KR101962999B1 - 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 PDFInfo
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- KR101962999B1 KR101962999B1 KR1020150178665A KR20150178665A KR101962999B1 KR 101962999 B1 KR101962999 B1 KR 101962999B1 KR 1020150178665 A KR1020150178665 A KR 1020150178665A KR 20150178665 A KR20150178665 A KR 20150178665A KR 101962999 B1 KR101962999 B1 KR 101962999B1
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- meth
- acrylate
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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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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- 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
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- C09J2205/11—
Abstract
(Meth) acrylate, an alkylene glycol unit-containing (meth) acrylate and an alkyl group-containing (meth) acrylate having an elongation of Formula 1 at 25 占 폚 of not less than 900%, a peel strength at 25 占 폚 of not less than 1000 gf / ) Acrylate, an optical member including the adhesive film, and an optical display device including the adhesive film.
Description
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. The transparent adhesive film may be laminated between two kinds of window films, conductive films, polarizing plates and organic light emitting devices.
In recent years, a flexible display device having flexibility that can be folded and unfolded in an optical display device has been developed. The flexible display device can be folded and unfolded, so that it can be manufactured in various forms, and is thin, light and strong against impact.
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, the folding property should be good.
The background art of the present invention is disclosed in Korean Patent Publication No. 2007-0055363.
A problem to be solved by the present invention is to provide an adhesive film excellent in elongation and peeling strength and excellent in restoring force.
Another problem to be solved by the present invention is to provide an adhesive film having good foldability, excellent optical transparency, and stably exhibiting viscoelasticity at a high temperature and a low temperature.
Another object of the present invention is to provide an optical member and an optical display device including the adhesive film.
The pressure-sensitive adhesive film of the present invention is characterized in that the elongation of the formula 1 at 25 ° C is 900% or more, the peel strength at 25 ° C is 1000 gf / in or more, and the content of the (meth) acrylate containing a hydroxyl group And a monomer mixture comprising an alkyl group-containing (meth) acrylate and an alkyl group-containing (meth) acrylate.
The pressure-sensitive adhesive film of the present invention is formed by a pressure-sensitive adhesive composition comprising a monomer mixture containing a hydroxyl group-containing (meth) acrylate, an alkylene glycol unit-containing (meth) acrylate and an alkyl group-containing (meth) acrylate, organic nanoparticles and an initiator .
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 an adhesive film excellent in elongation and peel strength and excellent in restoring force.
The present invention provides a pressure-sensitive adhesive film having good foldability, excellent optical transparency, and stable viscoelasticity at a high temperature and a low temperature.
The present invention provides an optical member and an optical display device including the pressure-sensitive adhesive film.
1 is a cross-sectional view of an optical display device according to an embodiment of the present invention.
2 is a cross-sectional view and a plan view of a specimen for measuring elongation and restoring force.
3 is a graph for calculation of the elongation and restitution force.
4 is a conceptual diagram of a specimen for peel strength measurement.
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" may mean acrylic and / or methacrylic.
As used herein, "copolymer" may include oligomers, polymers or resins.
2 (a) and 2 (b), the terms "elongation" and "restoring force" refer to the case where both end portions of a PET (polyethylene terephthalate) film (thickness: 75 μm) The end portions of the two PET films were adhered to each other by a pressure-sensitive adhesive film having a length and a length (20 mm x 20 mm), respectively, at the first end portion and the second end portion, And the second end, and the contact area between the PET film and the pressure sensitive adhesive film is measured as a test piece having a width and a length (20 mm x 20 mm). 2 (a), a jig is fixed to both end portions of a PET film not adhered to the specimen at 25 ° C, one jig is fixed, and the other jig is fixed at a speed of 300 mm / min (10 times X 3 of the initial thickness of the pressure-sensitive adhesive film) of 1000% of the thickness (initial thickness: X 0 , unit: 탆) of the pressure-sensitive adhesive film and then held for 10 seconds, The length of the adhesive film stretched when a force of 0 kPa is applied to the adhesive film restored to the speed (300 mm / min) is X 2 (unit: 탆). Referring to FIG. 3, a graph is obtained with the stretched length of the adhesive film as the X-axis and the force applied to the adhesive film as the Y-axis. When the length of the adhesive film stretched when a force of 90 kPa is applied to the adhesive film is X 1 (unit: 탆), the elongation is a value calculated by the following formula 1 and the restoring force is a value calculated by the following formula 2:
<Formula 1>
Elongation = (X 1 ) / (X 0 ) x 100
<Formula 2>
Restoring force = (1 - (X 2 ) / (X 3 )) x 100
At this time, the initial thickness of the adhesive film may be 20 탆 to 300 탆. Elongation and resilience can be measured with TA.XT_Plus Texture Analyzer (Stable Micro System). Elongation and restitution can be measured at 25 ° C respectively.
In the present specification, "folding condition" means that the adhesive film is placed between a corona-treated polyethylene terephthalate (PET) film (thickness: 125 μm) and a corona-treated PET film (thickness: 50 μm) (70 mm x 140 mm), and PET film / adhesive film / PET film specimens were used. The specimen was fixed to a flexural evaluation equipment (CFT-200, Covotech) using an adhesive (4965, Tesa), and the length (length: 140 mm) of the specimen was measured at room temperature And a cycle of 100,000 cycles was repeated by repeating bending at a rate of 30 cycles per minute (bending the adhesive film one time in half and setting it as one cycle). In the present specification, "good folding" means that there is no streaking or the like at the folding portion when the folding condition is applied, and there is no breakage, lifting, peeling, bubbling or the like of the adhesive film.
The "average particle diameter" of the organic nanoparticles in the present specification is the particle diameter of the organic nanoparticles expressed by the Z-average value measured by a Zetasizer nano-ZS instrument of Malvern in an aqueous or organic solvent.
Hereinafter, an adhesive film according to an embodiment of the present invention will be described.
The pressure-sensitive adhesive film according to an embodiment of the present invention may have an elongation at 25 ° C of 900% or more and a peel strength at 25 ° C of 1000 gf / in or more. In this range, the pressure-sensitive adhesive film can provide good adhesion between the adherends and good stress relaxation force, thereby providing good folding and being used in a flexible display device. Further, in the above range, the pressure-sensitive adhesive film can stably exhibit viscoelasticity at a high temperature (e.g., 80 DEG C) and a low temperature (e.g., -20 DEG C). Specifically, the pressure-sensitive adhesive film may have a elongation of 900% to 1300% at 25 ° C. Specifically, the pressure-sensitive adhesive film has a peel strength of 1000 gf / in to 5000 gf / in, specifically 1200 gf / in to 4000 gf / in, more specifically 1300 gf / in at 25 캜 for a corona- To 3000 gf / in. In the above range, the adhesive film has good adhesion to the adherend at 25 DEG C, and can be bonded to various devices of the flexible device, and the reliability can be excellent. The pressure-sensitive adhesive film may have a modulus of 10 kPa to 500 kPa at 80 ° C, specifically 10 kPa to 30 kPa, and a modulus of 10 kPa to 1000 kPa, specifically 50 kPa to 100 kPa at -20 ° C. Within this range, it is possible to have an excellent folding property at a low temperature and a high temperature and to prevent the adhesive film from being broken.
The adhesive film 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 may be 20 占 퐉 to 300 占 퐉, specifically 30 占 퐉 to 150 占 퐉. In the above range, it can be used in an optical display device. The adhesive film may have a restoring force of 40% or more, specifically 40% to 98% at 25 ° C. In the above range, it has a viscoelastic recovery property and may have an excellent effect of folding.
The adhesive film comprises a pressure-sensitive adhesive composition comprising a monomer mixture comprising an hydroxyl group-containing (meth) acrylate (a1), an alkylene glycol unit-containing (meth) acrylate (a2) and an alkyl group-containing (meth) And the pressure-sensitive adhesive composition may further comprise organic nanoparticles. The adhesive film can be produced by a conventional method. For example, the pressure-sensitive adhesive composition may be coated on a release film and cured. Curing may include irradiation of the irradiation dose 400mJ / cm 2 to 3000mJ / cm 2 at a wavelength of 300nm to 400nm into a low-pressure lamp in an oxygen-free state.
Hereinafter, a pressure-sensitive adhesive composition according to an embodiment of the present invention will be described.
The pressure-sensitive adhesive composition according to one embodiment of the present invention is a pressure-sensitive adhesive composition comprising a monomer (a2) containing a hydroxyl group-containing (meth) acrylate (a1), an alkylene glycol unit- (meth) Mixtures and initiators.
The monomer mixture comprising the hydroxyl group-containing (meth) acrylate (a1), the alkylene glycol unit-containing (meth) acrylate (a2) and the alkyl group-containing (meth) acrylate (a3) (-OH), an alkylene glycol unit and an alkyl group-containing (meth) acrylic copolymer. The glass transition temperature (Tg) of the hydroxyl group, alkylene glycol unit and alkyl group-containing (meth) acrylic copolymer may be -150 ° C to -13 ° C, specifically -100 ° C to -20 ° C. In the above range, the pressure-sensitive adhesive film has the above elongation and peel strength, and may have an excellent effect of folding. (A1), the alkylene glycol unit-containing (meth) acrylate (a2) and the alkyl group-containing (meth) acrylate (a3) are different from each other.
The hydroxyl group-containing (meth) acrylate (a1) can form a matrix of the adhesive film by cross-linking the copolymer and can realize an excellent effect of folding with good adhesion. The hydroxyl group-containing (meth) acrylate (a1) may be a (meth) acrylate containing at least one hydroxyl group. For example, the hydroxyl group-containing (meth) acrylate (a1) may be at least one selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Cyclohexanedimethanol mono (meth) acrylate, 1-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (Meth) acrylate, 1,6-hexanediol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, neopentyl glycol mono Acrylate, trimethylolethane di (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4-hydroxycyclopentyl (meth) 4-hydroxycyclohexyl (meth) acrylate, ) Acrylate, and cyclohexanedimethanol mono (meth) acrylate. These may be used alone or in combination of two or more. In this case, the productivity of the adhesive film is improved, and the adhesive force of the adhesive film can be further improved. The hydroxyl group-containing (meth) acrylate (a1) is used in an amount of 4 wt% to 40 wt%, for example 5 wt% to 45 wt%, 10 wt% to 30 wt%, 15 wt% to 30 wt% By weight to 20% by weight. The adhesive strength and endurance reliability of the adhesive film can be further improved in the above range.
The alkylene glycol unit-containing (meth) acrylate (a2) can increase the elongation of the adhesive film and provide good folding, making the adhesive film usable in a flexible display device. The (meth) acrylate (a2) containing an alkylene glycol unit contains a plurality of alkylene glycol units, thereby making the (meth) acrylic copolymer flexible, thereby further increasing the elongation of the adhesive film. The "plurality of alkylene glycol units" includes not only a plurality of alkylene glycol units of the same kind but also two or more, for example, a plurality of alkylene glycol units, as well as a plurality of different alkylene glycol units. Specifically, the alkylene glycol unit-containing (meth) acrylate (a2) may contain 3 mol% or more, more specifically 3 mol% to 13 mol%, of the alkylene glycol unit. Within the above range, the elongation of the pressure-sensitive adhesive film can be improved, and the folding can have an excellent effect. The above-mentioned "alkylene glycol unit" is an alkylene glycol unit having 2 to 5 carbon atoms such as an ethylene glycol group (-CH 2 CH 2 O-), a propylene glycol group (-CH 2 CH 2 CH 2 O-, -CH 2 CH (CH 3) O- or -CH (CH 3) CH 2 O- ), or butylene glycol group (-CH 2 CH 2 CH 2 CH 2 O-, -CH 2 CH 2 CH (CH 3) O - or -CH (CH 3) may represent a CH 2 CH 2 O-). Specifically, the alkylene glycol unit-containing (meth) acrylate (a2) may include at least one of (meth) acrylate containing at least one of an ethylene glycol unit and a propylene glycol unit, (Meth) acrylate. The (meth) acrylate (a2) containing an alkylene glycol unit may be a monofunctional (meth) acrylate. Therefore, the (meth) acrylate (a2) containing an alkylene glycol unit can realize an excellent effect of folding the adhesive film. The alkylene glycol unit-containing (meth) acrylate (a2) may contain C1 to C5 alkoxy groups such as a methoxy group and an ethoxy group at the terminal.
The (meth) acrylate (a21) containing an ethylene glycol unit may contain at least one (meth) acrylate containing at least two ethylene glycol units. For example, the (meth) acrylate (a21) containing ethylene glycol units may be selected from the group consisting of polyethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide monoethyl ether (meth) acrylate, polyethylene oxide monopropyl ether (Meth) acrylate, polyethylene oxide monobutyl ether (meth) acrylate, polyethylene oxide monoisobutyl ether (meth) acrylate, polyethylene oxide mono butyl ether (meth) acrylate, polyethylene oxide monopentyl (Meth) acrylate such as ethylene oxide (meth) acrylate, polyethylene oxide dimethylether (meth) acrylate, polyethylene oxide diethylether (meth) acrylate and the like. It is not. These may be used alone or in combination of two or more. The propylene glycol unit-containing (meth) acrylate (a22) is preferably selected from the group consisting of polypropylene oxide monomethyl ether (meth) acrylate, polypropylene oxide monoethyl ether (meth) acrylate, polypropylene oxide monopropyl ether (Meth) acrylate, propylene oxide monoisopropyl ether (meth) acrylate, polypropylene oxide monobutyl ether (meth) acrylate, polypropylene oxide monoisobutyl ether (meth) (Meth) acrylate such as polypropylene oxide monopentyl ether (meth) acrylate, polypropylene oxide dimethyl ether (meth) acrylate, and polypropylene oxide diethyl ether (meth) However, it is not limited to is. These may be used alone or in combination of two or more.
The alkylene glycol unit-containing (meth) acrylate (a2) may be contained in the monomer mixture in an amount of 0.1 wt% to 5 wt%, for example, 1 wt% to 5 wt%, and 1 wt% to 3 wt%. In the above range, the adhesive film can secure the elongation and peel strength.
The alkyl group-containing (meth) acrylate (a3) can form a matrix of an adhesive film. Specifically, the alkyl group-containing (meth) acrylate (a3) may include unsubstituted linear or branched alkyl group-containing (meth) acrylic acid esters having 1 to 20 carbon atoms or alicyclic or aromatic (meth) acrylic acid esters. For example, the alkyl group-containing (meth) acrylate (a3) may be at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Acrylate, isobutyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, Acrylates such as octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, isobornyl acrylate, tricyclodecane And tricyclodecane dimethanol di (meth) acrylate. More specifically, the alkyl group-containing (meth) acrylate (a3) may be a (meth) acrylic acid ester having an alkyl group having 4 to 8 carbon atoms, and may further increase the initial adhesion of the pressure-sensitive adhesive film. Specifically, the use of a (meth) acrylate having a branched alkyl group may further enhance the initial adhesion. The alkyl group-containing (meth) acrylate (a3) may be included in the monomer mixture in an amount of 55% by weight to 95% by weight, for example, 75% by weight to 90% by weight and 60% by weight to 80% by weight. The adhesive strength and endurance reliability of the adhesive film can be further improved in the above range.
A monomer mixture comprising a hydroxyl group containing (meth) acrylate (a1), an alkylene glycol unit containing (meth) acrylate (a2) and an alkyl group containing (meth) acrylate (a3) . More preferably, the comonomer having a glass transition temperature of -150 ° C to 0 ° C is preferred. In this case, the glass transition temperature of the (meth) acrylic copolymer formed from the monomer mixture can be lowered, and excellent adhesion can be maintained even at a low temperature (-20 캜), and a similar storage at a high temperature (80 캜) Modulus value.
(A44) having an amine group, a monomer (a42) having an amide group, a monomer (a43) having an alkoxy group, a monomer (a44) having a phosphoric acid group, a monomer (a45) having a sulfonic acid group, a monomer having a phenyl group a46) and a silane group-containing monomer (a47).
The monomer (a41) having an amine group may be at least one selected from the group consisting of monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, monoethylaminopropyl (meth) (Meth) acrylates such as aminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, N-tert-butylaminoethyl (meth) acrylate and methacryloxyethyltrimethylammonium chloride ) Acrylic monomer, but is not necessarily limited thereto.
The monomer (a42) having an amide group may be at least one monomer selected from the group consisting of (meth) acrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (Meth) acryl-based monomer such as N-methylene bis (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, dimethyl (meth) acrylamide, diethyl But it is not necessarily limited thereto.
The monomer (a43) having an alkoxy group is a non-alkylene glycol system free of an alkylene glycol unit, and examples thereof include 2-methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, Acrylate, 2-methoxypentyl (meth) acrylate, 2-ethoxypentyl (meth) acrylate, 2-butoxyhexyl (meth) acrylate, , 3-methoxypentyl (meth) acrylate, 3-ethoxypentyl (meth) acrylate, and 3-butoxyhexyl (meth) acrylate.
The monomer (a44) having a phosphoric acid group is preferably selected from the group consisting of 2- (meth) acryloyloxyethyldiphenyl phosphate (meth) acrylate, tri (meth) acryloyloxyethyl phosphate (meth) acrylate, tri (Meth) acrylate, and the like, but the present invention is not limited thereto.
The monomer (a45) having a sulfonic acid group is preferably an acrylic monomer having a sulfonic acid group such as sodium sulfopropyl (meth) acrylate, sodium 2-sulfoethyl (meth) acrylate and sodium 2-acrylamido- But are not necessarily limited to, monomers.
The monomer (a46) having a phenyl group can be an acrylic vinyl monomer having a phenyl group such as p-tert-butylphenyl (meth) acrylate, o-biphenyl (meth) acrylate and phenoxyethyl (meth) But it is not necessarily limited thereto.
The monomer (a47) 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, vinyltriacetoxysilane Methacryloyloxypropyltrimethoxysilane, and the like, but is not limited thereto.
The monomer having a glass transition temperature of -150 DEG C to 0 DEG C in the comonomer, particularly the homopolymer, may be contained in the monomer mixture in an amount of 30 wt% or less, specifically 0 wt% to 20 wt%. Within this range, an effect of excellent viscoelasticity at low temperature may be obtained.
The monomer mixture may further comprise a monomer having a carboxylic acid group. The monomer having a carboxylic acid group may be at least one monomer selected from the group consisting of (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, itaconic acid, Maleic anhydride, and the like, but are not necessarily limited thereto. The monomer having a carboxylic acid group may be contained in an amount of not more than 10% by weight, specifically not more than 3% by weight, more specifically not more than 1% by weight in the monomer mixture. In the above range, the pressure-sensitive adhesive composition can further improve the adhesive strength and durability of the pressure-sensitive adhesive film.
In one embodiment, the monomer mixture comprising a hydroxyl group-containing (meth) acrylate (a1), an alkylene glycol unit containing (meth) acrylate (a2) and an alkyl group-containing (meth) acrylate (a3) ) Acrylate (a1) in an amount of 4 to 40% by weight, specifically 5 to 20% by weight, an alkylene glycol unit (a2) in an amount of 0.1 to 5% by weight, specifically 1 to 5% (Meth) acrylate (a3) in an amount of from 55% by weight to 95% by weight, and more specifically from 75% by weight to 90% by weight. Within this range, there can be an excellent effect of folding along a high elongation.
(Meth) acrylate (a2), an alkyl group-containing (meth) acrylate (a3) and a macromonomer in a ratio of . Is the same as the pressure-sensitive adhesive composition according to one embodiment of the present invention, except that a macromonomer is further included. The macromonomer can further exert an excellent effect of adhesion on the adhesive film as the cohesive force improves.
The macromonomer has a functional group which can be cured by an active energy ray, and the macromonomer is a compound having a functional group curable by an active energy ray, and the (meth) acrylate (a1), the alkylene glycol unit (meth) acrylate Can be polymerized with one or more.
The macromonomer may be represented by the following formula:
≪ Formula 1 >
(In Formula 1, R 1 is hydrogen or a methyl group, X represents a single bond or a divalent coupler, Y is methyl (meth) acrylate, ethyl (meth) acrylate, n- butyl (meth) acrylate, iso- butyl (Meth) acrylate, t-butyl (meth) acrylate, styrene, and (meth) acrylonitrile.
2 the coupler is an arylene group, -NR a C1 to C10 alkyl groups, C7 to C13 aryl alkyl group, C6 to C12 2 - (wherein, R 2 is an alkyl group of hydrogen, or a C1 to C5), COO-, - O-, -S-, -SO 2 NH-, -NHSO 2 -, may be a group derived from -NHCOO-, -OCONH, or heterocyclic.
The macromonomer may have a number average molecular weight of 2,000 to 20,000, specifically 2,000 to 10,000, more specifically 4,000 to 8,000. Within the above range, sufficient adhesive strength can be obtained, heat resistance is excellent, and deterioration of workability due to an increase in viscosity of the pressure-sensitive adhesive composition can be suppressed. The macromonomer may have a glass transition temperature of from 40 캜 to 150 캜, specifically from 60 캜 to 140 캜, more specifically from 80 캜 to 130 캜. In the above range, the pressure-sensitive adhesive film can exhibit sufficient cohesive strength, and the degree of stickiness and deterioration of the adhesive force can be suppressed. More specifically, the divalent linking group represented by X in the formula (1) may be represented by the following formulas (1a) to (1d):
<Formula 1a>
≪ EMI ID =
≪ Formula 1c >
<Formula 1d>
(In the above Chemical Formulas (1a) to (1d), * denotes the connecting site of the element)
Commercial macromonomers may be used. For example, the terminal is a methacryloyl group; And a macromonomer having a Y segment of methyl methacrylate, a macromonomer having a Y segment of styrene, a macromonomer having a Y segment of styrene / acrylonitrile, and a macromonomer having a Y segment of butyl acrylate. The macromonomer may be contained in an amount of 0.1 to 20% by weight, specifically 0.5 to 10% by weight in the adhesive film. Within the above range, the viscoelasticity of the pressure-sensitive adhesive film can be balanced with the modulus and the restoring force, and the peeling force is increased.
In one embodiment, a monomer mixture comprising a hydroxyl group containing (meth) acrylate (a1), an alkylene glycol unit containing (meth) acrylate (a2), an alkyl group containing (meth) acrylate (a3) Containing (meth) acrylate (meth) acrylate (a1), the alkylene glycol unit containing (meth) acrylate (a2), the alkyl group containing (meth) (a2) 0.1 wt% to 5 wt%, specifically 1 wt% to 5 wt% of an alkylene glycol unit (meth) acrylate (a2), 4 wt% to 40 wt%, specifically 5 wt% to 20 wt% From 55% by weight to 95% by weight, specifically from 75% by weight to 90% by weight, of the (meth) acrylate (a3), from 0.1% by weight to 20% by weight, specifically from 0.5% by weight to 10% by weight of the macromonomer. Within this range, there may be an excellent effect of folding performance at a high temperature (60 DEG C).
The initiator may cure the (meth) acrylic copolymer formed from the monomer mixture. As the initiator, a photopolymerization initiator or a thermal polymerization initiator can be used. The initiator may be the same as or different from the initiator used in preparing the partially polymerized prepolymer. The photopolymerization initiator may be any as long as it can induce polymerization reaction of the radical polymerizing compound described above during the curing process by photoirradiation to realize the second crosslinking structure. For example, benzoin, acetophenone, hydroxy ketone, amino ketone or phosphine oxide photoinitiators can be used. Specific examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzo Benzoin isobutyl ether, acetophenone, dimethyl anino acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenyl Methyl-1- [4- (methylthio) phenyl] -2-morpholino-acetamide, acetophenone, 2-hydroxy- Propane) ketone, benzophenone, p-phenylbenzophenone, 4,4-non-cydiethylaminobenzophenone, dichloro (2-hydroxypropyl) Benzoquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, 2-amino anthraquinone, thioxanthone, 2-ethyl thioxanthone, 2- , 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoic acid ester, oligo [2-hydroxy- (1-methylvinyl) phenyl] propanone] and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. In the present application, one kind or more kinds of the above can be used, but the present invention is not limited thereto. The type of the thermal polymerization initiator is not particularly limited as long as it can induce polymerization reaction of the polymerizable compound and can realize the second crosslinking structure, and examples thereof include an azo compound, a peroxide compound or a redox compound Conventional initiators such as compounds may be used. Examples of the azo compound include 2,2-azobis (2-methylbutyronitrile), 2,2-triyl azo bis (isobutyronitrile), 2,2-triazabis 2-methyl azo bis (2-methylpropionate) and 2,2-phylazobis (4- (4-methoxyphenyl) Methoxy-2,4-dimethylvaleronitrile), and the like, and examples of the peroxide compound include inorganic peroxides such as potassium persulfate, ammonium persulfate or hydrogen peroxide; Or peroxydicarbonate, peroxydicarbonate, peroxy ester, tetramethyl butyl peroxyneodecanoate, bis (4-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxycarbonate, Hexyl peroxy dicarbonate, dimethoxy butyl peroxy dicarbonate, hexyl peroxy dicarbonate, hexyl peroxy dicarbonate, diisopropyl peroxy dicarbonate, diethoxy ethyl peroxy dicarbonate, diethoxyhexyl peroxy dicarbonate, , Bis (3-methoxy-3-methoxybutyl) peroxy dicarbonate, dibutyl peroxy dicarbonate, dicetyl peroxy dicarbonate, dimyristyl peroxy dicarbonate, 1,1 , 3,3-tetramethylbutyl peroxypivalate, hexyl peroxypivalate, butyl peroxypivalate, trimethylhexanoyl peroxide, dimethylhydroxybutyl peroxy Amyl peroxyneodecanoate, t-butyl peroxyneoheptanoate, amyl peroxy pivalate, t-butyl peroxy pivalate, t-amyl peroxide, Organic peroxides such as peroxy-2-ethylhexanoate, lauryl peroxide, dilauroyl peroxide, didecanoyl peroxide, benzoyl peroxide or dibenzoyl peroxide, Examples of the system compound include, but are not limited to, a mixture of a peroxide compound and a reducing agent in combination. In the present application, one kind or a mixture of two or more kinds of azo type, peroxide type or redox type compound as described above can be used. The initiator may be included in an amount of 0.01 to 5 parts by weight, specifically 0.05 to 3 parts by weight, more specifically 0.1 to 1 part by weight, based on 100 parts by weight of the monomer mixture for forming the (meth) acrylic copolymer have. In the above range, the curing reaction can be completely carried out, and the remaining amount of the initiator remains, the permeability can be prevented from being lowered, the bubble generation can be lowered, and the reactivity can be improved.
The pressure-sensitive adhesive composition may further include a crosslinking agent. The cross-linking agent can increase the degree of crosslinking of the pressure-sensitive adhesive composition and increase the mechanical strength of the pressure-sensitive adhesive film. 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 Neopentylglycol adipate di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di Acrylate, di (meth) acryloxyethyl isocyanurate, allyl cyclohexyl di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, dimethylol dicyclopentanedi (meth) Ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, neopentyl glycol modified trimethylpropane di (meth) acrylate, Bifunctional acrylates such as adamantane di (meth) acrylate or 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene; (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. The crosslinking agent may be contained in an amount of 0.01 to 10 parts by weight, specifically 0.03 to 7 parts by weight, specifically 0.1 to 5 parts by weight, based on 100 parts by weight of the monomer mixture for forming the (meth) acrylic copolymer There is an effect of excellent adhesion and reliability in the above range.
The pressure-sensitive adhesive composition may further include a silane coupling agent. As the silane coupling agent, those conventionally known to those skilled in the art can be used. For example, there can be mentioned 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl tri A silicon compound having an epoxy structure such as methoxysilane; 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. Preferably, a silane coupling agent having an epoxy structure can be used. The silane coupling agent may be contained in an amount of 0.01 part by weight to 0.1 part by weight, specifically 0.05 part by weight to 0.1 part by weight, based on 100 parts by weight of the monomer mixture for forming the (meth) acrylic copolymer. There is an effect of increasing the reliability in the above range.
The pressure-sensitive adhesive composition may optionally contain a curing accelerator, an ionic liquid, a lithium salt, an inorganic filler, a softener, a molecular weight modifier, an antioxidant, an antioxidant, a stabilizer, a tackifier resin, a modifying resin (polyol resin, phenol resin, (Coloring pigments, extender pigments, etc.), treating agents, ultraviolet light blocking agents, fluorescent whitening agents, dispersing agents, heat stabilizers, antioxidants, antioxidants, A light stabilizer, an ultraviolet absorber, an antistatic agent, a coagulant, a lubricant and a solvent. The pressure-sensitive adhesive composition may have a viscosity at 25 DEG C of from 300 cPs to 50,000 cPs, and excellent coating properties and thickness uniformity within the above range may be obtained.
Hereinafter, a pressure-sensitive adhesive composition according to another embodiment of the present invention will be described.
The pressure-sensitive adhesive composition according to another embodiment of the present invention is a pressure-sensitive adhesive composition comprising a monomer (a2) containing a hydroxyl group-containing (meth) acrylate (a1), an alkylene glycol unit- Mixtures, initiators and organic nanoparticles. Is substantially the same as the pressure-sensitive adhesive composition according to one embodiment of the present invention, except that it further comprises organic nanoparticles. Hereinafter, the organic nanoparticles will be described.
The organic nanoparticles have good foldability at room temperature and high temperature of the adhesive film, have excellent low temperature and / or room temperature viscoelasticity of the adhesive film, have a crosslinked structure, and stably exhibit high temperature viscoelasticity of the adhesive film. (Meth) acryl-based copolymer formed from the monomer mixture, for example, the refractive index difference between the hydroxyl group, the alkylene glycol unit and the alkyl group-containing (meth) acrylic copolymer and the nanoparticle containing the alkyl group By adjusting, the adhesive film can have excellent transparency even though it contains nanoparticles.
The organic nanoparticles may have an average particle diameter of 10 nm to 400 nm, specifically 10 nm to 300 nm, more specifically 10 nm to 200 nm, more specifically 50 nm to 150 nm. Within this range, aggregation of the organic nanoparticles can be prevented, the folding of the adhesive film is not affected, and the transparency of the adhesive film can be good. The organic nanoparticles have a refractive index difference of 0.05 or less, specifically 0 or more and 0.03 or less, with respect to the (meth) acrylic copolymer formed from the monomer mixture, for example, a hydroxyl group, an alkylene glycol unit and an alkyl group- 0.0 > 0.0 < / RTI > In the above range, the transparency of the adhesive film can be excellent. The refractive index of the organic nanoparticles may be 1.40 to 1.70, specifically 1.45 to 1.60. Within the above range, the transparency of the adhesive film may be excellent.
The organic nanoparticles are core-shell type organic nanoparticles, and the core and the shell can satisfy the following formula 3: When the particle type as described above is used, the folding property of the pressure-sensitive adhesive film is good and it is effective for balance and physical properties of elasticity and flexibility Can be.
<Formula 3>
Tg (c) < Tg (s)
(Unit: 占 폚), and Tg (s) is the glass transition temperature (unit: 占 폚) of the shell.
As used herein, the term "shell" means the outermost layer of the organic nanoparticles. The core may be a single spherical particle. However, the core may further comprise additional layers surrounding the spherical particles if they have the above glass transition temperature.
Specifically, 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. Within this range, there may be a low temperature and / or room temperature viscoelastic effect of the adhesive film. The core may include at least one of polyalkyl (meth) acrylate or polysiloxane having the above glass transition temperature.
The polyalkyl (meth) acrylate may be at least one selected from the group consisting of polymethyl acrylate, polyethylacrylate, polypropyl acrylate, polybutyl acrylate, polyisopropyl acrylate, polyhexyl acrylate, polyhexyl methacrylate, polyethylhexyl acrylate And polyethylhexyl methacrylate, polysiloxane, and is not necessarily limited thereto.
The polysiloxane can be, for example, an organosiloxane (co) polymer. The organosiloxane (co) polymer may be one which is not cross-linked, or a cross-linked (co) polymer may be used. In order to impart impact resistance and colorability, an organosiloxane (co) polymer in a crosslinked state can be used. It is a crosslinked form of organosiloxane, specifically crosslinked dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane or a mixture of two or more thereof. By using a copolymerized form of two or more organosiloxanes, the refractive index can be adjusted from 1.41 to 1.50.
The crosslinking state of the organosiloxane (co) polymer can be determined by the degree of dissolution by various organic solvents. As the crosslinking state deepens, the degree of dissolution by the solvent becomes smaller. As the solvent for determining the crosslinking state, acetone, toluene and the like can be used. Specifically, the organosiloxane (co) polymer may have a portion which is not dissolved by acetone or toluene. The insoluble matter to the toluene of the organosiloxane copolymer may be 30% or more.
Additionally, the organosiloxane (co) polymer may further comprise an alkyl acrylate crosspolymer. The alkyl acrylate crosslinked polymer may be selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. For example, n-butyl acrylate or 2-ethylhexyl acrylate having a low glass transition temperature may be used.
Specifically, 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. In the above range, the dispersibility of the organic nanoparticles in the (meth) acrylic copolymer may be excellent. The shell may comprise a polyalkyl methacrylate having said glass transition temperature. For example, it is possible to use polymethylmethacrylate (PMMA), polyethylmethacrylate, polypropylmethacrylate, polybutylmethacrylate, polyisopropylmethacrylate, polyisobutylmethacrylate and polycyclohexylmethacrylate Rate, < / RTI > but is not necessarily limited thereto.
The core may comprise from 30 wt% to 99 wt%, specifically from 40 wt% to 95 wt%, and more specifically from 50 wt% to 90 wt%, of the organic nanoparticles. Within the above range, the folding property of the pressure-sensitive adhesive film may be good in a wide temperature range. The shell may comprise from 1 wt% to 70 wt%, specifically from 5 wt% to 60 wt%, more specifically from 10 wt% to 50 wt%, of the organic nanoparticles. Within the above range, the folding property of the pressure-sensitive adhesive film may be good in a wide temperature range.
The organic nanoparticles may be contained in an amount of 0.1 part by weight to 20 parts by weight, specifically 0.1 part by weight to 1 part by weight, based on 100 parts by weight of the monomer mixture for forming the (meth) acrylic copolymer. Within this range, there is an excellent effect of folding at a high temperature (60 DEG C), and a balance between the viscoelasticity, the modulus and the recovery force of the pressure-sensitive adhesive film can be achieved.
Organic nanoparticles can be prepared by an emulsion polymerization method.
Hereinafter, a method for producing a pressure-sensitive adhesive composition according to an embodiment of the present invention will be described.
The pressure-sensitive adhesive composition is prepared by mixing a monomer mixture containing the above-mentioned monomer mixture such as a hydroxyl group-containing (meth) acrylate (a1), an alkylene glycol unit containing (meth) acrylate (a2) and an alkyl group-containing (meth) (Meth) acrylic copolymer (prepolymer) containing a hydroxyl group, an alkylene glycol unit and an alkyl group, and a monomer mixture which is not polymerized, and then an initiator and / or an organic nanoparticle is incorporated into the pressure- Can be produced. A crosslinking agent, a silane coupling agent, an additive, and the like may be further included. (Meth) acrylate (a1), an alkylene glycol unit (meth) acrylate (a2) and an alkyl group-containing (meth) acrylate (a3) (Meth) acrylic copolymer (prepolymer) containing an alkylene glycol unit and an alkyl group, and a monomer mixture which is not polymerized is prepared by partially polymerizing a mixture containing a monomer mixture containing a monomer mixture and an organic nanoparticle After that, a pressure-sensitive adhesive composition may be prepared by incorporating an initiator. A crosslinking agent, a silane coupling agent, an additive, and the like may be further included. Partial polymerization may include solution polymerization, suspension polymerization, photopolymerization, bulk polymerization, or emulsion polymerization. Specifically, the solution polymerization can be carried out at 50 DEG C to 100 DEG C by adding an initiator to the monomer mixture. The initiator may be an acetophenone radical photopolymerization initiator including 2,2-dimethoxy-2-phenylacetophenone and the like. The partial polymerization can be polymerized at 25 DEG C with a viscosity of 1,000 to 10,000 cPs, specifically a viscosity of 2,000 to 9,000 cPs.
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. However, the optical member can also be used in non-flexible display devices.
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, a transparent conductive film containing any one of indium tin oxide (FTO), fluorinated tin oxide (FTO), aluminum doped zinc oxide (AZO), carbon nanotube (CNT), and nanowire. 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.
The optical display device of the present invention may include the pressure-sensitive adhesive film of the present invention. The optical display device may include an organic light emitting diode display, a liquid crystal display, and the like. The optical display device may include a flexible display device. However, the optical display device may include a non-flexible display device.
Hereinafter, a flexible display device according to an embodiment of the present invention will be described with reference to FIG. 1 is a cross-sectional view of a flexible display device according to an embodiment of the present invention.
1, a
The
The
The
The
1, an adhesive layer is further formed between the
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 should be understood, however, that the same is by way of illustration and example only and is not to be construed in any way as limiting the invention.
Manufacturing example
Organic nanoparticles were prepared by emulsion polymerization. The core is polybutyl acrylate, the shell is polymethyl methacrylate, the shell is 35 weight% of the organic nanoparticles, the core is 65 weight% of the organic nanoparticles, the average particle diameter is 100 nm and the refractive index is 1.48 .
Example One
, 15 parts by weight of 4-hydroxybutyl acrylate (4-HBA), 83 parts by weight of 2-ethylhexyl acrylate (2-EHA), MTG-A (ethylene glycol unit containing 3 mol% , Kyoeisha Chemical), and 0.03 part by weight of Irgacure 651 (2,2-dimethoxy-2-phenylacetophenone, BASF) as an initiator were mixed well in the reactor. (Meth) acrylic copolymer (prepolymer) containing an alkylene glycol unit and an alkyl group, and a polymerizable (meth) acrylic copolymer (a prepolymer) by partially polymerizing the mixture by irradiating ultraviolet rays for a few minutes after exchanging dissolved oxygen in the reactor with a nitrogen gas. A viscous liquid (viscosity: 4000 cps) consisting of a mixture of monomers was prepared. 0.5 part by weight of Irgacure 184 (1-hydroxycyclohexyl phenyl ketone, BASF) as an initiator was added to the viscous liquid and mixed to prepare a pressure-sensitive adhesive composition.
(50 mW / cm < 2 >, wavelength: 350 nm, manufactured by Sankyo Co., Ltd.) for 6 minutes on both sides of a release film of 75 mu m in thickness was coated on a PET (polyethylene terephthalate) To obtain a transparent pressure-sensitive adhesive sheet.
Example 2
Except that 2 parts by weight of AM-90G (ethylene glycol unit: 9 mol%, Shin-Nakamura Chemical) serving as an ethylene glycol unit (meth) acrylate was used instead of 2 parts by weight of MTG-A in Example 1 Sheet.
Example 3
Except that 2 parts by weight of AM-130G (ethylene glycol unit: 13 mol%, Shin-Nakamura Chemical) which is an ethylene glycol unit-containing (meth) acrylate was used instead of 2 parts by weight of MTG-A in Example 1 Sheet.
Example 4
100 parts by weight of a monomer mixture comprising 15 parts by weight of 4-HBA, 83 parts by weight of 2-EHA and 2 parts by weight of MTG-A, 0.03 parts by weight of Irgacure 651 and 0.5 parts by weight of organic nanoparticles of Preparation Example were mixed well in a reactor. After the dissolved oxygen in the reactor is replaced with a nitrogen gas, the mixture is partially polymerized by irradiation with ultraviolet light for a few minutes using a low-pressure mercury lamp to obtain a mixture of a hydroxyl group, an alkylene glycol unit and an alkyl group-containing (meth) acrylic copolymer (prepolymer) A viscous liquid (viscosity: 4000 cps) consisting of particles and a mixture of un polymerized monomers was prepared. 0.5 part by weight of initiator Irgacure 184 was added to the viscous liquid and mixed to prepare a pressure-sensitive adhesive composition. A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 using the pressure-sensitive adhesive composition.
Example 5 - Example 6
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 4 except that the type and content of the alkylene glycol unit-containing (meth) acrylate were changed as shown in Table 1 instead of 2 parts by weight of MTG-A.
Example 7
100 parts by weight of a monomer mixture comprising 10 parts by weight of 4-HBA, 88 parts by weight of 2-EHA, 1 part by weight of MTG-A and 1 part by weight of a macromonomer AA-6 (Toagosei) and 0.03 parts by weight of Irgacure 651 . (Meth) acrylic copolymer (prepolymer) containing an alkylene glycol unit and an alkyl group, and a polymerizable (meth) acrylic copolymer (a prepolymer) by partially polymerizing the mixture by irradiating ultraviolet rays for a few minutes after exchanging dissolved oxygen in the reactor with a nitrogen gas. A viscous liquid (viscosity: 4000 cps) consisting of a mixture of monomers was prepared. 0.5 part by weight of initiator Irgacure 184 was added to the viscous liquid and mixed to prepare a pressure-sensitive adhesive composition. A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 using the pressure-sensitive adhesive composition.
Example 8
100 parts by weight of a monomer mixture comprising 10 parts by weight of 4-HBA, 88 parts by weight of 2-EHA, 1 part by weight of MTG-A and 1 part by weight of AA-6, 0.03 parts by weight of Irgacure 651, and 0.5 parts by weight of organic nano- Lt; / RTI > After the dissolved oxygen in the reactor is replaced with a nitrogen gas, the mixture is partially polymerized by irradiation with ultraviolet light for a few minutes using a low-pressure mercury lamp to obtain a mixture of a hydroxyl group, an alkylene glycol unit and an alkyl group-containing (meth) acrylic copolymer (prepolymer) A viscous liquid (viscosity: 4000 cps) consisting of particles and a mixture of un polymerized monomers was prepared. 0.5 parts by weight of Irgacure 184 was added to the viscous liquid and mixed to prepare a pressure-sensitive adhesive composition. A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 using the pressure-sensitive adhesive composition.
Comparative Example One
A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the content of each component was changed as shown in Table 1 below.
The properties of the pressure-sensitive adhesive sheet prepared in Examples and Comparative Examples were evaluated in the following Table 1, and the results are shown in Table 1 below.
(1) Elongation and restoring force: Release films were released on the pressure-sensitive adhesive sheets of Examples and Comparative Examples to obtain an adhesive film. The elongation and restitution were evaluated by TA.XT_Plus Texture Analyzer (Stable Micro System) at 25 ° C.
2 (a) and 2 (b), when both end portions of a PET (polyethylene terephthalate) film (thickness: 75 μm) of width × length (50 mm × 20 mm) are respectively referred to as a first end portion and a second end portion (20 mm x 20 mm) in the order of the first end portion of the PET film / the second end portion of the PET film and the second end portion of the PET film, and the PET film (20 mm x 20 mm) between the adhesive film and the adhesive film. 2 (a), a jig is fixed to both end portions of a PET film not adhered to the specimen at 25 ° C, one jig is fixed, and the other jig is fixed at a speed of 300 mm / min (10 times X 3 of the initial thickness of the pressure-sensitive adhesive film) of 1000% of the thickness (initial thickness: X 0 , unit: 탆) of the pressure-sensitive adhesive film and then held for 10 seconds, The length of the adhesive film stretched when a force of 0 kPa is applied to the adhesive film restored to the speed (300 mm / min) is X 2 (unit: 탆). Referring to FIG. 3, a graph is obtained with the stretched length of the adhesive film as the X-axis and the force applied to the adhesive film as the Y-axis. When the stretched length of the adhesive film when a force of 90 kPa is applied to the adhesive film is X 1 (unit: 탆), the elongation is calculated by the following formula 1, and the restoring force is a value calculated by the following formula 2:
<Formula 1>
Elongation = (X 1 ) / (X 0 ) x 100
<Formula 2>
Restoring force = (1 - (X 2 ) / (X 3 )) x 100
(2) Peel Strength: The corona was treated with a corona twice (total dose: 156 dose) on a PET film of width x length x thickness (150 mm x 25 mm x 75 m) while discharging the plasma at a dose of 78 dose using a corona processor. An adhesive film sample was obtained in the size of 100 mm x 25 mm x 50 m (width x length x thickness) in the pressure-sensitive adhesive sheets of Examples and Comparative Examples. A corona-treated PET film was laminated on both sides of the adhesive film sample to prepare the specimen shown in Fig. 4 (a). The specimen was autoclaved at a pressure of 3.5 bar at 50 ° C for 1000 seconds and the specimens were fixed on a TA.XT_Plus Texture Analyzer (Stable Micro System). Referring to FIG. 4 (b), one PET film was fixed and another PET film was pulled at a rate of 50 mm / min at 25 ° C in a TA.XT_Plus Texture Analyzer to measure the T-Peel peel strength.
(3) Haze: Haze meter (Nippon Denshoku Model NDH 5000) was used. The haze was measured for an adhesive film having a thickness of 50 탆 according to ASTM D 1003-95 5 ("Standard Test for Haze and Luminous Transmittance of Transparent Plastic").
(4) Folding evaluation: Both release films were separated from the pressure-sensitive adhesive sheet produced in the examples and comparative examples to obtain an adhesive film (thickness: 50 m). The adhesive film was placed between a corona-treated polyethylene terephthalate (PET) film (thickness: 125 μm) and a corona-treated PET film (thickness: 50 μm) and adhered with a roller, aged at room temperature for 12 hours, (70 mm x 140 mm) and used as a specimen. The specimen was fixed to a flexural evaluation equipment (CFT-200, Covotech) using an adhesive (4965, Tesa), and the length of the specimen (length: 140 mm) was measured at room temperature The bending was repeated at a rate of 30 cycles per minute (one cycle of bending and spreading the adhesive film in half) was repeated. Determine the maximum number of cycles for which there are no streaks in the folding area during folding, and where there is no rupture, peeling, peeling, or bubble in the adhesive film. When the maximum cycle number is 100,000 times or more, O, 70,000 times or more than 100,000 times is indicated by?, And when it is less than 70,000 times, X is taken.
(5) Storage modulus: A pressure-sensitive adhesive composition of the release film was coated (for example, polyethylene terephthalate, PET film) and covering the release film of the 75㎛ thickness on top, a low-pressure lamp for 6 minutes on both sides (50mw / cm 2, (BL Lamp manufactured by Sankyo Co., Ltd.) to produce an adhesive film. The viscoelasticity was measured by ARES (Anton Paar MCR-501), a dynamic viscoelasticity measuring device, at a shear rate of 1 rad / sec and strain 1% under an auto strain condition. After removing the release film, the adhesive film was laminated to a thickness of 1 mm, and the laminate was perforated with a perforator having a diameter of 8 mm and used as a specimen. Measurements were carried out at a temperature rise rate of 5 DEG C / min in the temperature range of -60 DEG C to 90 DEG C, and the modulus of elasticity was recorded at -20 DEG C, 25 DEG C and 80 DEG C.
(Meth) acrylate
(Parts by weight)
(Meth) acrylate
(Parts by weight)
(Meth) acrylate
(Parts by weight)
(Parts by weight)
(Parts by weight)
As shown in Table 1, the pressure-sensitive adhesive film of the present invention was excellent in elongation and peel strength. In addition, the adhesive film of the present invention was excellent in restoring force and exhibited good folding property at 25 캜. On the other hand, Comparative Example 1 including a copolymer containing no alkylene glycol unit exhibited poor elongation and peel strength at the same time, and the elongation was out of the range of the present invention, so that it did not exhibit good folding property during folding evaluation.
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 (18)
The peel strength at 25 占 폚 is from 1000 gf / in to 5000 gf / in,
A pressure-sensitive adhesive composition formed from a pressure-sensitive adhesive composition comprising a monomer mixture comprising a hydroxyl group-containing (meth) acrylate, an alkylene glycol unit-containing (meth) acrylate and an alkyl group-
<Formula 1>
Elongation = (X 1 ) / (X 0 ) x 100
(The first end portion / the adhesive film (length X length, 20 mm X 20 mm) of the PET film / the PET film (the polyethylene terephthalate film) The jig was fixed to both end portions of the PET film at 25 ° C, one jig was fixed, and the other jig was pulled at a speed of 300 mm / min to form the adhesive film When a length of 1000% of the thickness (X 0 ) (unit: μm) was reached and then held for 10 seconds, a graph was obtained with the stretched length of the adhesive film as the X axis and the force applied to the adhesive film as the Y axis , And the stretched length of the pressure-sensitive adhesive film when a force of 90 kPa is applied to the pressure-sensitive adhesive film is X 1 (unit: μm)))
Wherein the adhesive film has a restoring force of 40% to 98% at 25 DEG C according to the following formula:
<Formula 2>
Restoring force = (1 - (X 2 ) / (X 3 )) x 100
(In the formula 2, the jig is fixed to both ends of the PET film at 25 ° C with respect to the specimen of the formula 1, one jig is fixed, and the other jig is pulled at a rate of 300 mm / min, After reaching the length (10 times the thickness, X 3 ) of 1000% of the thickness (unit: 탆) and keeping it for 10 seconds, the stretched length of the adhesive film is taken as X axis and the force applied to the adhesive film as Y axis When the graph was obtained, the adhesive film was stretched to a length of 1000% of the thickness of the adhesive film and then restored to the same speed (300 mm / min) as the pulling speed to increase the adhesive film when a force of 0 kPa was applied to the adhesive film And the length is X 2 (unit: 탆)).
<Formula 3>
Tg (c) < Tg (s)
(Unit: 占 폚), and Tg (s) is the glass transition temperature (unit: 占 폚) of the shell.
Wherein the adhesive film comprises the adhesive film according to claim 1 or 2.
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| KR1020150178665A KR101962999B1 (en) | 2015-12-14 | 2015-12-14 | Adhesive film, optical member comprising the same and optical display apparatus comprising the same |
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| KR101951111B1 (en) * | 2017-07-05 | 2019-02-22 | 희성전자 주식회사 | Substrate for flexible display apparatus and flexible display apparatus having the substrate |
| WO2019151822A1 (en) | 2018-02-02 | 2019-08-08 | 주식회사 엘지화학 | Adhesive composition for foldable display, adhesive film using same, and foldable display comprising same |
| KR102317975B1 (en) * | 2018-10-10 | 2021-10-27 | 삼성에스디아이 주식회사 | Adhesive film, optical member comprising the same and optical display apparatus comprising the same |
| KR102319559B1 (en) * | 2018-10-10 | 2021-10-29 | 삼성에스디아이 주식회사 | Porous adhesive film, optical member comprising the same and optical display apparatus comprising the same |
| KR102259745B1 (en) | 2018-12-07 | 2021-06-02 | 주식회사 엘지화학 | Adhesive resin and adhesive composition for optical member |
| US20220332988A1 (en) * | 2019-12-03 | 2022-10-20 | Lg Chem, Ltd. | Foldable adhesive film and fabrication method therefor |
| KR102486598B1 (en) * | 2020-04-07 | 2023-01-09 | 삼성에스디아이 주식회사 | Adhesive composition, adhesive layer prepared from the same and optical display apparatus comprising the same |
| KR102338420B1 (en) | 2020-12-23 | 2021-12-10 | 삼성에스디아이 주식회사 | Adhesive film, optical member comprising the same and optical display apparatus comprising the same |
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| US7195820B2 (en) * | 2003-12-09 | 2007-03-27 | Arkema Inc. | Core-shell polymers having hydrophilic shells for improved shell coverage and anti-blocking properties |
| KR20100002638A (en) * | 2008-06-30 | 2010-01-07 | 동우 화인켐 주식회사 | Adhesive composition for optical film, optical film and liquid crystal display device using the composition |
| KR101266195B1 (en) * | 2009-09-16 | 2013-05-21 | 주식회사 엘지화학 | Double-sided pressure-sensitive adhesive tape, preparation method thereof and touch panel |
| KR101566061B1 (en) * | 2012-12-27 | 2015-11-04 | 제일모직주식회사 | Adhesive film, adhesive composition for the same and display member comprising the same |
| JP6222698B2 (en) * | 2014-02-21 | 2017-11-01 | 藤森工業株式会社 | Adhesive film and surface protective film |
| KR101716543B1 (en) * | 2014-04-30 | 2017-03-15 | 제일모직주식회사 | Adhesive film and optical display comprising the same |
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