KR101900545B1 - Adhesive film, optical member comprising the same and optical display apparatus comprising the same - Google Patents

Adhesive film, optical member comprising the same and optical display apparatus comprising the same Download PDF

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KR101900545B1
KR101900545B1 KR1020150177496A KR20150177496A KR101900545B1 KR 101900545 B1 KR101900545 B1 KR 101900545B1 KR 1020150177496 A KR1020150177496 A KR 1020150177496A KR 20150177496 A KR20150177496 A KR 20150177496A KR 101900545 B1 KR101900545 B1 KR 101900545B1
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meth
adhesive layer
film
silicone
acrylate
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KR20170069819A (en
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문성현
곽병도
이우진
김일진
김지호
조익환
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삼성전자주식회사
삼성에스디아이 주식회사
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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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • 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

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

Wherein the (meth) acrylic adhesive layer comprises an emulsifier, and a (meth) acrylic adhesive layer formed on one side or both sides of the silicone adhesive layer and the silicone adhesive layer, and an optical member including the adhesive film Is provided.

Description

TECHNICAL FIELD [0001] The present invention relates to an adhesive film, an optical member including the adhesive member, and an optical display device including the adhesive member. [0002]

The present invention relates to an adhesive film, an optical member including the same, and an optical display device including the same.

The optical display device includes a display element including a window film, a conductive film, and an organic light emitting element. A touch pad has a structure in which a transparent clear adhesive (OCA) is laminated between a window film and a conductive film. The touch pad is operated by a signal generated by changing the capacitance due to contact of a window film of a human hand or a predetermined object or the like.

BACKGROUND ART [0002] In recent years, a transparent pressure-sensitive adhesive film has been produced by laminating a plurality of different pressure-sensitive adhesive layers in order to satisfy various required physical properties. For example, the multilayered transparent pressure sensitive adhesive film may include a silicone-based pressure-sensitive adhesive layer and an acrylic pressure-sensitive adhesive layer. The acrylic adhesive layer can increase the adhesive force of the adhesive film, and the silicone adhesive layer can improve the reliability and durability of the adhesive film. However, the silicone adhesive layer and the acrylic adhesive layer are formed of different materials, so that the interface peel strength is low and can be peeled off from each other.

On the other hand, flexible display devices having flexibility that can be folded and unfolded in recent optical display devices are being developed. Flexible display devices require that the various optical elements included in the apparatus have flexibility. Since the transparent pressure-sensitive adhesive film is formed between the window film and the conductive film, the adhesive force of both sides must be excellent. Further, in order to be used in a flexible display device, bending property and / or folding property should be good.

The background art of the present invention is disclosed in Japanese Laid-Open Patent Application No. 2013-067737.

A problem to be solved by the present invention is to provide a multi-layered pressure-sensitive adhesive film comprising a silicone-based pressure-sensitive adhesive layer and a (meth) acrylic pressure-sensitive adhesive layer having a high interfacial peeling strength between a silicone pressure sensitive adhesive layer and a (meth) acrylic pressure sensitive adhesive layer.

Another object to be solved by the present invention is to provide a multilayer adhesive film free from yellowing and having high reliability at high temperature and / or high humidity.

Another problem to be solved by the present invention is to provide a multi-layer pressure-sensitive adhesive film having low resistance change rate and excellent reliability.

Another object to be solved by the present invention is to provide an optically transparent multi-layer pressure-sensitive adhesive film.

Another object to be solved by the present invention is to provide a multilayer adhesive film having good bending and / or good folding properties under bending and / or folding conditions.

The pressure-sensitive adhesive film of the present invention includes a silicone-based pressure-sensitive adhesive layer and a (meth) acrylic pressure-sensitive adhesive layer formed on one or both sides of the silicone pressure-sensitive adhesive layer, and the (meth) acrylic pressure-sensitive adhesive layer may include an emulsifier.

The optical member of the present invention may include an optical film and the adhesive film formed on at least one side of the optical film.

The optical display device of the present invention may include the above-mentioned pressure-sensitive adhesive film.

The present invention provides a multilayer pressure-sensitive adhesive film comprising a silicone-based pressure-sensitive adhesive layer and a (meth) acrylic pressure-sensitive adhesive layer having a high interface peel strength between a silicone-based pressure-sensitive adhesive layer and a (meth) acrylic pressure-sensitive adhesive layer.

The present invention provides a multilayer pressure-sensitive adhesive film free from yellowing and having high reliability at high temperature and / or high humidity.

The present invention provides a multi-layer pressure-sensitive adhesive film having low resistance change rate and excellent reliability.

The present invention provides an optically transparent multilayer adhesive film.

The present invention provides a multilayer adhesive film having good bending and / or good folding properties under bending and / or folding conditions.

1 is a cross-sectional view of an adhesive film according to an embodiment of the present invention.
2 is a cross-sectional view of an adhesive film according to another embodiment of the present invention.
3 is a cross-sectional view of an optical display device according to an embodiment of the present invention.

The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments of the invention are shown. 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.

The terms "upper" and "lower" in this specification are defined with reference to the drawings, wherein "upper" may be changed to "lower", "lower" What is referred to as "on" may include not only superposition, but also intervening other structures in the middle. On the other hand, what is referred to as "directly on" or "directly above"

As used herein, "(meth) acrylic" means acrylic and / or methacrylic, and "copolymer" may include oligomers, polymers or resins. In the present specification, at least one hydrogen atom substituted in the "substituted or unsubstituted" is a C1 to C10 alkyl group, a C1 to C10 thioalkyl group, a C1 to C10 alkoxy group, a halogen (F, Cl, Br or I) To C10 cycloalkyl groups, or C6 to C20 aryl groups.

In the present specification, the term " interfacial peel strength "between the silicone adhesive layer and the acrylic adhesive layer in the adhesive film in the present specification means that when the adhesive film has a three-layer structure of an acrylic adhesive layer, a silicone adhesive layer and an acrylic adhesive layer, Sensitive adhesive layer to a polyethylene terephthalate film and peel strength when peeled at a temperature of 25 DEG C at 180 DEG C at a speed of 300 mm / min. When the adhesive film has a two-layer structure of an acrylic adhesive layer and a silicone adhesive layer, Layer is adhered to a corona-treated PET film and peel strength when peeled at 180 DEG C at 25 DEG C at a speed of 300 mm / min.

In the present specification, the "modulus" of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive film is a storage modulus, and a plurality of pressure-sensitive adhesive layers or adhesive films are laminated and perforated to prepare specimens having a thickness of 500 μm and a diameter of 8 mm. At an auto strain condition, a measurement was carried out at a temperature rise rate of 5 DEG C / min in a temperature range of -60 DEG C to 90 DEG C using an 8 mm jig, and at each of -20 DEG C, 25 DEG C and 80 DEG C, Respectively. The "average particle diameter" of the organic particles in this specification is the particle diameter of the organic particles expressed by the Z-average value measured by a Zetasizer nano-ZS instrument of Malvern in water or organic solvent.

Hereinafter, an adhesive film according to an embodiment of the present invention will be described with reference to FIG. 1 is a cross-sectional view of an adhesive film according to an embodiment of the present invention.

1, the adhesive film 100 includes a first (meth) acrylic adhesive layer 110 and a silicone adhesive layer 120, and the first (meth) acrylic adhesive layer 110 includes an emulsifier (Not shown in FIG.

The silicone adhesive layer 120 is formed directly on the first (meth) acrylic adhesive layer 110. Means that no adhesive layer or adhesive layer is interposed between the first (meth) acrylic adhesive layer 110 and the silicone adhesive layer 120. The adhesive film 100 includes the first (meth) acrylic adhesive layer 110 to increase the interface peeling strength between the silicone adhesive layer 120 and the first (meth) acrylic adhesive layer 110, And the first (meth) acrylic adhesive layer 110 are not separated from each other, so that the reliability of the adhesive film 100 can be improved. Specifically, the interface peel strength between the silicone adhesive layer 120 and the first (meth) acrylic adhesive layer 110 is 600 gf / in or more, more specifically 600 gf / in to 5,000 gf / in, more specifically 600 gf / 1,500 gf / in.

Since the adhesive film 100 includes the silicone adhesive layer 120, the stress relaxation property is good and the silicone adhesive layer 120 and the first (meth) acrylic adhesive layer 110 have high interface peel strength and are not separated from each other . Thus, the adhesive film 100 has good bending and / or good folding properties under bending and / or folding conditions and can be used in a flexible display device.

Specifically, the pressure-sensitive adhesive film 100 satisfies the following formula (1), and has good bending and / or good folding properties at 25 占 폚 as well as excellent reliability and workability:

<Formula 1>

G2 (25) x2? G1 (25)? G2 (25) x10

(25) is the modulus of the silicone-based adhesive layer at 25 ° C, and G1 (25) is the modulus of the first (meth) acrylic adhesive layer at 25 ° C.

Specifically, the pressure-sensitive adhesive film 100 satisfies the following formula (2), has satisfactory bending and / or good folding characteristics even at a low temperature, can maintain the peeling strength of the pressure-sensitive adhesive film, and can be excellent in reliability and workability:

<Formula 2>

G2 (-20) x 10? G1 (-20)

(-20) is the modulus of the silicone-based adhesive layer at -20 ° C, and G1 (-20) is the modulus of the first (meth) acrylic adhesive layer at -20 ° C.

Specifically, the pressure-sensitive adhesive film 100 satisfies the following formula (3), has satisfactory bending and / or good folding properties even at a high temperature, and maintains the peeling force between the silicone-based pressure-sensitive adhesive layer and the first (meth) Reliability and workability can also be excellent:

<Formula 3>

G1 (80)? G2 (80)

(In the formula 3, G2 (80) is the modulus of the silicone-based adhesive layer at 80 DEG C, and G1 (80) is the modulus of the first (meth) acrylic adhesive layer at 80 DEG C).

Since the adhesive film 100 includes the first (meth) acrylic adhesive layer 110, the adhesive strength to the adherend is good and the durability reliability can be improved by including the silicone adhesive layer 120. As used herein, the term "adherend" may include, but is not limited to, a window film, a transparent conductive film, a polarizer, a polarizing plate, an organic light emitting device barrier layer and the like.

The pressure-sensitive adhesive film (100) may have a modulus of 10 KPa to 500 KPa at -20 ° C, a modulus of 10 KPa to 400 KPa at 25 ° C, and a modulus of 10 KPa to 300 KPa at 80 ° C. In the above range, folding can be excellent at a low temperature and a high temperature. The adhesive film 100 may have a haze of 1% or less, specifically 0.1% to 0.9% and a total light transmittance of 90% or more, specifically 95% to 99% in a visible light region (e.g., a wavelength of 380 nm to 780 nm). Within this range, transparency is good and can be used in optical display devices. The thickness of the adhesive film 100 may be 20 占 퐉 to 300 占 퐉, specifically 70 占 퐉 to 200 占 퐉. In the above range, it can be used in an optical display device.

Hereinafter, the first (meth) acrylic adhesive layer 110 will be described.

The first (meth) acrylic adhesive layer 110 can provide adhesive force and endurance reliability to the adhesive film 100.

Thickness of the first (meth) acryl-based adhesive layer 110: The thickness ratio of the silicone-based adhesive layer 120 may be 1: 0.5 to 1: 5, specifically 1: 1 to 1: 5. Within this range, the pressure-sensitive adhesive film has good adhesive strength and durability reliability, exhibits good bending and / or good folding, and can be flexible. The thickness of the first (meth) acrylic adhesive layer 110 may be 10 탆 to 100 탆, specifically 10 탆 to 50 탆. In the above range, it can be used in an optical display device, and has an appropriate thickness in comparison with the silicone adhesive layer, so that both the stress relaxation property and the adhesive force can be provided to the adhesive film. The first (meth) acrylic adhesive layer 110 may have a modulus of 10 KPa to 400 KPa, specifically 50 KPa to 300 KPa at 25 ° C. In the above range, the adhesive film may have good reliability and adhesion. The first (meth) acrylic adhesive layer 110 has a glass transition temperature (Tg) of 0 ° C or less, specifically -150 ° C to 0 ° C, more specifically -150 ° C to -10 ° C, -20 &lt; 0 &gt; C. In the above-mentioned range, the pressure-sensitive adhesive film has excellent viscoelastic properties at low temperature and at room temperature.

The first (meth) acrylic adhesive layer 110 is formed of a first (meth) acrylic adhesive layer containing a monomer mixture containing a non-hydroxylated monomer having no hydroxyl group and (meth) acrylate having a hydroxyl group, / RTI &gt; The first (meth) acrylic adhesive layer may include a (meth) acrylic copolymer obtained by polymerizing the monomer mixture. (Meth) acrylic copolymer can be partially polymerized to obtain a viscous liquid having a viscosity of 500 to 5000 cps, followed by coating and curing to prepare a first (meth) acrylic adhesive layer.

The partially polymerized (meth) acrylic copolymer may have a weight average molecular weight of 500,000 g / mol to 2,500,000 g / mol, specifically 700,000 g / mol to 2,000,000 g / mol. Within this range, reliability improvement effects may be obtained in high temperature and high humidity tests. (Meth) acrylic copolymer may have a glass transition temperature (Tg) of -20 占 폚 or less, specifically -150 占 폚 to -20 占 폚, more specifically -150 占 폚 to -30 占 폚. In the above range, the viscoelastic characteristics at low temperature and room temperature can be excellent. In one embodiment, the (meth) acrylic copolymer may be a copolymer of a monomer mixture comprising a non-hydroxylic monomer having no hydroxyl group and a (meth) acrylate having a hydroxyl group. At this time, the adhesive film 100 has a glass transition temperature (Tg) of 0 占 폚 or less, specifically -80 占 폚 to -10 占 폚, a resistance change rate? R of the following formula 4 is 5% 5%. &Lt; / RTI &gt; In this case, it is possible to lower the capacitance value at the touch and raise the sensing sensitivity by reducing the occurrence of time delay in the signal:

<Formula 4>

Figure 112015121834773-pat00001

(In the formula 4, P 1 is the initial resistance (unit: Ω) measured on a sample where electrodes are formed at both ends of the adhesive film, and P 2 is the sample left at 60 ° C. and 90% relative humidity for 240 hours (Unit: Ω)).

The non-hydrothermal monomer may have a glass transition temperature of the homopolymer of -20 占 폚 or lower, specifically -150 占 폚 to -20 占 폚, and may be an alkyl (meth) acrylate monomer, a monomer having ethylene oxide, May include at least one of a monomer, a monomer having an amine group, a monomer having an amide group, a monomer having an alkoxy group, a monomer having a phosphoric acid group, a monomer having a sulfonic acid group, a monomer having a phenyl group and a monomer having a silane group.

The alkyl (meth) acrylate monomers may include unsubstituted linear or branched alkyl (meth) acrylates of 1 to 20 carbon atoms. (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, (Meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, ethylhexyl (meth) acrylate, octyl Acrylate, decyl (meth) acrylate, and lauryl (meth) acrylate. Preferably, the use of an alkyl (meth) acrylic monomer having 4 to 8 carbon atoms, more preferably ethylhexyl (meth) acrylate, may further enhance the initial adhesion.

As the monomer having an ethylene oxide, one or more (meth) acrylate monomers containing an ethylene oxide group (-CH 2 CH 2 O-) may be used. (Meth) acrylate, polyethylene oxide monoethyl ether (meth) acrylate, polyethylene oxide monopropyl ether (meth) acrylate, polyethylene oxide monobutyl ether (meth) acrylate, (Meth) acrylate, polyethylene oxide monoethyl ether (meth) acrylate, polyethylene oxide monopentyl ether (meth) acrylate, polyethylene oxide dimethylacetate (Meth) acrylate such as isobutyl ether (meth) acrylate, polyethylene oxide mono-t-butyl ether (meth) acrylate, but is not limited thereto.

The monomer having propylene oxide may be at least one selected from the group consisting of polypropylene oxide monomethyl ether (meth) acrylate, polypropylene oxide monoethyl ether (meth) acrylate, polypropylene oxide monopropyl ether (meth) acrylate, polypropylene oxide monobutyl (Meth) acrylate, polypropylene oxide diethyl ether (meth) acrylate, polypropylene oxide monoisopropyl ether (meth) acrylate, polypropylene oxide dimethylacetate (Meth) acrylate such as polypropylene oxide alkyl ether (meth) acrylate, polypropylene oxide monoisobutyl ether (meth) acrylate, and polypropylene oxide mono butyl ether (meth) acrylate , But are not necessarily limited thereto.

Monomers having an amine group include monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, monoethylaminopropyl (meth) acrylate, dimethylaminoethyl (Meth) acrylate, diethylaminoethyl (meth) acrylate, N-tert-butylaminoethyl (meth) acrylate, (meth) acryloxyethyltrimethylammonium chloride and the like.

(Meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N, Acrylamide, 2-hydroxyethyl (meth) acrylamide, and the like, but the present invention is not limited thereto.

Examples of the monomer having an alkoxy group include 2-methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 2-ethoxypropyl (meth) (Meth) acrylate, methoxypentyl (meth) acrylate, 3-ethoxypentyl (meth) acrylate, 2-ethoxypentyl ) Acrylate, 3-butoxyhexyl (meth) acrylate, and the like.

Examples of the monomer having a phosphoric acid group include 2- (meth) acryloyloxyethyldiphenyl phosphate (meth) acrylate, tri (meth) acryloyloxyethyl phosphate (meth) acrylate, tri (meth) acryloyloxyethyl (Meth) acrylic monomer having a phosphate group such as phosphate, but is not limited thereto.

The monomer having a sulfonic acid group is preferably a monomer having a sulfonic acid group such as sodium sulfopropyl (meth) acrylate, sodium 2-sulfoethyl (meth) acrylate and sodium 2- (meth) acrylamido- Meth) acrylic monomer, but it is not necessarily limited thereto.

The (meth) acrylic monomer having a phenyl group such as p-tert-butylphenyl (meth) acrylate or o-biphenyl (meth) acrylate can be used as the monomer having a phenyl group.

The monomer having a silane group may be at least one selected from the group consisting of 2-acetoacetoxyethyl (meth) acrylate, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (beta -methoxyethyl) silane, vinyltriacetylsilane, Propyltrimethoxysilane, and the like, but the present invention is not limited thereto.

The (meth) acrylate having a hydroxyl group may be an alkyl group having 1-20 carbon atoms having at least one hydroxyl group, a cycloalkyl group having 5-20 carbon atoms having at least one hydroxyl group, or an aryl group having 6-20 carbon atoms having at least one hydroxyl group (Meth) acrylic acid esters having (meth) acrylic acid esters. (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 6- (Meth) acrylate, and hydroxyhexyl (meth) acrylate. In particular, by using a (meth) acrylic monomer containing an alkyl group having 1 to 5 carbon atoms and having a hydroxyl group, an adhesive strength increasing effect can be further obtained. In a specific example, the (meth) acrylate having a hydroxyl group may have a homopolymer having a glass transition temperature (Tg) of -80 ° C to -20 ° C. For example, 4-hydroxybutyl (meth) acrylate and the like can be used, but not always limited thereto. At the above glass transition temperature, the pressure-sensitive adhesive film has excellent viscoelastic properties at low temperatures and at room temperature.

For example, the monomer mixture may contain 60 to 95% by weight, specifically 60 to 80% by weight, of a non-hydroxylated monomer having a glass transition temperature (Tg) of -20 占 폚 or less and no hydroxyl group, (Meth) acrylate may comprise from 5 wt% to 40 wt%, specifically from 20 wt% to 40 wt%.

The monomer mixture may further include at least one of a vinyl monomer having a carboxylic acid group, a vinyl monomer having an alicyclic group, and a (meth) acrylic monomer having an alicyclic hetero group as a non-hydroxylic monomer.

The vinyl monomer having a carboxylic acid group may include a carboxylic acid having a vinyl group or a (meth) acrylic acid ester having a carboxylic acid group. For example, the vinyl monomer having a carboxylic acid group may be at least one selected from the group consisting of? -Carboxyethyl (meth) acrylate, (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, But is not limited to these. The vinyl monomer having a carboxylic acid group may be contained in an amount of less than 3% by weight, specifically 0% to 1% by weight of the monomer mixture. Within the above range, the rate of change in resistance can be lowered while obtaining a result of increasing the adhesive force of the adhesive film.

The vinyl monomer having an alicyclic group may be a monomer containing one olefinic double bond and at least one alicyclic group in the molecule. For example, there can be mentioned acrylic acid esters such as isobornyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, cyclododecyl acrylate, methylcyclohexyl acrylate, trimethyl cyclohexyl acrylate, tert-butyl cyclohexyl acrylate, Acrylate having an alicyclic structure such as ethoxy acrylate, cyclohexyl phenyl acrylate and the like; Isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentyl methacrylate, cyclododecyl methacrylate, methylcyclohexylmethacrylate, trimethylcyclohexylmethacrylate, tert-butylcyclohexylmethacrylate, Cyclohexyl α-ethoxy methacrylate, cyclohexyl phenyl methacrylate, biscyclohexylmethyl itaconate, dicyclooctyl itaconate, dicyclododecyl methyl succinate, vinyl cyclohexyl acetate, and the like. And the like. The vinyl monomer having an alicyclic group may be contained in the monomer mixture in an amount of 0 to 10% by weight, specifically 0 to 5% by weight. Within this range, there may be an effect of enhancing the adhesion of the glass base material.

The (meth) acrylic monomer having an alicyclic hetero group may include (meth) acrylic monomers having 4 to 6 carbon atoms and having a single alicyclic heterocycle having nitrogen, oxygen or sulfur. For example, the monomer may include (meth) acryloylmorpholine and the like. The (meth) acrylic monomer having an alicyclic hetero group may be contained in the monomer mixture in an amount of 0 to 10% by weight, specifically 0 to 5% by weight. Within this range, there may be an effect of enhancing the adhesion of the glass base material.

The initiator may comprise a photoinitiator. The photoinitiator may be activated by ultraviolet rays or electron beams to activate a carbon-carbon double bond in the adhesive film to cause a radical reaction. The initiator may be a hydroxy ketone compound, an acetophenone compound, a benzyl ketal compound, or a mixture thereof, but is not limited thereto. Examples of the hydroxyketone compound include 1-hydroxycyclohexyl phenyl ketone, acetophenone compound, 2,2-dimethoxy-2-phenylacetophenone, 2,2'-diethoxyacetophenone, 2,2'- 2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone , 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane- 1-one, or a mixture thereof. The initiator may be included in an amount of 0.01 part by weight to 10 parts by weight, specifically 0.1 part by weight to 1 part by weight, based on 100 parts by weight of the monomer mixture including the (meth) acrylate having a hydroxyl group and a non-hydroxyl group having no hydroxyl group . In the above range, excellent reliability at high temperature and / or high humidity can be achieved, and the modulus required in the present invention can be achieved, so that the adhesive film can be easily folded.

The emulsifier can improve the interface peel strength between the first (meth) acrylic adhesive layer and the silicone adhesive layer by modifying the surface of the first (meth) acrylic adhesive layer in contact with the silicone adhesive layer. Particularly, the emulsifier can be produced by laminating a first (meth) acrylic adhesive layer and a silicone adhesive layer in the production of an adhesive film, and then heat-treating the first (meth) acrylic adhesive layer and the silicone adhesive layer for a predetermined time to further improve the surface modifying effect, The strength can be increased. Generally, an emulsifier is an additive which is used in the production of a copolymer, which may deteriorate the stability over time after the copolymer is prepared, and is thus removed. However, the present invention is based on the fact that the interfacial peeling strength between the first (meth) acrylic adhesive layer and the silicone adhesive layer is improved by further including an emulsifier after the copolymer is prepared. The emulsifier may be contained in the whole of the first (meth) acrylic adhesive layer or may be included only in a part of the surface of the first (meth) acrylic adhesive layer in contact with the silicone adhesive layer. The emulsifier may be included in an amount of 0.01 to 8 parts by weight, specifically 0.1 to 5 parts by weight based on 100 parts by weight of the monomer mixture. Within the above range, the peeling strength between the silicone-based adhesive layer and the first (meth) acrylic-based adhesive layer can be increased, bubble generation can be suppressed, reliability can be improved, and yellowing can be prevented. The emulsifier is a liquid compound, and when included in the first (meth) acrylic adhesive layer, the haze can be lowered and the surface modification effect can be further enhanced. In addition, the emulsifier has a hydrophilic group and a hydrophobic group at the same time, thereby enhancing the interface peel strength between the silicone-based adhesive layer and the first (meth) acrylic-based adhesive layer. The emulsifier may be selected from the group consisting of fatty acid series, linear alkylbenzene series, higher alcohol series, alkylphenol series, alpha olefin series, normal paraffin series, alkyl glucoside series, sucrose fatty acid ester series, sorbitan fatty acid ester series, polyoxyethylene sorbitan fatty acid ester Based, rosin ester-based, and the like. Specific examples include potassium soap, potassium stearate, salt of half esters of succinic acid of sulfosuccinic acid, sorbitan monopalmitate, sorbitan monostearate , Polyoxyethylene sorbitan monostearate such as sorbitan tristearate and polyoxyethylene (20) sorbitan monostearate, and polyoxyethylene sorbitan tristearate such as polyoxyethylene (20) sorbitan tristearate , Polyoxyethylene (10) cetyl ether, polyoxyethylene (20) cetyl ether, and other polyoxyethylene cetyl ether.

The composition for the first (meth) acrylic adhesive layer may further comprise at least one of a crosslinking agent and a silane coupling agent. The crosslinking agent may comprise a multifunctional (meth) acrylate capable of curing with an active energy beam. In an embodiment, the crosslinking agent is selected from the group consisting of 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate, di (Meth) acrylate, trimethylolpropane di (meth) acrylate, acryloyloxyethyl isocyanurate, allyl cyclohexyl di (meth) acrylate, tricyclodecane dimethanol Di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, neopentyl glycol modified trimethylpropane di (meth) acrylate, adamantanedi (meth) 9,9-bis [4- (2-oxy-yl acrylate) phenyl] fluorene difunctional acrylate and the like; (Meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide Trifunctional acrylates such as modified trimethylolpropane tri (meth) acrylate, trifunctional urethane (meth) acrylate or tris (meth) acryloxyethylisocyanurate; Tetrafunctional acrylates such as diglycerin tetra (meth) acrylate or pentaerythritol tetra (meth) acrylate; Pentafunctional acrylates such as dipentaerythritol penta (meth) acrylate; (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate or urethane (meth) acrylate (ex. Isocyanate monomer and trimethylol propane tri (Meth) acrylates of polyhydric alcohols can be used as the crosslinking agent. The polyfunctional (meth) acrylates of polyhydric alcohols may be used alone or in combination of two or more. (Meth) acrylic adhesive layer having good adhesion to the silicone adhesive layer 120. The crosslinking agent may be used in an amount of 0.01 to 0.15 parts by weight, specifically 0.01 part by weight (based on 100 parts by weight of the monomer mixture) To 0.1 part by weight. In the above range, the solvent resistance and the crosslinking degree in the UV reaction can be suitably increased to improve the durability. As the coupling agent, those conventionally known to those skilled in the art can be used. For example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , Silicon compounds having an epoxy structure such as 2- (3,4-epoxycyclohexyl) ethyl trimethoxysilane, polymerization of vinyltrimethoxysilane, vinyltriethoxysilane, and (meth) acryloxypropyltrimethoxysilane Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxy But are not limited to, at least one selected from the group consisting of an amino group-containing silicon compound such as silane, and 3-chloropropyltrimethoxysilane. Preferably, 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 monomer mixture. Within the above range, The adhesive force is increased.

The composition for the first (meth) acrylic adhesive layer may further comprise organic particles. Since the pressure-sensitive adhesive composition or the pressure-sensitive adhesive film further contains organic particles, it has excellent low temperature and / or room temperature viscoelasticity, has a crosslinked structure, and stably exhibits high temperature viscoelasticity. In an embodiment, the organic particles may form a chemical bond with the hydroxyl group of the (meth) acrylic copolymer. The average particle size of the organic particles may be 10 nm to 400 nm, specifically 10 nm to 300 nm, more specifically 10 nm to 200 nm. Within this range, aggregation of the organic particles can be prevented, and the transparency of the adhesive film is excellent. The organic particles are core-shell structures, and the organic particles can satisfy the following formula 5:

&Lt; EMI ID =

Tg (c) < Tg (s)

(Unit: 占 폚), and Tg (s) is the glass transition temperature (unit: 占 폚) of the shell.

The glass transition temperature of the core may be -150 ° C to 10 ° C, specifically -150 ° C to -5 ° C, more specifically -150 ° C to -20 ° C. It is possible to realize a storage modulus value required at a low temperature (-20 DEG C) in the above range, and is excellent in low temperature and / or room temperature viscoelastic properties. The core may comprise at least one polyalkyl (meth) acrylate having the above glass transition temperature. For example, the core may be selected from the group consisting of polymethyl acrylate, polyethylacrylate, polypropyl acrylate, polybutyl acrylate, polyisopropyl acrylate, polyhexyl acrylate, polyhexyl methacrylate, polyethylhexyl acrylate, and poly Ethylhexyl methacrylate, and the like, but not always limited thereto. Specifically, it may include at least one of polybutyl acrylate and polyethyl hexyl acrylate. The glass transition temperature of the shell may be from 15 캜 to 150 캜, specifically from 35 캜 to 150 캜, more specifically from 50 캜 to 140 캜. There is an advantage that the dispersibility of the organic particles is excellent in the (meth) acrylic copolymer having a hydroxyl group within the above range. The shell may comprise a polyalkyl (meth) acrylate having a glass transition temperature as described above. For example, it is possible to use polymethylmethacrylate (PMMA), polyethylmethacrylate, polypropylmethacrylate, polybutylmethacrylate, polyisopropylmethacrylate, polyisobutylmethacrylate and polycyclohexylmethacrylate Rate, &lt; / RTI &gt; but is not necessarily limited thereto. Specifically, it may include polymethyl methacrylate. The organic particles may be included in an amount of 0.1 to 15 parts by weight, specifically 0.5 to 10 parts by weight, more specifically 0.5 to 8 parts by weight, based on 100 parts by weight of the monomer mixture. Within the above range, the viscoelasticity of the pressure-sensitive adhesive film, the storage modulus and the recovery force can be balanced.

The composition for the first (meth) acrylic adhesive layer may optionally contain a curing accelerator, an ionic liquid, a lithium salt, an inorganic filler, a softener, an antioxidant, an antioxidant, a stabilizer, a tackifier resin, , Leveling agents, defoaming agents, plasticizers, dyes, pigments (coloring pigments, extender pigments, etc.), treating agents, ultraviolet light blocking agents, fluorescent agents An antistatic agent, a lubricant, and a solvent, in addition to the above-mentioned additives. The additive may be included in an amount of 0.01 to 5 parts by weight, specifically 0.03 to 3 parts by weight, more specifically 0.05 to 2 parts by weight, based on 100 parts by weight of the monomer mixture.

Hereinafter, the silicone adhesive layer 120 will be described.

The silicone-based adhesive layer 120 can provide good bending and / or good folding properties to the adhesive film 100. The thickness of the silicone-based adhesive layer 120 may be 30 占 퐉 to 200 占 퐉, specifically 40 占 퐉 to 100 占 퐉. In the above range, the stress relaxation and lifting phenomenon in the bending / folding condition is less.

The silicone-based adhesive layer 120 may have a modulus lower than that of the first (meth) acryl-based adhesive layer at -20 ° C. Therefore, the pressure-sensitive adhesive film may have good bending and good folding property, and thus good flexibility. Specifically, the silicon-based adhesive layer 120 may have a modulus of 1 KPa to 300 KPa at -20 캜. The bending / folding property is good in the above range, the peeling force with the first (meth) acrylic adhesive layer is excellent, and the reliability and workability are good.

The silicone adhesive layer 120 may be formed of a composition for a silicone-based adhesive layer, which comprises a silicone polymer and a silicone compound having silicon-hydrogen (Si-H).

The silicone polymer comprises a siloxane polymer having a silicon-bonded vinyl group (Si-vinyl), and forms a matrix of the silicone-based adhesive layer by hydrosilylation with a silicon compound having silicon-hydrogen (Si-H) .

In one embodiment, the silicone polymer is one or more D units R a R b SiO 2/2 ( wherein, R a and R b are each independently, an alkyl group, a substituted or unsubstituted substituted or unsubstituted C 1 -C 10 a is c 3 -C 10 cycloalkyl group, or a substituted or unsubstituted c 6 -C 10 aryl group), and * -SiR c R d Vi (wherein, * is a connection portion of the element, R c And R d are each independently a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 3 -C 10 cycloalkyl group, or a substituted or unsubstituted C 6 -C 10 aryl group, And Vi is a vinyl group. Specifically, R a , R b may each independently be a C 1 -C 6 alkyl group, more specifically methyl, ethyl, propyl, butyl, pentyl or hexyl.

Specifically, the silicone polymer may comprise a siloxane polymer represented by the following formula:

&Lt; Formula 1 >

R 1 R 2 ViSiO- (R 3 R 4 SiO) n -SiR 5 R 6 Vi

(Wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is, independently of each other, a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 3 -C 10 cycloalkyl group, or a substituted or unsubstituted C 6 -C 10 aryl group, Vi is a vinyl group, and n is an integer. When the weight average molecular weight of the siloxane polymer is 25,000 g / mol to 200,000 g / mol, in this range, an adhesive film having good bending and good folding can be produced. More specifically, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may each independently be a C 1 -C 6 alkyl group, more specifically methyl, ethyl, propyl, butyl, pentyl or hexyl. n can be a natural number of 1 or more and can be adjusted according to the weight average molecular weight of the polymer. The silicone polymer may be included as a silicone polymer alone or as a mixture of two silicone polymers having different weight average molecular weights. Specifically, the silicone polymer comprises a first silicone polymer having a weight average molecular weight of greater than 100,000 g / mol to 200,000 g / mol and a second silicone polymer having a weight average molecular weight of 25,000 g / mol to 100,000 g / mol 80 to 90 parts by weight of the first silicone polymer and 10 to 20 parts by weight of the second silicone polymer may be included per 100 parts by weight of the sum of the first silicone polymer and the second silicone polymer. Within this range, the adhesive film may have good bending and / or good folding.

The silicon compound having silicon-hydrogen (Si-H) forms a matrix of the silicone-based adhesive layer by hydrosilylation reaction with the silicone polymer, and may include a conventional organohydrogensiloxane compound. In one embodiment, the silicon-hydrogen (Si-H) is a silicon compound having at least one D unit HR e SiO 2/2 (wherein, R e is an alkyl group a substituted or unsubstituted C 1 -C 10, substituted or unsubstituted A substituted or unsubstituted C 3 -C 10 cycloalkyl group, or a substituted or unsubstituted C 6 -C 10 aryl group). In another embodiment, the silicon compound with silicon-hydrogen (Si-H) has a D unit HR e SiO 2/2 (where R e is as defined above) and one or more D units R a R b SiO 2 / 2 , wherein R & lt ; a & gt ; and R &lt; b & gt ; are as defined above, in the presence of an organohydrogensiloxane compound. For example, a silicon compound having silicon-hydrogen (Si-H) can be represented by the following formula:

(2)

R 7 R 8 R 9 SiO- (HR 10 SiO) x- (R 11 R 12 SiO) y -SiR 13 R 14 R 15

(Wherein R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 each independently represent a substituted or unsubstituted C 1 -C 10 alkyl group, A substituted or unsubstituted C 3 -C 10 cycloalkyl group, or a substituted or unsubstituted C 6 -C 10 aryl group; x is a natural number of 1 or more; and y is an integer of 0 or more). When the silicone compound having silicon-hydrogen (Si-H) has a weight average molecular weight of 500 to 2,000, the silicone adhesive layer has good folding and bending properties. The silicon compound having silicon-hydrogen (Si-H) may be contained in an amount of 0.01 to 10 parts by weight, specifically 0.1 to 5 parts by weight, based on 100 parts by weight of the silicone polymer. Within this range, the modulus can be improved and there can be folding and bending effects.

In the composition for a silicone adhesive layer, the ratio of the number of moles of Si-H (the number of moles of Si-H / the number of moles of Si-vinyl) of the silicone compound to the number of moles of Si-vinyl of the silicone polymer in the composition for a silicone adhesive layer may be 0.6 to 0.95 have. In the above range, since flexibility and adhesive force are obtained at low temperatures, the adhesive film can have excellent effects in bending / folding. In the composition for a silicone adhesive layer, the ratio of the number of moles of Si-H to the number of moles of Si-vinyl (number of moles of Si-H / number of moles of Si-vinyl) can be more than 0.95 and 1.5 or less. In this case, the composition for a silicone adhesive layer may further comprise an MQ silicone resin essentially comprising a monovalent siloxane M unit and a tetravalent siloxane Q unit. As a result, not only the modulus can be improved but also the adhesive strength can be improved. Specifically, the MQ silicone resin is an M unit R'R "R"'SiO 1/2 wherein R', R "and R"'are each independently a substituted or unsubstituted C 1 -C 10 alkyl group, substituted or unsubstituted C 3 -C 10 is a cycloalkyl group, or a substituted or unsubstituted C 6 -C 10 aryl group) and a Q unit may include SiO 4/2. In the MQ silicone resin, the ratio of the number of moles of M units to the number of moles of Q units in the silicone resin may be 0.5: 1 to 1.5: 1, specifically 0.6: 1 to 1.2: 1. Within the above range, it is possible to produce a pressure-sensitive adhesive film which can be well mixed with a silicone polymer, a silicone compound having silicon-hydrogen (Si-H), and the like.

Silicone-based pressure-sensitive adhesive layer compositions D unit R'ViSiO 2/2 (R 'is a substituted or unsubstituted C 1 -C 10 alkyl group, a cycloalkyl group of the substituted or unsubstituted C 3 -C 10, or substituted or unsubstituted A C 6 -C 10 aryl group, and Vi is a vinyl group). At this time, the siloxane polymer may have a weight average molecular weight of 10,000 to 200,000, and may have an effect of improving the modulus in the above range.

The composition for a silicone adhesive layer may further comprise a siloxane compound having a (meth) acrylate group and a silicon-bonded vinyl group (Si-vinyl). The siloxane compound includes at least one (meth) acrylate group and at least one Si-vinyl group, so that the siloxane compound reacts with both the silicone-based adhesive layer and the first (meth) acrylic-based adhesive layer to further increase the interface peel strength. The siloxane compound may include, for example, (meth) acryloxypropyltris (vinyldimethylsiloxy) silane, (3- (meth) acryloxypropyl) bis (vinyldimethylsiloxy) It does not. The siloxane compound may be contained in an amount of 0.5 to 20 parts by weight, specifically 1 to 10 parts by weight based on 100 parts by weight of the silicone polymer. In the above range, the adhesive strength to the first (meth) acrylic adhesive layer may be excellent.

The composition for a silicone adhesive layer may further comprise a catalyst for the hydrosilylation reaction. The catalyst for the hydrosilylation reaction catalyzes the reaction between a silicone polymer, a siloxane compound having a (meth) acrylate group and a silicon-bonded vinyl group (Si-vinyl), and a silicon compound having a silicon-hydrogen (Si-H) So that the formation of the silicone-based adhesive layer can be accelerated. The catalyst for the hydrosilylation reaction may comprise a catalyst for the conventional hydrosilylation reaction. For example, the catalyst may include at least one of a platinum catalyst, a rhodium catalyst, and a palladium catalyst. Specifically, the catalyst can be exemplified by finely divided platinum powder, chloroplatinic acid, alcohol solution of chloroplatinic acid, platinum-alkenylsiloxane complex, platinum-olefin complex, and platinum-carbonyl complex. The alkenylsiloxane is 1,3-divinyl-1,1,3,3-

Tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, by replacing a portion of the methyl in the aforementioned alkenylsiloxane with, for example, ethyl or phenyl , And alkenylsiloxanes provided by replacing the vinyl group in the above-mentioned alkenylsiloxane with, for example, an allyl group or a hexenyl group. In addition, the stability of this platinum-alkenylsiloxane complex can be improved by the addition of alkenylsiloxanes such as 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3- Tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyl di Siloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, or the like, or an organosiloxane oligomer such as a dimethylsiloxane oligomer or the like can be added to the complex And therefore such addition is preferred. The catalyst for the hydrosilylation reaction may include from 0.01 ppm to 500 ppm based on the metal atom. Within this range, it is possible to catalyze the hydrosilylation reaction, and the remaining amount of the hydrosilylation reaction remains so that the transparency of the silicone-based adhesive layer can be prevented from being lowered.

Hereinafter, a method for producing an adhesive film according to this embodiment will be described.

The adhesive film according to this embodiment is prepared by coating and curing a composition for a first (meth) acrylic adhesive layer to prepare a first coating film for a first (meth) acrylic adhesive layer, coating the composition for a silicone adhesive layer, Layer, and then laminating the first coating film and the second coating film. The curing may include one or more of light curing, heat curing. Photocuring may include irradiating ultraviolet light at an UV wavelength of 10 mW / cm 2 to 500 mW / cm 2 . Thermal curing may include thermal curing at 100 ° C to 200 ° C for 1 minute to 1 hour. Acrylic acid adhesive layer of the emulsifier is increased by heat treatment at 50 ° C to 80 ° C for 12 to 24 hours to remove the first (meth) acrylic adhesive layer from the silicone adhesive layer The strength can be further increased. The composition for a first (meth) acrylic adhesive layer can be prepared by mixing an initiator in a monomer mixture for a (meth) acrylic polymer, polymerizing and then adding an emulsifier and optionally an initiator, a crosslinking agent, a silane coupling agent, have. The polymerization may include bulk polymerization. A total dose of 100 to 160 (e.g., 156) is applied to at least one of the first coating film and the second coating film in a dose of 50 to 80 (e.g., 78) and the interfacial peel strength may be further increased by corona treatment.

Hereinafter, an adhesive film according to another embodiment of the present invention will be described with reference to FIG. 2 is a cross-sectional view of an adhesive film according to another embodiment of the present invention.

2, the adhesive film 200 according to the present embodiment includes a first (meth) acrylic adhesive layer 110, a silicone adhesive layer 120, and a second (meth) acrylic adhesive layer 130 can do. The second adhesive layer 200 is further formed on one side of the silicone adhesive layer 120 so that the adhesive film 200 has an effect of increasing the adhesive force at low temperatures and high temperatures according to the adhesive agent. Except that a second (meth) acryl-based adhesive layer 130 is further formed on one side of the silicone-based adhesive layer 120. The adhesive film according to an embodiment of the present invention is substantially the same as the adhesive film according to an embodiment of the present invention. Hereinafter, only the second (meth) acrylic adhesive layer 130 will be described.

The second (meth) acryl-based adhesive layer 130 is formed on the other surface of the silicone-based adhesive layer 120, so that the adhesive force to the adherend can be further increased. The second (meth) acrylic adhesive layer 130 has a modulus ratio at a temperature of -20 ° C, 25 ° C, or 80 ° C relative to the first (meth) acrylic adhesive layer in the modulus of the first (meth) The modulus of the acrylic adhesive layer 130 may be 1: 0.5 to 1: 2. In the above range, the folding property can be controlled according to the coefficient of thermal expansion of the adherend. Specifically, the second (meth) acrylic adhesive layer 130 may have the same modulus as the first (meth) acrylic adhesive layer 110.

The thickness of the second (meth) acrylic adhesive layer 130 may be the same or different from that of the first (meth) acrylic adhesive layer 110. Specifically, the thickness of the first (meth) acrylic adhesive layer 110: the thickness of the second (meth) acrylic adhesive layer 130 may be 1: 0.5 to 1: 3. In the above range, the folding property can be controlled according to the coefficient of thermal expansion of the adherend. The thickness of the second (meth) acrylic adhesive layer 130 may be 10 탆 to 100 탆, specifically 10 탆 to 50 탆. Within the above range, it can be used in an optical display device, and has an appropriate thickness with respect to the silicone adhesive layer, so that both the stress relaxation property and the adhesive force can be provided to the adhesive film.

The second (meth) acrylic adhesive layer 130 may be formed of the same or different composition for the adhesive layer as the first (meth) acrylic adhesive layer 110. 2 shows a case where the second (meth) acrylic adhesive layer and the first (meth) acrylic adhesive layer have different compositions or different thicknesses, but the second (meth) acrylic adhesive layer has a first (meth) Layer may be formed of the same composition for the adhesive layer as the layer and / or may have the same thickness. In this case, it is possible to have physical properties such as the above-mentioned interface peel strength in one embodiment.

The optical member according to an embodiment of the present invention includes an optical film and an adhesive film formed on at least one side of the optical film, and the adhesive film may include an adhesive film according to embodiments of the present invention. Thus, the optical member has good bending and / or good folding properties and can be used in a flexible display device.

The optical film may be a polarizing plate, a color filter, a retardation film, an elliptically polarizing film, a reflective film, an antireflection film, a compensation film, a brightness enhancement film, an orientation film, a light diffusion film, indium tin oxide) film, and the like. The method for producing an optical film can be easily manufactured by a person having ordinary skill in the art to which the present invention belongs.

For example, the touch panel can be formed by attaching the touch pad to a window or an optical film using an adhesive film. Or may be applied to an ordinary polarizing film as an adhesive film as in the prior art.

Hereinafter, an optical display device according to an embodiment of the present invention will be described with reference to FIG. 3 is a cross-sectional view of an optical display device according to an embodiment of the present invention.

3, a flexible display device 300 according to an exemplary embodiment of the present invention includes a display 310, an adhesive layer 320, a polarizer 330, a touch screen panel 340, and a flexible window film 350, and the adhesive layer 320 may include a multilayered adhesive film according to an embodiment of the present invention.

The display unit 310 is for driving the flexible display device 300 and may include an optical element including an OLED, an LED, or an LCD device formed on a substrate and a substrate. Although not shown in FIG. 3, the display 310 may include a lower substrate, a thin film transistor, an organic light emitting diode, a planarization layer, a protective layer, and an insulating layer.

The polarizing plate 330 can implement the display by implementing the polarization of the inner light or preventing the reflection of the external light, or the contrast ratio of the display can be increased. The polarizing plate may be composed of a polarizer alone. Or the polarizing plate may include a polarizing film and a protective film formed on one or both sides of the polarizing film. Or the polarizing plate may include a polarizer and a protective coating layer formed on one or both sides of the polarizer. The polarizer, the protective film, and the protective coating layer may be conventional ones known to those skilled in the art.

The touch screen panel 340 senses a change in capacitance caused when a conductor such as a human body or a stylus touches, and generates an electrical signal. The display unit 310 can be driven by this signal. The touch screen panel 340 is formed by patterning a conductive conductive material. The touch screen panel 340 may include a first sensor electrode and a second sensor electrode formed between the first sensor electrode and the first sensor electrode. have. The conductors for the touch screen panel 340 may include, but are not limited to, metal nanowires, conductive polymers, carbon nanotubes, and the like.

The flexible window film 350 may be formed at the outermost portion of the flexible display device 300 to protect the display device.

Although not shown in FIG. 3, an adhesive layer is further formed between the polarizer 330 and the touch screen panel 340 and / or between the touch screen panel 340 and the flexible window film 350 to form a polarizing plate, a touch screen panel, It is possible to strengthen the bonding between the window films. In one embodiment, the adhesive layer may be formed of a pressure sensitive adhesive composition comprising a (meth) acrylate based resin, a curing agent, an initiator, and a silane coupling agent. In other embodiments, the adhesive layer may comprise an adhesive film according to one embodiment of the present invention.

Further, although not shown in FIG. 3, a polarizing plate is further provided under the display unit 310, so that polarized light can be realized.

Hereinafter, the present invention will be described in more detail by way of examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example  One

80 parts by weight of ethylhexyl acrylate, 20 parts by weight of 4-hydroxybutyl acrylate, and 50 parts by weight of Irgacure 651 were thoroughly mixed in a glass container, dissolved oxygen was replaced with nitrogen gas, and a low pressure lamp (50 mW / cm 2 , BL Lamp manufactured by Sankyo Co., Ltd.) to obtain a mixture of a (meth) acrylic polymer and a (meth) acrylic monomer in the form of a viscous liquid. 0.35 parts by weight of Irgacure 184, 0.5 parts by weight of emulsifier SB (potassium soap of rosin ester, Korea Nickle Co., Ltd., BUREZ K25 502D, solid content 25% by weight) based on 100 parts by weight of the sum of ethylhexyl acrylate and 4-hydroxybutyl acrylate, (Meth) acryl-based pressure-sensitive adhesive composition was prepared.

The resulting composition for a (meth) acrylic pressure-sensitive adhesive layer was coated on a release film (polyester film) having a thickness of 50 占 퐉 and covered with a 75 占 퐉 -thick release film to remove oxygen adversely affecting polymerization, (50 mW / cm 2 , BL Lamp manufactured by Sankyo Co., Ltd.) for 6 minutes to prepare a coating film for a (meth) acryl-based adhesive layer having a thickness of 50 탆.

100 parts by weight of silicone polymer (DMS-V41, weight average molecular weight 55,000 to 70,000), 1.084 parts by weight of silicone compound HMS-501 (Gelest) having silicon-hydrogen (Si-H), platinum catalyst (Umicore, Karstedt catalyst) Based adhesive layer were coated on a fluorine releasing film (polyester film) to a thickness of 50 占 퐉 and thermally cured in an oven at 120 占 폚 for 20 minutes to obtain a silicone-based pressure-sensitive adhesive layer Thereby preparing a coating film for the adhesive layer. (The number of moles of Si-H groups in the silicone compound / the number of moles of Si-vinyl groups in the silicone polymer) in the composition for the silicone adhesive layer was 0.8.

One side of a coating film for a (meth) acryl-based adhesive layer and a coating film for a silicone-based adhesive layer was subjected to corona treatment (corona treatment at a total dose of 156 dose, (Meth) acryl-based adhesive layer (thickness: 50 占 퐉) / silicone-based adhesive layer (thickness: 50 占 퐉) were laminated in this order and left at 50 占 폚 for 24 hours (Total thickness: 150 占 퐉) of a pressure-sensitive adhesive layer (thickness: 50 占 퐉) / (meth) acrylic adhesive layer (thickness: 50 占 퐉)

Example  2

100 parts by weight of a silicone polymer (DMS-V41, weight average molecular weight 55,000 to 70,000), 1.084 parts by weight of a silicone compound HMS-501 (Gelest) having silicon-hydrogen (Si-H) , Karstedt catalyst) and 1 part by weight of methacryloxypropyltris (vinyldimethylsiloxy) silane (MATVS, Gelest) were mixed and stirred for 5 minutes to prepare a composition for a silicone-based pressure-sensitive adhesive layer, .

Example  3 to Example  5

A pressure-sensitive adhesive film was prepared in the same manner as in Example 2, except that the content of the emulsifier SB (rosin ester, Korean Nickel Co., Ltd., BUREZ K25 502D) was changed as shown in Table 1 below.

Example  6

(Meth) acryl-based pressure-sensitive adhesive layer (thickness: 50 占 퐉) / silicone-based pressure-sensitive adhesive layer (thickness: 50 占 퐉) was prepared in the same manner as in Example 1, : 50 占 퐉) (total thickness: 100 占 퐉).

Comparative Example  One

An adhesive film was prepared in the same manner as in Example 2, except that the emulsifier SB (rosin ester, Korea NIKE Co., Ltd., BUREZ K25 502D) was not used.

The following properties of the pressure-sensitive adhesive films of Examples and Comparative Examples were evaluated and shown in Tables 2 and 3.

(1) Interfacial Peel Strength: One side (side of the (meth) acrylic adhesive layer) of the pressure-sensitive adhesive films of Examples 1-5 and Comparative Example 1 was coated with a PET (polyethylene terephthalate) film , And the other side of the adhesive film (side of the (meth) acrylic adhesive layer) was adhered to a glass plate and cut into samples of a width x length (1.27 cm x 15 cm). A two-kilogram roller was passed once over the sample. After attachment, specimens were prepared at 30 minutes at 25 ° C. Using a TA.XT_Plus Texture Analyzer (Stable Micro System), a 180 ° peel force was measured at 25 ° C at a speed of 300 mm / min. In the case of Example 6, the side of the (meth) acrylic adhesive layer in the adhesive film was adhered to a glass plate, and the side of the silicone adhesive layer was adhered to a 50 탆 thick PET film treated twice with a dose of 78 dose, Were measured.

(2) Yellowing: The pressure-sensitive adhesive films of Examples and Comparative Examples were allowed to stand for 24 hours at 60 ° C / 90% relative humidity, and the yellowing was visually judged. It was evaluated as good when no yellowing occurred, and bad when yellowing occurred.

(3) Reliability: A glass plate, an adhesive film of Examples and Comparative Examples, and an ITO film were sequentially laminated to prepare specimens. The specimens were left at 60 ° C / 90% relative humidity for 500 hours. Whether lifting or peeling of the ITO film from the pressure-sensitive adhesive film or occurrence of bubbles was visually observed and evaluated as good when there was no bubble or peeling, and poor when bubbles or peeling occurred a lot.

(4) Rate of change in resistance: The pressure-sensitive adhesive films prepared in Examples and Comparative Examples were attached to a PET film, and silver paste was used to form electrodes on the other surface to which no PET film was attached. Thereafter, the initial resistance (P 1 ) was measured for the prepared sample. The sample was left at 60 캜 and 90% relative humidity for 240 hours and the resistance (P 2 ) was measured. At this time, the resistance was measured using a Checkman portable resistance / voltage / current measuring device (manufactured by Tae Kwang Electronics Co., Ltd.). Thereafter, the resistance value measured in each of the above conditions was substituted into the formula (4), and the rate of change in resistance was measured. It was evaluated as good when the rate of change of resistance was 5% or less, and was evaluated as poor when the rate of change was 5% or more.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Emulsifier
(Parts by weight) 0.5 0.5 One 2.5 5 0.5 - Whether MAVTS is included - include include include include include include Interface peel strength
(gf / in) 600
1050
1110 1132 1158 1,100 190 Yellow Good Good Good Good Good Good Good responsibility Good Good Good Good Good Good Bad Rate of change in resistance Good Good Good Good Good Good Good

As shown in Table 1, the adhesive film of this example had a high interface peel strength between the silicone adhesive layer and the (meth) acrylic adhesive layer, making it difficult to peel the silicone adhesive layer from the (meth) acrylic adhesive layer, And reliability. On the other hand, in Comparative Example 1 which did not contain an emulsifier, it was confirmed that peeling strength was low because of the low interface peel strength between the silicone adhesive layer and the (meth) acrylic adhesive layer, and the reliability was not good.

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 (14)

Sensitive adhesive layer comprising a silicone-based adhesive layer and a (meth) acrylic-based adhesive layer formed on one or both surfaces of the silicone-based adhesive layer,
Wherein the (meth) acrylic adhesive layer comprises an emulsifier,
Wherein an interface peel strength between the silicone adhesive layer and the (meth) acrylic adhesive layer is 600 gf / in to 5,000 gf / in. delete The composition of claim 1, wherein the emulsifier is selected from the group consisting of potassium soap, potassium stearate, salt of half ester of succinic acid of sulfosuccinic acid, sorbitan monopalmitate , Sorbitan monostearate, sorbitan tristearate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, and polyoxyethylene cetyl ether. The pressure-sensitive adhesive sheet according to claim 1, wherein the (meth) acrylic adhesive layer comprises a monomer mixture comprising a non-hydroxylated monomer having no hydroxyl group and (meth) acrylate having a hydroxyl group, an initiator, Layer composition,
Wherein the emulsifier is contained in an amount of 0.01 to 8 parts by weight based on 100 parts by weight of the monomer mixture. The adhesive film according to claim 4, wherein the non-hydroxyl group monomer having no hydroxyl group has a glass transition temperature (Tg) of the homopolymer of -150 캜 to -20 캜. 6. The pressure-sensitive adhesive film of claim 5, wherein the monomer mixture comprises from 60% to 95% by weight of the non-hydroxylated monomer, and from 5% to 40% by weight of the (meth) acrylate having the hydroxyl group. The adhesive sheet according to claim 1, wherein the silicone-
Silicone polymers; And
(Meth) acrylate group and a siloxane compound having a silicon-bonded vinyl (Si-vinyl) group. The composition of claim 7, wherein the siloxane compound comprises at least one of (meth) acryloxypropyltris (vinyldimethylsiloxy) silane and (3- (meth) acryloxypropyl) bis (vinyldimethylsiloxy) Lt; / RTI &gt; The pressure-sensitive adhesive film according to claim 7, wherein the siloxane compound is contained in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the silicone polymer. The pressure-sensitive adhesive film according to claim 1, wherein the thickness of the (meth) acrylic pressure-sensitive adhesive layer: the thickness of the silicone pressure-sensitive adhesive layer is 1: 0.5 to 1: The pressure-sensitive adhesive sheet according to claim 1, wherein the (meth) acrylic adhesive layer comprises a first (meth) acrylic adhesive layer and a second (meth)
Wherein the adhesive film is formed in the order of the first (meth) acrylic adhesive layer, the silicone adhesive layer, and the second (meth) acrylic adhesive layer,
The thickness of the first (meth) acrylic adhesive layer: the thickness of the second (meth) acrylic adhesive layer is 1: 0.5 to 1: 3. An optical member comprising the optical film and the adhesive film according to any one of claims 1 to 11 formed on at least one side of the optical film. The optical film according to claim 12, wherein the optical film is a polarizing plate, a color filter, a retardation film, an elliptically polarizing film, a reflective film, an antireflection film, a compensation film, , A plastic LCD substrate, and a conductive film. An optical display device comprising the pressure-sensitive adhesive film according to any one of claims 1 to 11.
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