Adhesive film for encapsulation and manufacturing method therefor

Abstract

Provided is an adhesive film for encapsulation, comprising an adhesive layer comprising a polymer of an adhesive composition comprising a copolymer having a double bond, a peroxide-based molecular weight regulator, a curing agent having two or more functional groups, an aminoalkylphenone-based photoinitiator, and inorganic particles, wherein the adhesive composition comprises 15-30 parts by weight of the aminoalkylphenone-based photoinitiator relative to 100 parts by weight of the curing agent having two or more functional groups.

Description

Adhesive film for bags and method of manufacturing the same

[0001] The present invention relates to an adhesive film for packaging and a method for manufacturing the same.

[0002]

[0003] Recently, the Organic Light Emitting Diode (OLED) sector has been experiencing significant growth as a new display market. Compared to conventional light sources, OLEDs offer lower power consumption, faster response times, advantages for miniaturizing displays or lighting, and superior space efficiency; consequently, they are expected to be applied across a wide range of fields, including portable devices, monitors, laptops, and TVs. However, the primary challenge regarding the commercialization and expansion of OLED applications is durability. Organic materials and metal electrodes contained within OLEDs oxidize very easily due to external factors such as moisture. Consequently, products containing OLEDs are highly sensitive to environmental factors. Accordingly, methods have been proposed to effectively block the penetration of external oxygen or moisture into organic electronic devices, such as OLEDs.

[0004]

[0005] The objective of the present invention is to provide an adhesive film for packaging with excellent adhesive strength while effectively blocking the penetration of oxygen or moisture from the outside, and a method for manufacturing the same.

[0006] The objective of the present invention is to provide an adhesive film for packaging and a method for manufacturing the same, which are produced by an environmentally friendly process using a simplified process compared to a conventional wet process using solvents.

[0007] The objects of the present invention are not limited to those mentioned above, and other unmentioned objects and advantages of the present invention may be understood from the following description and will be more clearly understood by the embodiments of the present invention. Furthermore, it will be readily apparent that the objects and advantages of the present invention can be realized by the means and combinations thereof set forth in the claims.

[0008]

[0009] In one embodiment of the present invention,

[0010] The adhesive layer comprises a polymer of an adhesive composition comprising a copolymer having double bonds, a peroxide-based molecular weight regulator, a curing agent having two or more functional groups, an aminoalkylphenone-based photoinitiator, and inorganic particles, and

[0011] The above adhesive composition provides an adhesive film for encapsulation comprising 15 to 30 parts by weight of the aminoalkylphenone-based photoinitiator relative to 100 parts by weight of the curing agent having two or more functional groups.

[0012] The copolymer having the above double bond may be an olefinic rubber.

[0013] The copolymer having the double bond above may include at least one selected from the group consisting of a copolymer of a butylene-based monomer and another polymerizable monomer; a butylene-based reactive oligomer; and combinations thereof.

[0014] The copolymer having the above double bond may include a copolymer of an olefin compound and a diene compound.

[0015] The copolymer having the above double bond may have a weight-average molecular weight of 100,000 to 1,000,000 g / mol.

[0016] The above peroxide-based molecular weight regulators are 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane, dicumyl peroxide, benzoyl peroxide, 1,1-bis-(t-butylperoxy)-3,5,5-trimethylcyclohexane, diisobutyryl peroxide, cumylperoxy neodecanoate, di-n-propylperoxy decarbonate, di-isopropyl peroxy decarbonate, and di-sec-butylperoxy Dicarbonate (di-sec-butylperoxy decarbonate), 1,1,3,3-tetramethyl-butylperoxy neodecanoate, di-(4-t-butylcyclohexyl)peroxy dicarbonate, di(2-ethylhexyl)peroxy dicarbonate, t-hexylperoxy neodecanoate, t-butylperoxy neodecanoate, t-butylperoxy neoheptanoate, t-hexylperoxy pivalate, t-butylperoxy Pivalate (t-butylperoxy pivalate), di(3,5,5-trimethyl-hexanoyl)peroxide, dilauroyl peroxide, 1,1,3,3-tetramethyl-butylperoxy-2-ethylhexanoate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, di(4-methyl-benzoyl) peroxide, t-butylperoxy-2-ethylhexanoate, di(3-methyl-benzoyl) peroxide, benzoyl(3-methyl-benzoyl) Peroxide (benzoyl(3-methyl-benzoyl) peroxide), dibenzoyl peroxide, 1,1-di(t-butylperoxy)-2-methyl-cyclohexane, 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(4,4-di(t-butylperoxy)cyclohexyl)propane), t-hexylperoxyisopropyl monocarbonate, t-butylperoxy maleic acid, t-butylperoxy-3,5,5-trimethyl hexanoate,t-butylperoxylaurate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2-di-(t-butylperoxy)butane, t-butylperoxybenzoate, n-butyl-4,4-di-(t-butylperoxy)valerate, di(2-t-butylperoxyisopropyl)benzene, di-t-hexyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, It may include at least one selected from the group consisting of 1,1,3,3-tetramethyl-butyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and combinations thereof.

[0017] The above curing agent may be a polyfunctional active energy line polymerizable compound.

[0018] The above curing agent is 1,4-butanediol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate (HDDA), 1,8-octanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, cyclohexane-1,4-dimethanol di(meth)acrylate, tricyclodecanedimethanol (meth)diacrylate, dimethylol dicyclopentane di(meth)acrylate, neopentyl glycol modified trimethylpropane di(meth)acrylate, and adamantane. It may include at least one selected from the group consisting of di(meth)acrylate, trimethylolpropane tri(meth)acrylate (TMPTA), and combinations thereof.

[0019] The above aminoalkylphenone-based photoinitiator may include at least one selected from the group consisting of 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(morpholinyl-4)phenyl]butanone, 2-(benzyl)-2-(dimethylamino)-1)-[4-(morpholinyl-4)phenyl]butanone, 2-(methyl)-1-[4-(methylthiol)phenyl]-2-(morpholino)-1-propanone and combinations thereof.

[0020] The above photoinitiator may further include at least one selected from the group consisting of benzoin-based, hydroxy ketone-based, amino ketone-based, phosphine oxide-based, and combinations thereof.

[0021] The above inorganic particles may be a moisture adsorbent material comprising at least one selected from the group consisting of metal oxides, sulfates, organometallic oxides, and combinations thereof; or may be an anti-spot agent comprising at least one selected from the group consisting of Li, Ni, Ti, Rb, Be, Mg, Ca, Sr, Ba, Al, Zn, In, Pt, Pd, Fe, Cr, Si, combinations thereof, oxides thereof, nitrides thereof, and combinations thereof.

[0022] The above adhesive composition may further include an additive comprising at least one selected from the group consisting of a tackifier, a curable material, a crosslinking agent, a softening agent, a filler, an anti-aging agent, a UV absorber, and combinations thereof.

[0023] The above adhesive layer is manufactured by an extrusion process and can be manufactured in a solvent-free manner.

[0024] The above adhesive layer may have a gel content of 60% or more and an adhesive strength of 5000 gf / inch to 8000 gf / inch.

[0025] The above adhesive film for the bag may further include one selected from the group consisting of a metal barrier layer, a release film, and combinations thereof.

[0026] The adhesive layer is formed as a single layer, and the thickness of the adhesive layer may be 10㎛ to 100㎛.

[0027]

[0028] In one embodiment of the present invention,

[0029] (a) a step of preparing a mixture comprising a copolymer having double bonds and a peroxide-based molecular weight regulator;

[0030] (b) a step of preparing an adhesive composition by adding a curing agent having two or more functional groups, an aminoalkylphenone-based photoinitiator, and inorganic particles to the above mixture and mixing; and

[0031] A method for manufacturing an adhesive film for packaging is provided, comprising the step (c) of photopolymerizing the adhesive composition above.

[0032] A mixture comprising the copolymer having the above double bond and the above peroxide-based molecular weight regulator can be mixed at 170°C or higher.

[0033] Step (a), Step (b), or both can be performed by an extrusion process.

[0034] In the method for manufacturing the adhesive film for the above-mentioned packaging, the adhesive composition may include 15 to 30 parts by weight of the aminoalkylphenone-based photoinitiator relative to 100 parts by weight of the curing agent having two or more functional groups.

[0035]

[0036] The above-mentioned excellent adhesive film for bags effectively blocks the penetration of oxygen or moisture from the outside, while also having excellent adhesive strength.

[0037] The method for manufacturing the above adhesive film for bags is a simplified process compared to the existing wet process that uses solvents, and is an eco-friendly method that does not use solvents while reducing costs.

[0038] In addition to the effects described above, the specific effects of the present invention are described together with the specific details for implementing the invention below.

[0039]

[0040] Hereinafter, embodiments of the present invention will be described in detail. However, these are presented as examples and are not intended to limit the present invention, and the present invention is defined only by the scope of the claims set forth below.

[0041]

[0042] In one embodiment of the present invention,

[0043] The adhesive layer comprises a polymer of an adhesive composition comprising a copolymer having double bonds, a peroxide-based molecular weight regulator, a curing agent having two or more functional groups, an aminoalkylphenone-based photoinitiator, and inorganic particles, and

[0044] The adhesive composition comprises 15 to 30 parts by weight of the aminoalkylphenone-based photoinitiator per 100 parts by weight of the curing agent having two or more functional groups.

[0045] Provides an adhesive film for bags.

[0046] The above adhesive layer has the inorganic particles well dispersed therein, effectively blocking the penetration of oxygen or moisture from the outside while having excellent adhesive strength.

[0047] The above adhesive layer can be manufactured by applying an extrusion process, so that the inorganic particles can be well dispersed.

[0048]

[0049] The above-mentioned adhesive film for encapsulation can be applied to various organic electronic devices, including organic light-emitting diodes. For example, since various optical components used in organic light-emitting diodes are prone to deterioration due to moisture or the like depending on the material, low moisture permeability is required in the adhesive film for encapsulation so as not to allow moisture to pass through. Because the above-mentioned adhesive film for encapsulation has excellent low moisture permeability, it can be usefully applied as an encapsulation material for various organic electronic devices.

[0050] In addition, the above adhesive film for bags can be manufactured in an eco-friendly manner by applying a solvent-free extrusion process.

[0051] In one embodiment, the copolymer having the double bond may be an olefinic rubber. Specifically, the olefinic rubber may include, but is not limited to, at least one selected from the group consisting of a copolymer formed by copolymerizing a butylene-based monomer with another polymerizable monomer; a butylene-based reactive oligomer; and combinations thereof. Examples of the butylene-based monomer include, for instance, 1-butene, 2-butene, or isobutylene. The types of the butylene-based monomer may include not only butylene but also derivatives thereof, such as forms having substituents. For instance, the olefinic rubber may include an isobutylene monomer as a polymerization unit.

[0052] In this specification, the term “combination of these” means a mixture or combination with one or more of the described components.

[0053] Other monomers capable of polymerizing with the above butylene-based monomer may include, for example, isoprene, styrene, or butadiene. The above olefinic rubber as a copolymer can maintain physical properties such as processability and degree of crosslinking, thereby ensuring the heat resistance of the adhesive itself when applied to organic electronic devices.

[0054] In one embodiment, the copolymer having the double bond may be a copolymer of an olefin compound and a diene compound. For example, the olefin compound may include at least one butylene-based monomer, such as butylene. The diene compound may be a monomer capable of polymerizing with the olefin compound, and may include, for example, isoprene or butadiene. For example, the copolymer of the olefin compound and the diene compound may be butyl rubber.

[0055] The butylene-based reactive oligomer may be a butylene oligomer having a reactive functional group. The butylene-based reactive oligomer may have a weight-average molecular weight of 500 g / mol to 5000 g / mol. The butylene-based reactive oligomer may be combined with another oligomer having a reactive functional group to form a block copolymer or a graft copolymer, etc. The other oligomer having a reactive functional group may be, for example, an alkyl (meth)acrylate oligomer, but is not limited thereto. The reactive functional group may be a hydroxyl group, a carboxyl group, an isocyanate group, or a nitrogen-containing group.

[0056] In one embodiment, the butylene-based reactive oligomer and the other oligomer having the reactive functional group may be crosslinked by a polyfunctional crosslinking agent. The polyfunctional crosslinking agent may be, for example, one selected from the group consisting of isocyanate crosslinking agents, epoxy crosslinking agents, aziridine crosslinking agents, metal chelate crosslinking agents, and combinations thereof.

[0057] In one embodiment, the copolymer having the double bond has a weight-average molecular weight such that it can be molded into a film shape of the adhesive layer. For example, the copolymer having the double bond may have a weight-average molecular weight of 100,000 to 1,000,000 g / mol, specifically 120,000 to 500,000 g / mol, and more specifically 150,000 to 300,000 g / mol, but is not limited thereto.

[0058] In another embodiment, the copolymer having the double bond may not have a weight-average molecular weight sufficient to be molded into a film shape of the adhesive layer, and in this case, the adhesive composition may further include a binder resin in addition to the copolymer having the double bond. The binder resin may be, for example, an acrylic resin, but is not limited thereto.

[0059] In this specification, weight-average molecular weight refers to a converted value for standard polystyrene measured by a Gel Permeation Chromatograph (GPC), and unless otherwise specified, the unit is g / mol.

[0060] The above peroxide-based molecular weight regulator is at least one peroxide compound included in the adhesive composition, and the weight-average molecular weight of the copolymer having double bonds can be controlled by the above peroxide-based molecular weight regulator. For example, the above peroxide-based molecular weight regulators include 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane, dicumyl peroxide, benzoyl peroxide, 1,1-bis-(t-butylperoxy)-3,5,5-trimethylcyclohexane, diisobutyryl peroxide, cumylperoxy neodecanoate, di-n-propylperoxy decarbonate, di-isopropyl peroxy decarbonate, and di-sec-butylperoxy Dicarbonate (di-sec-butylperoxy decarbonate), 1,1,3,3-tetramethyl-butylperoxy neodecanoate, di-(4-t-butylcyclohexyl)peroxy decarbonate, di(2-ethylhexyl)peroxy decarbonate, t-hexylperoxy neodecanoate, t-butylperoxy neodecanoate, t-butylperoxy neoheptanoate, t-hexylperoxy pivalate,t-butylperoxy pivalate, di(3,5,5-trimethyl-hexanoyl)peroxide, dilauroyl peroxide, 1,1,3,3-tetramethyl-butylperoxy-2-ethylhexanoate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, di(4-methyl-benzoyl) Peroxide (di(4-methyl-benzoyl) peroxide), t-butylperoxy-2-ethylhexanoate, di(3-methyl-benzoyl) peroxide, benzoyl(3-methyl-benzoyl) peroxide, dibenzoyl peroxide, 1,1-di(t-butylperoxy)-2-methyl-cyclohexane, 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(4,4-di(t-butylperoxy)cyclohexyl)propane,t-hexylperoxyisopropyl monocarbonate, t-butylperoxy maleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy laurate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxy benzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxy acetate, 2,2-di-(t-butylperoxy)butane, t-butylperoxy benzoate, n-butyl-4,4-di-(t-butylperoxy) valerate, di(2-t-butylperoxyisopropyl)benzene, di-t-hexyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 (2,5-dimethyl-2,5-di(t-butylperoxy) hexyne-3), diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethyl-butyl hydroperoxide (1,1,3,It may include at least one selected from the group consisting of 3-tetramethyl-butyl hydroperoxide), cumene hydroperoxide, t-butyl hydroperoxide, and combinations thereof.

[0061] The curing agent having two or more functional groups mentioned above may be used without limitation if it is a polyfunctional active energy beam polymerizable compound that can be polymerized by irradiation with an active energy beam. For example, the curing agent having two or more functional groups is 1,4-butanediol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate (HDDA), 1,8-octanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, cyclohexane-1,4-dimethanol di(meth)acrylate, tricyclodecanedimethanol (meth)diacrylate, dimethylol dicyclopentane di(meth)acrylate, neopentyl glycol modified trimethylpropane di(meth)acrylate, It may include at least one selected from the group consisting of adamantane di(meth)acrylate, trimethylolpropane tri(meth)acrylate (TMPTA), and combinations thereof, but is not limited thereto.

[0062] By including the above aminoalkylphenone-based photoinitiator, the adhesive composition may have physical properties suitable for molding by an extrusion process. The adhesive composition comprises 15 to 30 parts by weight of an aminoalkylphenone-based photoinitiator per 100 parts by weight of a curing agent having two or more functional groups. By including the aminoalkylphenone-based photoinitiator within the above content range, the adhesive composition can impart excellent heat resistance, thereby enabling molding by an extrusion process. Furthermore, the gel fraction resulting from UV curing of the adhesive layer can be improved, and accordingly, the moisture barrier effect of the adhesive layer is improved, and the adhesive layer can have excellent adhesive strength. Specifically, the adhesive composition may comprise more than 20 to 30 parts by weight of an aminoalkylphenone-based photoinitiator per 100 parts by weight of a curing agent having two or more functional groups. More specifically, the adhesive composition may comprise 23 to 30 parts by weight of an aminoalkylphenone-based photoinitiator per 100 parts by weight of a curing agent having two or more functional groups.

[0063] Specifically, the aminoalkylphenone-based photoinitiator may include at least one selected from the group consisting of 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(morpholinyl-4)phenyl]butanone, 2-(benzyl)-2-(dimethylamino)-1)-[4-(morpholinyl-4)phenyl]butanone, 2-(methyl)-1-[4-(methylthiol)phenyl]-2-(morpholino)-1-propanone and combinations thereof, but is not limited thereto.

[0064] In addition to the aminoalkylphenone-based photoinitiator, the above adhesive composition may optionally include other types of photoinitiators depending on the intended use, taking into account the curing speed and the possibility of yellowing. For example, the above-mentioned other types of photoinitiators may further include at least one type of benzoin-based, hydroxy ketone-based, amino ketone-based, or phosphine oxide-based photoinitiator, and specifically, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaninoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(morpholinyl-4)phenyl]butanone, rhobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethylketal, acetophenone dimethylketal, p-dimethylaminobenzoic acid ester, It may further include at least one type such as oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone], 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

[0065] In one embodiment, the inorganic particles serve as moisture adsorbents to block moisture, and may refer to chemically reactive adsorbents capable of removing infiltrated moisture or humidity through a chemical reaction. For example, the inorganic particles may exist in a particle form and be evenly dispersed within the adhesive layer. Here, an evenly dispersed state may refer to a state in which the moisture adsorbents exist at the same or substantially the same density in any part of the adhesive layer.

[0066] The above adhesive layer is manufactured according to the manufacturing method described below, and thus the inorganic particles exhibit excellent dispersibility. When the dispersibility of the inorganic particles within the adhesive layer is improved, the moisture permeability barrier function of the adhesive layer is also improved, and additionally, the adhesive strength of the adhesive layer is enhanced. Therefore, the adhesive layer exhibits excellent moisture barrier properties and excellent adhesive strength.

[0067] The above-mentioned inorganic particles may be, for example, metal oxides, metal salts, or organometallic oxides, and may include at least one of these. Specific examples of the metal oxides include phosphorus pentoxide (P2O5), lithium oxide (Li2O), sodium oxide (Na2O), barium oxide (BaO), calcium oxide (CaO), or magnesium oxide (MgO). Examples of the metal salts include lithium sulfate (Li2SO4), sodium sulfate (Na2SO4), and calcium sulfate ( CaSO4)Sulfates such as magnesium sulfate (MgSO4), cobalt sulfate (CoSO4), gallium sulfate (Ga2(SO4)3), titanium sulfate (Ti(SO4)2) or nickel sulfate (NiSO4); metal halides such as calcium chloride (CaCl2), magnesium chloride (MgCl2), strontium chloride (SrCl2), yttrium chloride (YCl3), copper chloride (CuCl2), cesium fluoride (CsF), tantalum fluoride (TaF5), niobium fluoride (NbF5), lithium bromide (LiBr), calcium bromide (CaBr2), cesium bromide (CeBr3), selenium bromide (SeBr4), vanadium bromide (VBr3), magnesium bromide (MgBr2), barium iodide (BaI2) or magnesium iodide (MgI2); Examples include metal chlorates such as barium perchlorate (Ba(ClO4)2) or magnesium perchlorate (Mg(ClO4)2); but are not limited thereto. Examples of the above organometallic oxides include aluminum oxide octylate.

[0068] In one embodiment, the inorganic particles may act as anti-bright spots in addition to serving as moisture adsorbents. Accordingly, for example, the adhesive film for the encapsulant may be applied to an organic electronic device to prevent bright spots on the panel of the organic electronic device. In an inorganic deposition layer of silicon oxide, silicon nitride, or silicon oxynitride deposited on the electrode of the organic electronic device, oxygen, H2 gas, ammonia (NH3) gas, and H + , NH 2+ , NHR2 or NH2R (wherein R may be an organic group, such as an alkyl group, alkenyl group, alkynyl group, etc., but not limited thereto). The inorganic particles may be a material capable of adsorbing the outgas.

[0069] Specifically, the inorganic particles capable of acting as the anti-spot agent are not limited as long as they satisfy the adsorption energy value, and may be, for example, metals or non-metals. Examples of the inorganic particles as the anti-spot agent may include Li, Ni, Ti, Rb, Be, Mg, Ca, Sr, Ba, Al, Zn, In, Pt, Pd, Fe, Cr, Si, or combinations thereof, may include oxides or nitrides thereof, and may also include alloys thereof. In one embodiment, the inorganic particles may include at least one selected from the group consisting of nickel particles, nickel oxide particles, titanium nitride, iron-titanium titanium alloy particles, iron-manganese manganese alloy particles, magnesium-nickel magnesium alloy particles, rare earth alloy particles, carbon nanotubes, graphite, aluminophosphate molecular sieve particles, mesosilica particles, and combinations thereof.

[0070] The above adhesive composition may further include, depending on the application, an additive comprising at least one selected from the group consisting of tackifiers, curable materials, crosslinking agents, softeners, fillers, anti-aging agents, UV absorbers, and combinations thereof. In addition to the above additive, known materials used in the adhesive composition may be further selected and included according to their known functions to suit the application.

[0071] As described above, the adhesive layer can be manufactured by an extrusion process and can be manufactured in a solvent-free manner that does not use solvents.

[0072] In addition, the adhesive layer can be manufactured by the manufacturing method described below so that the side reaction between the peroxide-based molecular weight regulator and the aminoalkylphenone-based photoinitiator is minimized, and thus exhibits an excellent gel content upon photocuring.

[0073] In one embodiment, the adhesive layer may have a gel content of 60% or more and an adhesive strength of 5000 gf / inch to 8000 gf / inch.

[0074] In one embodiment, the adhesive film for the bag may further include one selected from the group consisting of a metal barrier layer, a release film, and combinations thereof.

[0075] The adhesive film for the above-mentioned bag may further include a metal barrier layer. The metal barrier layer may be laminated to the adhesive layer to more effectively block oxygen, moisture, etc.

[0076] The above metal barrier layer may be, for example, an Al layer, a SUS layer, etc., and may be formed with a known metal barrier layer material and thickness.

[0077] In one embodiment, the adhesive layer may be formed as a single layer. As described above, since the adhesive layer has excellent adhesive strength, it may be formed as a single layer without the need to introduce an additional adhesive layer or adhesive coating layer with excellent adhesive strength.

[0078] For example, the single layer thickness of the adhesive layer may be 10㎛ to 100㎛, and by forming the adhesive layer to have a thickness within the above range, a predetermined moisture barrier effect can be achieved.

[0079] A release film may be laminated on one or both sides of the adhesive layer to protect it from the attachment of external foreign substances or physical damage so that the adhesive layer is not exposed on the outermost surface of the above-mentioned adhesive film for packaging. After peeling off the release film, the exposed side of the adhesive layer can be used by directly attaching it to an attachment target, for example, within the panel lamination structure of an organic electronic device.

[0080] In one embodiment, the adhesive film for the bag comprises one or more layers of the adhesive layer, and may be used in a manner where a release film is interposed between each layer of the adhesive layer, and the layers are attached one by one while removing the release film.

[0081]

[0082] In one embodiment of the present invention,

[0083] (a) a step of mixing a mixture comprising a copolymer having double bonds and a peroxide-based molecular weight regulator;

[0084] (b) a step of preparing an adhesive composition by adding a curing agent having two or more functional groups, an aminoalkylphenone-based photoinitiator, and inorganic particles to the above mixture and mixing; and

[0085] (c) step of photopolymerizing the above adhesive composition;

[0086] A method for manufacturing an adhesive film for packaging comprising

[0087] The above adhesive film for packaging can be manufactured by the method for manufacturing the above adhesive film for packaging. The copolymer having double bonds, the peroxide-based molecular weight regulator, the curing agent having two or more functional groups, the aminoalkylphenone-based photoinitiator, and the inorganic particles are as described above in the detailed description of the above adhesive film for packaging.

[0088] In one embodiment, step (a), step (b), or both can be performed by an extrusion process. Specifically, step (a) and step (b) can be performed by a Twin Screw Extruder (TSE) extrusion method in a high-temperature environment. Since the inorganic particles within the adhesive layer can be well dispersed by performing the process by an extrusion method, the dispersibility is improved compared to a wet coating method using a solvent. As previously mentioned, when the dispersibility of the inorganic particles in the adhesive layer is improved, the moisture barrier properties and adhesive strength are also improved.

[0089] In this way, compared to an adhesive layer manufactured by, for example, a wet coating method, the dispersion of the inorganic particles in the adhesive layer is improved when an extrusion process is applied, and consequently, the adhesive strength is also improved, so there is no need to additionally form a separate adhesive layer or adhesive coating layer to impart a predetermined level of adhesion to the adhesive film. Accordingly, the adhesive film for packaging may include the adhesive layer as a single layer. Since additional adhesive layers or adhesive coating layers can be omitted in this manner, the method of manufacturing the adhesive film for packaging results in a simplified process step compared to the conventional wet coating method, and consequently, costs are reduced.

[0090] In addition, the extrusion process can not only improve the dispersibility of inorganic particles but also be an eco-friendly process because it can proceed as a solvent-free process.

[0091] In one embodiment, a mixture comprising the copolymer having the double bond and the peroxide-based molecular weight regulator can be mixed at 170°C or higher, specifically from 170°C to 230°C.

[0092] The above method for manufacturing an adhesive film for packaging can effectively prevent unnecessary side reactions between the peroxide-based molecular weight regulator and other components, such as an aminoalkylphenone-based photoinitiator, by proceeding with steps (a) and (b) separately, thereby allowing the peroxide-based molecular weight regulator to react sufficiently with the copolymer having double bonds first, and then mixing with other components.

[0093]

[0094] In step (c) above, photocuring is performed by irradiating light, such as UV irradiation. By proceeding with photocuring in step (c), the durability of the adhesive layer is enhanced. As durability is enhanced, a stable moisture barrier effect can be exhibited even in high temperature and high humidity environments.

[0095] The above method for manufacturing an adhesive film for packaging uses an adhesive composition suitable for an extrusion process, so not only is the extrusion process possible, but stable photocuring is also carried out to secure a predetermined gel fraction, thereby enabling the adhesive layer to have excellent durability.

[0096]

[0097] Examples and comparative examples of the present invention are described below. The following examples are merely embodiments of the present invention, and the present invention is not limited to the following examples.

[0098]

[0099] (Example)

[0100] Comparative Example 1

[0101] 26.5 parts by weight of butyl rubber resin (Mw: 600,000 g / mol), 23.4 parts by weight of tackifying resin (SUKOREZ® SU525, Melting point: 125℃, Kolon), 3.97 parts by weight of polyfunctional acrylate (tricyclodecane dimethanol diacrylate, Miwon) as a curing agent, 0.13 parts by weight of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane as a peroxide-based molecular weight regulator, 0.79 parts by weight of 2,2-dimethoxy-1,2-diphenylethane-1-one as a benzyl ketal-based photoinitiator, and 43.7 parts by weight of CaO and 1.50 parts by weight of Ni as inorganic particles were added, homogenized, and then kneaded for 1 hour to prepare an adhesive composition, and the stirred adhesive composition was mixed with toluene until the solid content was approximately 20% by weight. A coating solution was prepared by dilution. The prepared solution was applied to the release surface of a release PET and dried in an oven at 120°C for 5 minutes to produce an adhesive film with a thickness of 40 μm, and UV radiation was applied at 3 J / cm² 2 An adhesive layer was prepared by proceeding with curing with an amount of irradiation, and an adhesive film for packaging containing the same was prepared.

[0102]

[0103] Comparative Example 2

[0104] An adhesive composition was prepared by adding 26.5 parts by weight of butyl rubber resin (Mw: 600,000 g / mol), 23.4 parts by weight of tackifying resin (SU525, Melting point: 125℃, Kolon), 3.97 parts by weight of polyfunctional acrylate (tricyclodecane dimethanol diacrylate, Miwon) as a curing agent, 0.13 parts by weight of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane as a peroxide-based molecular weight regulator, 0.79 parts by weight of 2,2-dimethoxy-1,2-diphenylethane-1-one as a benzyl ketal-based photoinitiator, and 43.7 parts by weight of CaO and 1.5 parts by weight of Ni as inorganic particles, homogenizing, and mixing for 1 hour. The above stirred adhesive composition was extruded through a twin-screw extruder at 180°C to form an adhesive layer with a thickness of 40 μm, and ultraviolet rays were applied at 3 J / cm² 2 An adhesive layer was prepared by proceeding with curing with an amount of irradiation, and an adhesive film for packaging containing the same was prepared.

[0105]

[0106] Comparative Example 3

[0107] An adhesive composition was prepared by adding 26.5 parts by weight of butyl rubber resin (Mw: 600,000 g / mol), 23.4 parts by weight of tackifying resin (SU525, Melting point: 125℃, Kolon), 3.97 parts by weight of polyfunctional acrylate (tricyclodecane dimethanol diacrylate, Miwon) as a curing agent, 0.13 parts by weight of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane as a peroxide-based molecular weight regulator, 0.79 parts by weight of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide as an acrylionic oxide-based photoinitiator, and 43.7 parts by weight of CaO and 1.5 parts by weight of Ni as inorganic particles, homogenizing, and mixing for 1 hour. The above stirred adhesive composition was extruded through a twin-screw extruder at 180°C to form an adhesive layer with a thickness of 40 μm, and ultraviolet rays were applied at 3 J / cm² 2 An adhesive layer was prepared by proceeding with curing with an amount of irradiation, and an adhesive film for packaging containing the same was prepared.

[0108]

[0109] Comparative Example 4

[0110] An adhesive composition was prepared by adding 26.5 parts by weight of butyl rubber resin (Mw: 600,000 g / mol), 23.4 parts by weight of tackifying resin (SU525, Melting point: 125℃, Kolon), 4.00 parts by weight of polyfunctional acrylate (tricyclodecane dimethanol diacrylate, Miwon) as a curing agent, 0.13 parts by weight of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane as a peroxide-based molecular weight regulator, 0.40 parts by weight of 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(morpholinyl-4)phenyl]butanone as an aminoalkylphenone-based photoinitiator, and 43.7 parts by weight of CaO and 1.5 parts by weight of Ni as inorganic particles, homogenizing, and mixing for 1 hour. The above stirred adhesive composition was extruded through a twin-screw extruder at 180°C to form an adhesive layer with a thickness of 40 μm, and ultraviolet rays were applied at 3 J / cm² 2 An adhesive layer was prepared by proceeding with curing with an amount of irradiation, and an adhesive film for packaging containing the same was prepared.

[0111]

[0112] Example 1

[0113] A tackifying composition was prepared by adding 26.4 parts by weight of butyl rubber resin (Mw: 600,000 g / mol), 23.4 parts by weight of tackifying resin (SU525, Melting point: 125℃, Kolon), 3.96 parts by weight of polyfunctional acrylate (tricyclodecane dimethanol diacrylate, Miwon) as a curing agent having two or more functional groups, 0.13 parts by weight of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane as a peroxide-based molecular weight regulator, 0.91 parts by weight of 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(morpholinyl-4)phenyl]butanone as an aminoalkylphenone-based photoinitiator, and 43.7 parts by weight of CaO and 1.5 parts by weight of Ni as inorganic particles, homogenizing, and kneading for 1 hour. The above stirred adhesive composition was extruded through a twin-screw extruder at 180°C to form an adhesive layer with a thickness of 40 μm, and ultraviolet rays were applied at 3 J / cm² 2 An adhesive layer was prepared by proceeding with curing with an amount of irradiation, and an adhesive film for packaging containing the same was prepared.

[0114]

[0115] Example 2

[0116] An adhesive composition was prepared by adding 26.3 parts by weight of butyl rubber resin (Mw: 600,000 g / mol), 23.3 parts by weight of tackifying resin (SU525, Melting point: 125℃, Kolon), 3.94 parts by weight of polyfunctional acrylate (tricyclodecane dimethanol diacrylate, Miwon) as a curing agent having two or more functional groups, 0.13 parts by weight of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane as a peroxide-based molecular weight regulator, 1.18 parts by weight of 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(morpholinyl-4)phenyl]butanone as an aminoalkylphenone-based photoinitiator, and 43.7 parts by weight of CaO and 1.5 parts by weight of Ni as inorganic particles, homogenizing, and kneading for 1 hour. The above stirred adhesive composition was extruded through a twin-screw extruder at 180°C to form an adhesive layer with a thickness of 40 μm, and ultraviolet rays were applied at 3 J / cm² 2 An adhesive layer was prepared by proceeding with curing with an amount of irradiation, and an adhesive film for packaging containing the same was prepared.

[0117]

[0118] Evaluation example

[0119] The following properties were evaluated for the adhesive films for packaging prepared in Comparative Examples 1 to 4, Example 1, and Example 2, and are shown in Table 1.

[0120]

[0121] 1) Gel content

[0122] The gel evaluation method (gel fraction, gel content) for evaluating UV curability involves soaking the UV-cured adhesive in toluene for 24 hours, filtering it through a 200-mesh screen, and measuring the ratio of the dry mass of the insoluble portion of the adhesive composition that did not pass through the screen. The detailed method is as follows.

[0123] As shown in [Equation 1] below, A represents the mass of the adhesive, and B represents the dry mass of the insoluble portion of the adhesive that did not pass through the mesh after immersing the adhesive in toluene at 60°C for 24 hours and filtering it through a 200-mesh (pore size 200㎛) mesh.

[0124] [Formula 1] Gel content (weight%) = B / A × 100

[0125]

[0126] 2) Moisture penetration distance

[0127] Glass substrates measuring 100mm x 100mm were laminated onto both sides of the adhesive layer prepared in the examples and comparative examples, and heat-pressed at 80°C for 1 minute using a vacuum press. Then, after being left for 400 hours and 900 hours in a constant temperature and humidity chamber at a temperature of 85°C and 85% relative humidity, the distance of moisture penetration (the distance of the adhesive film becoming transparent) was measured.

[0128]

[0129] 3) Measurement of adhesion strength

[0130] The adhesive layer prepared in the example or comparative example was placed on a SUS metal sheet, heated and pressed at 80°C using a vacuum press, and cut to a size of 25mm x 150mm. Then, using a tensile testing machine, the force at which the attached specimen separated was measured under conditions of a speed of 0.3m / min in the 90-degree direction.

[0131]

[0132] Gel Content (%) 400-Hour Moisture Penetration Distance (mm) 900-Hour Moisture Penetration Distance (mm) Adhesion (gf / 25mm) Comparative Example 18 8.4 1.1 5 21.7 49 3400 Comparative Example 2 21.4 4.2 5 08.3 00 6600 Comparative Example 3 20.0 5.1 00 9.5 00 6500 Comparative Example 4 5 5.1 4.1 5 6 2.1 79 6600 Example 18 0.8 0.8 6 61.0 44 5800 Example 2 7 2.8 0.8 7 61.0 71 6100

[0133] In the above Examples 1 and 2, an aminoalkylphenone-based photoinitiator was used to manufacture an adhesive film for packaging, and an adhesive composition was prepared by ensuring the content was at a predetermined level relative to a curing agent having two or more functional groups. From the evaluation results in Table 1, it can be confirmed that the adhesive films for packaging in Examples 1 and 2 exhibited a higher gel fraction, excellent moisture penetration, and excellent adhesive strength compared to cases where the aminoalkylphenone-based photoinitiator of Comparative Examples 1 to 3 was not used, and cases where the aminoalkylphenone-based photoinitiator of Comparative Example 4 was used but at a predetermined level relative to the curing agent.

[0134] Although the present invention has been described above with reference to embodiments, the present invention is not limited by the embodiments disclosed in this specification, and it is obvious that various modifications can be made by a person skilled in the art within the scope of the technical concept of the present invention. Furthermore, even if the effects of the configuration of the present invention were not explicitly described while describing the embodiments of the present invention above, it is natural to acknowledge that the effects predictable by said configuration should also be recognized.

Claims

1. A pressure-sensitive layer comprising a polymer of a pressure-sensitive composition comprising a copolymer having double bonds, a peroxide-based molecular weight regulator, a curing agent having two or more functional groups, an aminoalkylphenone-based photoinitiator, and inorganic particles, and The adhesive composition comprises 15 to 30 parts by weight of the aminoalkylphenone-based photoinitiator per 100 parts by weight of the curing agent having two or more functional groups. Adhesive film for bags.

2. In Paragraph 1, The copolymer having the above double bond is an olefinic rubber. Adhesive film for bags.

3. In Paragraph 1, The copolymer having the double bond comprises at least one selected from the group consisting of a copolymer formed by copolymerizing a butylene-based monomer with another polymerizable monomer; a butylene-based reactive oligomer; and combinations thereof. Adhesive film for bags.

4. In Paragraph 1, The copolymer having the above double bond comprises a copolymer of an olefin compound and a diene compound. Adhesive film for bags.

5. In Paragraph 1, The copolymer having the above double bond has a weight-average molecular weight of 100,000 to 1,000,000 g / mol. Adhesive film for bags.

6. In Paragraph 1, The above peroxide-based molecular weight regulators are 2,5-dimethyl-2,5-di-(t-butylperoxy)hexane, dicumyl peroxide, benzoyl peroxide, 1,1-bis-(t-butylperoxy)-3,5,5-trimethylcyclohexane, diisobutyryl peroxide, cumylperoxy neodecanoate, di-n-propylperoxy decarbonate, di-isopropyl peroxy decarbonate, and di-sec-butylperoxy Dicarbonate (di-sec-butylperoxy decarbonate), 1,1,3,3-tetramethyl-butylperoxy neodecanoate, di-(4-t-butylcyclohexyl)peroxy dicarbonate, di(2-ethylhexyl)peroxy dicarbonate, t-hexylperoxy neodecanoate, t-butylperoxy neodecanoate, t-butylperoxy neoheptanoate, t-hexylperoxy pivalate, t-butylperoxy Pivalate (t-butylperoxy pivalate), di(3,5,5-trimethyl-hexanoyl)peroxide, dilauroyl peroxide, 1,1,3,3-tetramethyl-butylperoxy-2-ethylhexanoate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, di(4-methyl-benzoyl) peroxide, t-butylperoxy-2-ethylhexanoate, di(3-methyl-benzoyl) peroxide, benzoyl(3-methyl-benzoyl) Peroxide (benzoyl(3-methyl-benzoyl) peroxide), dibenzoyl peroxide, 1,1-di(t-butylperoxy)-2-methyl-cyclohexane, 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(4,4-di(t-butylperoxy)cyclohexyl)propane), t-hexylperoxyisopropyl monocarbonate, t-butylperoxy maleic acid, t-butylperoxy-3,5,5-trimethyl hexanoate,t-butylperoxylaurate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2-di-(t-butylperoxy)butane, t-butylperoxybenzoate, n-butyl-4,4-di-(t-butylperoxy)valerate, di(2-t-butylperoxyisopropyl)benzene, di-t-hexyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, Comprising at least one selected from the group consisting of 1,1,3,3-tetramethyl-butyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and combinations thereof, Adhesive film for bags.

7. In Paragraph 1, The above curing agent is a polyfunctional active energy beam polymerizable compound. Adhesive film for bags.

8. In Paragraph 1, The above curing agent is 1,4-butanediol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate (HDDA), 1,8-octanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, cyclohexane-1,4-dimethanol di(meth)acrylate, tricyclodecanedimethanol (meth)diacrylate, dimethylol dicyclopentane di(meth)acrylate, neopentyl glycol modified trimethylpropane di(meth)acrylate, and adamantane. Comprising at least one selected from the group consisting of di(meth)acrylate, trimethylolpropane tri(meth)acrylate (TMPTA), and combinations thereof Adhesive film for bags.

9. In Paragraph 1, The above aminoalkylphenone-based photoinitiator comprises at least one selected from the group consisting of 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(morpholinyl-4)phenyl]butanone, 2-(benzyl)-2-(dimethylamino)-1)-[4-(morpholinyl-4)phenyl]butanone, 2-(methyl)-1-[4-(methylthiol)phenyl]-2-(morpholino)-1-propanone, and combinations thereof. Adhesive film for bags.

10. In Paragraph 1, The above photoinitiator further comprises at least one selected from the group consisting of benzoin-based, hydroxy ketone-based, amino ketone-based, phosphine oxide-based, and combinations thereof. Adhesive film for bags.

11. In Paragraph 1, The above-mentioned inorganic particles are moisture adsorbent materials comprising at least one selected from the group consisting of metal oxides, sulfates, organometallic oxides, and combinations thereof; or anti-spotting agents comprising at least one selected from the group consisting of Li, Ni, Ti, Rb, Be, Mg, Ca, Sr, Ba, Al, Zn, In, Pt, Pd, Fe, Cr, Si, combinations thereof, oxides thereof, nitrides thereof, and combinations thereof. Adhesive film for bags.

12. In Paragraph 1, The above adhesive composition further comprises an additive including at least one selected from the group consisting of a tackifier, a curable material, a crosslinking agent, a softening agent, a filler, an anti-aging agent, a UV absorber, and combinations thereof. Adhesive film for bags.

13. In Paragraph 1, The above adhesive layer is manufactured by an extrusion process and is manufactured using a solvent-free method. Adhesive film for bags.

14. In Paragraph 1, The above adhesive layer has a gel content of 60% or more and an adhesive strength of 5000 gf / inch to 8000 gf / inch. Adhesive film for bags.

15. In Paragraph 1, A further comprising one selected from the group consisting of a metal blocking layer, a release film, and combinations thereof. Adhesive film for bags.

16. In Paragraph 1, The adhesive layer is formed as a single layer, and the thickness of the adhesive layer is 10㎛ to 100㎛. Adhesive film for bags.

17. (a) a step of mixing a mixture comprising a copolymer having double bonds and a peroxide-based molecular weight regulator; (b) a step of preparing an adhesive composition by adding a curing agent having two or more functional groups, an aminoalkylphenone-based photoinitiator, and inorganic particles to the above mixture and mixing; and (c) step of photopolymerizing the above adhesive composition; Method for manufacturing adhesive film for bags.

18. In Paragraph 17, A mixture comprising the copolymer having the above double bond and the peroxide-based molecular weight regulator is mixed at 170°C or higher. Method for manufacturing adhesive film for bags.

19. In Paragraph 17, Step (a), Step (b), or both are performed by an extrusion process Method for manufacturing adhesive film for bags.

20. In Paragraph 17, The adhesive composition comprises 15 to 30 parts by weight of the aminoalkylphenone-based photoinitiator per 100 parts by weight of the curing agent having two or more functional groups. Method for manufacturing adhesive film for bags.