000 34,600 3H ○ ○ ○ ○ Comparative Example 1 278 421 110,000 33,500 H ○ ○ ○ ○ Comparative Example 2 204 687 158,000 48,300 H ○ ○ ○ ○ Comparative Example 3 355 451 79,000 45,500 4B ○ ○ ○ ○

As shown in Table 3, the polarizing plate for a polarizing plate of the present invention had a low creep at room temperature and a high modulus, so that the pencil hardness of the polarizing plate on the adhesive film was high, the creep was high and the modulus was low at high temperature.

On the other hand, the pressure-sensitive adhesive films for the polarizing plate of Comparative Examples 1 and 2 which did not contain the cellulose ester binder had a high creep at room temperature, and the pencil hardness of the polarizing plate was low. The polarizing plate on the polarizing plate on the pressure-sensitive adhesive film had a low pencil hardness in Comparative Example 3 in which a copolymer containing a cellulose ester binder but not having an alicyclic group and / or a heteroalicyclic group was used.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (21)

(Meth) acrylic copolymer having an alkyl group, a hydroxyl group, an alicyclic group and a heterocyclic group, and a cellulose ester binder,
And a modulus of at least 100,000 Pa at 30 占 폚. The creep is not more than 200 mu m at 25 DEG C,
A pressure-sensitive adhesive film for a polarizing plate having a modulus of 1.5 or more and a modulus of 100,000 Pa or more at 30 DEG C:
<Formula 1>
Modulus ratio = A / B
(In the above formula 1, A is the modulus of the polarizing plate adhesive film at 30 ° C, and B is the modulus of the polarizing plate adhesive film at 120 ° C). The adhesive film for a polarizing plate according to claim 1 or 2, wherein the adhesive film for a polarizing plate has a creep of at least 250 탆 at 85 캜. The pressure-sensitive adhesive film for a polarizing plate according to claim 1 or 2, wherein the pressure-sensitive adhesive film for a polarizing plate has a modulus of 80,000 Pa or less at 120 ° C. The pressure-sensitive adhesive sheet for polarizing plate according to claim 2, wherein the pressure-sensitive adhesive film for a polarizing plate is formed of a pressure-sensitive adhesive composition for a polarizing plate comprising a (meth) acrylic copolymer having an alkyl group, a hydroxyl group, an alicyclic group and a heterocyclic group and a cellulose ester binder film. The composition according to any one of claims 1 to 5, wherein the (meth) acrylic copolymer having an alkyl group, a hydroxyl group, an alicyclic group and a heteroalicyclic group is selected from the group consisting of (meth) acrylic monomers having an alkyl group, (meth) acrylic monomers having a hydroxyl group (Meth) acrylate monomer having a (meth) acrylic group and a (meth) acrylic monomer having a heteroalicyclic group. The pressure sensitive adhesive film for a polarizing plate according to claim 6, wherein the (meth) acrylic monomer having an alicyclic group is contained in an amount of 1 mol% to 30 mol% of the monomer mixture. The pressure-sensitive adhesive film for a polarizing plate according to claim 6, wherein the (meth) acrylic monomer having the hetero-alicyclic group is contained in an amount of 1 mol% to 20 mol% of the monomer mixture. The composition according to claim 6, wherein the (meth) acrylic monomer having an alicyclic group and the (meth) acrylic monomer having a heteroalicyclic group in the monomer mixture are contained in a mole ratio of 1: 0.5 to 1:40. Adhesive film. The adhesive film for a polarizing plate according to claim 1 or 5, wherein the cellulose ester binder comprises at least one of cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate, and cellulose propionate. The adhesive film for a polarizing plate according to any one of claims 1 to 5, wherein the cellulose ester binder is contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the (meth) acrylic copolymer. The adhesive film for a polarizing plate according to claim 1 or 5, wherein the pressure-sensitive adhesive composition for a polarizing plate further comprises a curing agent. The pressure sensitive adhesive film for a polarizing plate according to claim 12, wherein the curing agent comprises at least one of an isocyanate curing agent, a metal chelating curing agent, and an aziridine curing agent. The adhesive film for a polarizing plate according to claim 1 or 5, wherein the (meth) acrylic copolymer further has a tertiary amine group. The thermoplastic resin composition according to claim 14, wherein the (meth) acrylic copolymer is a copolymer comprising 40 mol% to 95 mol% of a (meth) acrylic monomer having an alkyl group, 0.1 mol% to 20 mol% of a (meth) acrylic monomer having a hydroxyl group, Wherein the copolymer is a copolymer of 1 mol% to 30 mol% of an acrylic monomer, 1 mol% to 20 mol% of a (meth) acrylic monomer having a heteroalicyclic group and 0.001 mol% to 15 mol% of a (meth) acrylic monomer having a tertiary amine group . The adhesive film for a polarizing plate according to claim 1 or 5, wherein the (meth) acrylic copolymer further has a tertiary amine group and a carboxylic acid group. The thermoplastic resin composition according to claim 16, wherein the (meth) acrylic copolymer is a copolymer of 40 mol% to 95 mol% of a (meth) acrylic monomer having an alkyl group, 0.1 mol% to 20 mol% of a (meth) acrylic monomer having a hydroxyl group, (Meth) acrylate monomer having a carboxylic acid group in an amount of 1 mol% to 30 mol%, a (meth) acrylic monomer having a tertiary amine group in an amount of 0.001 mol% to 15 mol% mol% to 10 mol% of the copolymer. A pressure-sensitive adhesive film for a polarizing plate, a polarizer and an optical film are sequentially laminated,
Wherein the polarizer has a pencil hardness of 2H or more,
Wherein the polarizing plate adhesive film has a creep of 250 占 퐉 or more at 85 占 폚,
Wherein the adhesive film for a polarizing plate has a creep of 200 占 퐉 or less at 25 占 폚. The polarizing plate according to claim 18, wherein the pressure-sensitive adhesive film for a polarizing plate comprises the pressure-sensitive adhesive film for a polarizing plate according to claim 1 or 2. The polarizing plate according to claim 18, wherein an optical film is further laminated between the polarizing plate and the polarizing plate adhesive film. An optical display device comprising the adhesive film for a polarizing plate of claim 1 or 2 or the polarizing plate of claim 18.
KR1020150177495A 2015-11-24 2015-12-11 Adhesive film for polarizing plate, polarizing plate comprising the same and optical display apparatus comprising the same KR101943694B1 (en)

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KR1020150177495A KR101943694B1 (en) 2015-12-11 2015-12-11 Adhesive film for polarizing plate, polarizing plate comprising the same and optical display apparatus comprising the same
TW105137997A TWI642742B (en) 2015-11-24 2016-11-21 Adhesive film for polarizing plate, polarizing plate and optical display comprising the same
CN201611048768.1A CN106978111B (en) 2015-11-24 2016-11-23 Polarizer adhesive film, polarizer and optical display including it
US15/360,557 US10358581B2 (en) 2015-11-24 2016-11-23 Adhesive film for polarizing plate, polarizing plate and optical display comprising the same

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190004562A (en) * 2017-07-04 2019-01-14 삼성에스디아이 주식회사 Adhesive composition for polarizing plate, adhesive film for polarizing plate prepared using the same, polarizing plate comprising the same and optical display apparatus comprising the same
KR20200100202A (en) * 2018-03-30 2020-08-25 닛토덴코 가부시키가이샤 Polarizing film and image display device with pressure-sensitive adhesive layer

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007108592A (en) * 2005-10-17 2007-04-26 Nitto Denko Corp Laminate for liquid crystal display apparatus, and liquid crystal display apparatus with same
KR101010889B1 (en) * 2006-03-15 2011-01-25 닛토덴코 가부시키가이샤 Adhesive optical film, multilayer optical film and image display
KR101351620B1 (en) * 2010-12-29 2014-01-15 제일모직주식회사 Binder for adhesive composition, adhesive composition comprising the same and optical member using the same
JP2014038180A (en) * 2012-08-15 2014-02-27 Konica Minolta Inc Optical film, production method of optical film, polarizing plate and liquid crystal display device
KR20150062088A (en) * 2013-11-28 2015-06-05 제일모직주식회사 Adhesive composition, adhesive film prepared using the same and optical display apparatus comprising the same
KR20150102625A (en) * 2014-02-28 2015-09-07 제일모직주식회사 Adhesive composition for polarizing plate, polarizing plate comprising the same and optical display comprising the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007108592A (en) * 2005-10-17 2007-04-26 Nitto Denko Corp Laminate for liquid crystal display apparatus, and liquid crystal display apparatus with same
KR101010889B1 (en) * 2006-03-15 2011-01-25 닛토덴코 가부시키가이샤 Adhesive optical film, multilayer optical film and image display
KR101351620B1 (en) * 2010-12-29 2014-01-15 제일모직주식회사 Binder for adhesive composition, adhesive composition comprising the same and optical member using the same
JP2014038180A (en) * 2012-08-15 2014-02-27 Konica Minolta Inc Optical film, production method of optical film, polarizing plate and liquid crystal display device
KR20150062088A (en) * 2013-11-28 2015-06-05 제일모직주식회사 Adhesive composition, adhesive film prepared using the same and optical display apparatus comprising the same
KR20150102625A (en) * 2014-02-28 2015-09-07 제일모직주식회사 Adhesive composition for polarizing plate, polarizing plate comprising the same and optical display comprising the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190004562A (en) * 2017-07-04 2019-01-14 삼성에스디아이 주식회사 Adhesive composition for polarizing plate, adhesive film for polarizing plate prepared using the same, polarizing plate comprising the same and optical display apparatus comprising the same
KR20200100202A (en) * 2018-03-30 2020-08-25 닛토덴코 가부시키가이샤 Polarizing film and image display device with pressure-sensitive adhesive layer
US11169312B2 (en) 2018-03-30 2021-11-09 Nitto Denko Corporation Pressure-sensitive-adhesive-layer-attached polarizing film, and image display device

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