KR20170110811A - Carrier film using flexible organic electronic device - Google Patents

Abstract

The present application is directed to a carrier film for flexible organic electronic devices.
The carrier film of the present application exhibits a degree of increase in adhesive force to such an extent that it can be effectively peeled off without surface residues even after the heat treatment process of the substrate for flexible organic electronic devices, and the application of the carrier film in a roll-to- Lt; / RTI >

Description

Technical Field [0001] The present invention relates to a carrier film for a flexible organic electronic device,

The present application is directed to a carrier film for flexible organic electronic devices.

BACKGROUND ART Organic electronic devices (OEDs) are devices that perform functions through charge exchange between an electrode layer and an organic material, and examples thereof include organic light emitting devices (OLED), organic solar cells, organic photoconductors ) Or an organic transistor.

An organic light emitting device, which is a typical organic electronic device, typically includes a substrate, a first electrode layer, an organic layer including a light emitting layer, and a second electrode layer in sequence.

For example, a glass substrate, a plastic substrate, or the like can be used as the substrate used in the organic light emitting device. Recently, research on a flexible OLED to which a flexible substrate having flexibility is applied is actively being studied.

In order to manufacture the organic light emitting device, for example, it may include a step of depositing an organic / inorganic vapor deposition layer on a substrate for a flexible OLED. In this deposition process, the substrate is placed on a carrier film, A roll-to-roll process.

Since the carrier film and the substrate for OLED must be separated after the deposition process, the adhesive layer existing in a portion where the carrier film and the substrate for OLED are in contact must adhere the two layers properly during the deposition process. After the deposition process, Adhesive strength should be maintained such that the two layers can be separated smoothly.

(Patent Document 1) Korean Patent Laid-Open Publication No. 2015-0037704

The present application is adhered to a substrate with appropriate adhesive force before a vapor deposition and heat treatment process carried out on a substrate of a flexible organic electronic device and an increase in adhesive force after deposition and heat treatment is not so large, The present invention relates to a carrier film for a flexible organic electronic device.

The present application is directed to a carrier film for flexible organic electronic devices.

The carrier film of the present application may be used in a roll-to-roll process for a deposition process performed on a flexible organic electronic device, for example, a substrate of a flexible organic light-emitting device, As shown in FIG.

The substrate of the flexible organic light emitting device is attached via a pressure-sensitive adhesive layer existing on the carrier film. The adhesive force of the conventional pressure sensitive adhesive layer is rapidly increased after the vapor deposition process or heat treatment process performed on the substrate of the flexible organic light emitting device , A problem such as leaving a surface residue when peeling off the substrate and the carrier film occurs.

However, in the case of using the carrier film according to the present application, the content and type of the crosslinking agent in the pressure-sensitive adhesive layer and the equivalence ratio of the crosslinkable functional group contained in the crosslinking agent and the crosslinkable functional group of the acrylic copolymer are controlled, The substrate and the carrier film can be effectively peeled off without leaving a surface residue.

That is, the present application relates to a substrate layer; And a first pressure-sensitive adhesive layer formed on one surface of the base layer and including an acrylic copolymer. The carrier film of the present application also satisfies the following formula (1).

[Equation 1]

P ₂ -P _1? 0.5 N / cm

P ₁ is the peeling force (N / cm ₂ ) of the first pressure-sensitive adhesive layer on the flexible substrate measured at a peeling speed of 0.3 m / min and a peeling angle of 180 degrees before heat treatment, P ₂ is 150 ° C (N / cm) of the first pressure-sensitive adhesive layer to the flexible substrate measured at a peeling speed of 0.3 m / min and a peeling angle of 180 degrees after the heat treatment for 2 hours in the second pressure-sensitive adhesive layer.

The carrier film 1000 of the present application comprises a substrate layer 100 as shown in Fig. 1; And a first pressure-sensitive adhesive layer (200) formed on the base layer (100). In addition, the first pressure-sensitive adhesive layer 200 serves to attach the substrate 2000 of the flexible organic electronic device and the carrier film 1000 as shown in FIG.

The carrier film of the present application includes the first pressure-sensitive adhesive layer having a small change in adhesive force before and after the heat treatment process, thereby peeling off the substrate for the flexible organic electronic device without leaving surface residue, Which may be useful in a roll-to-roll process.

The carrier film of the present application comprises a substrate layer.

The base layer of the carrier film serves as a support for forming the first pressure-sensitive adhesive layer and a second pressure-sensitive adhesive layer to be described later. For example, the base layer may be made of polycarbonate, acrylic resin, poly (ethylene terephthalate) But is not limited to, a polymer substrate layer including PES (poly (ether sulfide)) or PS (polysulfone).

The thickness of the base layer is not particularly limited. For example, the base layer may have a thickness ranging from 10 to 300 占 퐉 or from 50 to 250 占 퐉.

The carrier film includes a first pressure-sensitive adhesive layer on one surface of the substrate layer. The first pressure-sensitive adhesive layer includes an acrylic copolymer as a portion to which a substrate for flexible organic electronic devices to be described later is adhered.

The acrylic copolymer of the present application contains 30% by weight or more of (meth) acrylic acid ester monomer as polymerized units. In order to realize a crosslinking structure by a crosslinking agent described later, polymerization of monomers having a crosslinkable functional group and other functional monomers Unit.

In one example, the acrylic copolymer may comprise polymerized units of a monomer comprising a (meth) acrylic acid ester monomer and a crosslinkable functional group. In the above, the term " the copolymer includes a polymerized unit of a monomer " means a state in which the monomer is polymerized and contained in a skeleton such as a main chain or a side chain of a polymer formed by polymerizing the monomer.

The term "(meth) acrylic acid ester monomer" in the present application means (meth) acrylic acid or a derivative thereof, and the (meth) acrylic acid means acrylic acid or methacrylic acid.

In one embodiment, the (meth) acrylic acid ester monomer may be an alkyl (meth) acrylate, and the alkyl (meth) acrylate may be an alkyl (meth) acrylate having an alkyl group of 1 to 20 carbon atoms. In the above, (meth) acrylate means acrylate or methacrylate.

Specifically, the alkyl (meth) acrylate is at least one compound selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, dodecyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (Meth) acrylate, tetradecyl (meth) acrylate, octadecyl (meth) acrylate, isobonyl (meth) acrylate, and the like.

Further, the monomer containing a crosslinkable functional group contained as a polymerization unit in the acrylic copolymer may be a polymer which is capable of providing a crosslinkable functional group to the copolymer by being polymerized with the (meth) acrylic acid ester monomer forming the acrylic copolymer Can be selected without limitation.

Specifically, the above-mentioned crosslinkable functional group can be selected without limitation, for example, as long as it can cause a crosslinking reaction with a crosslinking agent described later at a temperature within a range of about 50 to 300.

In one example, the crosslinkable functional group may be any one or more selected from the group consisting of a hydroxyl group, an isocyanate group, a glycidyl group, an epoxy group, an amine group and a carboxyl group.

Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl Hydroxyalkyl (meth) acrylates such as acrylate or 8-hydroxyoxyl (meth) acrylate and the like; Hydroxypolyalkylene glycol (meth) acrylate such as hydroxypolyethylene glycol (meth) acrylate or hydroxypolypropylene glycol (meth) acrylate; But are not limited thereto.

Examples of the monomer having a carboxyl group include monomers such as (meth) acrylic acid, 2- (meth) acryloyloxyacetic acid, 3- (meth) acryloyloxypropyl acid, 4- (meth) acryloyloxybutyric acid, Dimer, itaconic acid, maleic acid, or maleic anhydride, but is not limited thereto.

The monomer having an amine group may be, for example, 2-aminoethyl (meth) acrylate, 3-aminopropyl (meth) acrylate, N, N- dimethylaminoethyl (meth) acrylate or N, (Meth) acrylate, and the like.

Among the monomers having various crosslinkable functional groups, a suitable type can be selected in consideration of the desired glass transition temperature of the acrylic copolymer or reactivity with a crosslinking agent described later.

The acrylic copolymer may contain a polymerization unit of a monomer containing a (meth) acrylic acid ester monomer and a crosslinkable functional group in a predetermined ratio.

In one example, the acrylic copolymer may include 70 to 97 parts by weight of a (meth) acrylic acid ester monomer and 3 to 30 parts by weight of a monomer containing a crosslinkable functional group.

In another example, the acrylic copolymer includes 75 to 95 parts by weight of a (meth) acrylic acid ester monomer and 5 to 25 parts by weight of a monomer containing a crosslinkable functional group, or 80 to 90 parts by weight of a (meth) acrylic acid ester monomer, And 10 to 20 parts by weight of a monomer containing a polymerizable monomer.

The term " parts by weight " as used above means the weight ratios between the components unless otherwise defined.

The acrylic copolymer of the present application may further comprise polymerized units of other functional monomers to achieve the desired glass transition temperature and weight average molecular weight.

The functional monomer may be, for example, (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butoxymethyl Nitrogen-containing monomers such as lauridone or N-vinylcaprolactam; Alkylene oxide group-containing monomers such as alkoxy alkylene glycol (meth) acrylic acid esters, alkoxy dialkylene glycol (meth) acrylic acid esters or alkoxypolyethylene glycol (meth) acrylic acid esters; Or a styrene-based monomer such as styrene or methylstyrene, but is not limited thereto.

The functional monomer may be contained in the acrylic copolymer in a proportion of, for example, 0 to 70 parts by weight, 5 to 50 parts by weight or 10 to 30 parts by weight.

The acrylic copolymer of the present application can be prepared in various ways. For example, the copolymer may be obtained by selecting a desired monomer among the above-described monomers and then subjecting the mixture of the monomers containing the selected monomer to a desired ratio by solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization, and may be suitably prepared by solution polymerization. The manner of preparing the polymer through solution polymerization is not particularly limited.

The solution polymerization method may be carried out at a polymerization temperature of 50 to 140 占 폚 for about 6 to 15 hours, for example, by mixing the above-mentioned monomer components in an appropriate weight ratio, mixing the radical polymerization initiator and the solvent.

The radical polymerization initiator used for producing the acrylic copolymer is known, and examples thereof include azo-based polymerization initiators such as azobisisobutyronitrile and azobiscyclohexanecarbonitrile; Or oxides such as benzoyl peroxide or acetyl peroxide; And the like.

The polymerization initiator may be used alone or in combination of two or more. The content thereof may be in the range of 0.005 to 5 parts by weight or 0.005 to 1 part by weight.

In addition, the solvent used for preparing the acrylic copolymer is known, and for example, ethyl acetate or toluene may be used, but the present invention is not limited thereto.

The acrylic copolymer contained in the first pressure sensitive adhesive layer of the present application may have, for example, a glass transition temperature (Tg) in the range of -100 ° C to 0 ° C. In another example, the glass transition temperature (Tg) of the acrylic copolymer is in the range of -80 캜 to 0 캜, -70 캜 to 0 캜, -60 캜 to -10 캜, or -60 캜 to -20 캜 .

The acrylic copolymer of the present application may also have a weight average molecular weight ranging from 200,000 to 2,000,000. The term weight average molecular weight in the present application may mean a conversion value relative to standard polystyrene measured by GPC (Gel Permeation Chromatograph), and unless otherwise specified, the molecular weight of any polymer means the weight average molecular weight of the polymer . In another example, the weight average molecular weight of the acrylic copolymer may range from 250,000 to 1,500,000 or from 500,000 to 1,000,000.

The first pressure-sensitive adhesive layer of the carrier film may further comprise a crosslinking agent for crosslinking the acrylic copolymer.

In one example, the first pressure sensitive adhesive layer may further comprise a multifunctional crosslinking agent comprising a crosslinkable functional group for crosslinking the acrylic copolymer.

The polyfunctional crosslinking agent is a bifunctional or more polyfunctional compound having at least two or more crosslinkable functional groups and is capable of binding with a crosslinkable functional group contained in the acrylic copolymer to cure the first pressure sensitive adhesive layer .

Particularly, in the present application, the type and content of the multifunctional crosslinking agent can be appropriately controlled so that the adhesive strength can be prevented from increasing greatly even after the heat treatment process of the substrate for flexible organic electronic devices.

In one example, the multifunctional crosslinking agent may be included in the first pressure sensitive adhesive layer in a proportion of 1 to 50 parts by weight based on 100 parts by weight of the acrylic copolymer.

In another example, the multifunctional crosslinking agent may be included in the first pressure sensitive adhesive layer at a ratio of 5 parts by weight to 50 parts by weight, 10 parts by weight to 50 parts by weight, or 20 parts by weight to 50 parts by weight, based on 100 parts by weight of the acrylic copolymer.

Furthermore, the present application can minimize the increase in the adhesive force that can be increased after heat treatment by controlling the equivalent of the crosslinkable functional group of the acrylic copolymer and the equivalent of the crosslinkable functional group contained in the crosslinking agent.

In one example, the equivalent weight of the crosslinkable functional group contained in the polyfunctional crosslinking agent may be in the range of 0.3 to 1.5 equivalent to 1 equivalent of the crosslinkable functional group contained in the acrylic copolymer. The increase in width of the pressure-sensitive adhesive can be minimized within the range of the equivalent amount of the crosslinkable functional group contained in such a polyfunctional crosslinking agent, and the carrier film satisfying the above-mentioned formula 1 can be provided.

In another example, the equivalent amount of the crosslinkable functional group contained in the polyfunctional crosslinking agent may be in the range of 0.4 to 1.3 equivalents or 0.5 to 1.25 equivalents to 1 equivalent of the crosslinkable functional group contained in the acrylic copolymer.

The kind of the polyfunctional crosslinking agent may vary depending on the kind of the crosslinkable functional group contained in the acrylic copolymer.

In one example, the polyfunctional crosslinking agent is selected from the group consisting of an alkoxysilane group, a carboxyl group, an acid anhydride group, a vinyl ether group, an amine group, a carbonyl group, an isocyanate group, an epoxy group, an aziridinyl group, a carbodiimide group and an oxazoline group And may be a bifunctional or more polyfunctional compound containing at least one crosslinkable functional group.

Examples of the cross-linking agent containing a carboxyl group include o-phthalic acid, isophthalic acid, terephthalic acid, 1,4-dimethylterephthalic acid, 1,3-dimethylisophthalic acid, 5-sulfo-1,3-dimethylisophthalic acid, 4-biphenyldicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, norbornenedicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid Or aromatic dicarboxylic acids such as phenyl dodecarboxylic acid; Aromatic dicarboxylic acid anhydrides such as phthalic anhydride, 1,8-naphthalene dicarboxylic acid anhydride or 2,3-naphthalene dicarboxylic acid anhydride; Alicyclic dicarboxylic acids such as hexahydrophthalic acid; Alicyclic dicarboxylic acid anhydrides such as hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride or 1,2-cyclohexanedicarboxylic anhydride; Or an organic acid such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, chloromaleic acid, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid or itaconic acid Aliphatic dicarboxylic acids, and the like.

The cross-linking agent comprising the acid anhydride group may be, for example, anhydride pyromellitic acid, benzophenonetetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, diphenylsulfonetetracarboxylic acid dianhydride , Diphenyl sulfide tetracarboxylic acid dianhydride, butane tetracarboxylic acid dianhydride, perylene tetracarboxylic dianhydride, or naphthalene tetracarboxylic dianhydride.

The cross-linking agent containing the vinyl ether group is, for example, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, propylene glycol divinyl Ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, neopentyl glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, glycerin divinyldecenter, trimethylol Propane divinyl ether, 1,4-dihydroxycyclohexane divinyl ether, 1,4-dihydroxymethylcyclohexane divinyl ether, hydroquinone divinyl ether, ethylene oxide modified hydroquinone divinyl ether, ethylene oxide modified Resorcin divinyl ether, ethylene oxide modified bisphenol A divinyl ether, ethylene oxide modified bisphenol S divinyl But are not limited to, terpolymers such as terpolymers, terpolymers, terpolymers, terpolymers, terpolymers, terpolymers, terpolymers, terpolymers, terpolymers, terpolymers, Trimethylolpropane tetravinyl ether or ditrimethylolpropane polyvinyl ether, and the like.

Examples of the crosslinking agent containing an amine group include aliphatic diamines such as ethylenediamine and hexamethylenediamine; Alicyclic diamines such as 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexyl, diaminocyclohexane or isophoronediamine Ryu; Or aromatic diamines such as xylenediamine.

Examples of the crosslinking agent containing an isocyanate group include 2,2-dimethylpentane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, 1,3-butadiene- 1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecatriisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate- Aliphatic isocyanate compounds such as cyanatomethyloctane, bis (isocyanatoethyl) carbonate and bis (isocyanatoethyl) ether; (Isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, Alicyclic isocyanate compounds such as dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane isocyanate, and 2,2-dimethyldicyclohexylmethane isocyanate; (Isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatoethyl) Isocyanatomethyl) diphenyl ether, phenylenediisocyanate, ethylphenylenediisocyanate, isopropylphenylenediisocyanate, dimethylphenylenediisocyanate, diethylphenylenediisocyanate, diisopropylphenylenediisocyanate, trimethylbenzene triisocyanate, benzene tri Isocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4-diphenylmethane diisocyanate, 3,3-dimethyldiphenylmethane-4,4-diisocyanate, bibenzyl-4,4-diisocyanate, bis Cyanatophenyl) ethylene, 3,3-dimethoxybiphenyl-4,4-diisocyanate, hexahydrobenzene diisocyanate, hexa Aromatic isocyanate compounds such as hydroiodiphenylmethane-4,4-diisocyanate; Bis (isocyanatoethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis Bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatoethylthio) ethane, bis (isocyanatoethylthio) Aliphatic isocyanate compounds such as isocyanatomethylthio) ethane and 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane; Diphenylsulfide-2,4-diisocyanate, diphenylsulfide-4,4-diisocyanate, 3,3-dimethoxy-4,4-diisocyanatodibenzylthioether, bis (4- Diisocyanate, diphenyldisulfide-4,4-diisocyanate, 2,2-dimethyl diphenyldisulfide-5,5 Diisocyanate, 3,3-dimethyldiphenyldisulfide-5,5-diisocyanate, 3,3-dimethyldiphenyldisulfide-6,6-diisocyanate, 4,4- A sulfided aromatic isocyanate compound such as 5-diisocyanate, 3,3-dimethoxy diphenyl disulfide-4,4-diisocyanate and 4,4-dimethoxydiphenyl disulfide-3,3-diisocyanate; 2,5-bis (isocyanatomethyl) thiophene, 2,5-diisocyanatotetrahydrothiophene, 2,5-bis (isocyanatomethyl) (Isocyanatomethyl) tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-bis (isocyanatomethyl) Dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis (isocyanatomethyl) -1,3-dithiolane, 4,5-bis Isocyanatomethyl) -2-methyl-1,3-dithiolane; and adducts of the above isocyanate compounds.

Examples of the cross-linking agent containing an epoxy group include ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N, N, N, N'-tetraglycidyl- Xylene diamine, or glycerin diglycidyl ether.

The specific kind of the polyfunctional crosslinking agent may be determined according to the type of the crosslinkable functional group contained in the acrylic copolymer. For example, when the crosslinkable functional group is a glycidyl group, a polyfunctional crosslinking agent including a carboxyl group, an acid anhydride group, a vinyl ether group or an amine group may be selected. When the crosslinkable functional group is a hydroxy group, an isocyanate group When the crosslinkable functional group is a carboxyl group, a multifunctional crosslinking agent including a glycidyl group, an aziridinyl group, a carbodiimide group, an oxazoline group and the like may be selected.

In a specific example, the polyfunctional crosslinking agent may be an isocyanate compound, and the isocyanate compound may be an aliphatic acyclic diisocyanate compound and an aliphatic cyclic diisocyanate compound. The ratio of the two compounds is not particularly limited. For example, the ratio of the two compounds is, for example, 1: 9 to 9: 1, 2: 8 to 8: 2, or 3: 7 To 7: 3 by weight.

The thickness of the first pressure-sensitive adhesive layer formed on the base layer of the carrier film may be in the range of, for example, 2 탆 to 100 탆, 5 탆 to 50 탆 or 10 탆 to 40 탆. A substrate for a flexible, flexible electronic device to be described later can be effectively adhered within such a thickness range and can be peeled off without leaving a surface residue or the like even after the heat treatment process.

The method of forming the first pressure-sensitive adhesive layer on the base layer can be carried out, for example, by coating a pressure-sensitive adhesive composition comprising the above-mentioned acrylic copolymer and a polyfunctional crosslinking agent on the base layer using a known coating method, But the present invention is not limited thereto.

The composition for forming the first pressure sensitive adhesive layer may contain, in addition to the above components, a crosslinking catalyst, a crosslinking retarder and the like.

The crosslinking catalyst functions to accelerate the crosslinking of the acrylic copolymer and the polyfunctional crosslinking agent. The crosslinking catalyst is not particularly limited, and examples of the crosslinking catalyst include a tin-based metal compound, a zinc metal compound, an amine compound, a titanium- A bismuth-based metal compound, and an aluminum-based metal compound, and preferably a tin-based metal compound can be used. Specific examples of the tin-based metal compound include divalent tin dilaurate, dioctyltin dilaurate, dibutyltin bis (acetylacetonate), dibutyl tin oxide, dibutyl tin maleate, divalent tin dimaleate, Divalent organotin compounds, and the like, but the present invention is not limited thereto.

In addition, the crosslinking retarder can suppress the excessive viscosity increase of the pressure-sensitive adhesive composition by the acrylic copolymer and the crosslinking agent. Examples of the crosslinking retarder include, but are not limited to, beta -D-glucoside such as acetylacetone, methyl acetoate, ethyl acetoacetate, octyl acetoate, oleyl acetoacetate, lauryl acetoacetate, Keto ester, 2,4-hexanedione, benzoyl acetone and the like can be used, but acetylacetone can be preferably used.

The composition for forming the first pressure-sensitive adhesive layer may further comprise a tackifier as necessary. Examples of the tackifier include a hydrocarbon resin or hydrogenated product thereof, a rosin resin or hydrogenated product thereof, a rosin ester resin or hydrogenated product thereof, a terpene resin or hydrogenated product thereof, a terpene phenol resin or hydrogenated product thereof, Polymerized rosin ester resin, and the like, or a mixture of two or more of them may be used, but the present invention is not limited thereto.

The composition for forming the first pressure-sensitive adhesive layer may contain, in addition to the components described above, known additives such as a coupling agent; Epoxy resin; Ultraviolet stabilizer; Antioxidants; Coloring agent; Reinforcing agents; Filler; Defoamer; Surfactants; Or a plasticizer and the like may be further included.

Since the carrier film of the present application contains the above-described first pressure-sensitive adhesive layer on either side of the substrate layer, the rate of increase of the adhesive force is not high even after the heat treatment process performed after the substrate for a flexible organic electronic device is attached, It can be effectively peeled without leaving.

That is, the carrier film of the present application satisfies the following formula (1).

[Equation 1]

P ₂ -P _1? 0.5 N / cm

P ₁ is the peeling force (N / cm ₂ ) of the first pressure-sensitive adhesive layer on the flexible substrate measured at a peeling speed of 0.3 m / min and a peeling angle of 180 degrees before heat treatment, P ₂ is 150 ° C (N / cm) of the first pressure-sensitive adhesive layer to the flexible substrate measured at a peeling speed of 0.3 m / min and a peeling angle of 180 degrees after the heat treatment for 2 hours in the second pressure-sensitive adhesive layer.

The above equation (1) may be a value measured at room temperature using, for example, a tensile tester (Texture Analyzer).

The fact that the carrier film of the present application satisfies the expression (1) means that the increase in adhesion of the carrier film is not large even by the vapor deposition and heat treatment processes performed after the flexible organic electronic device substrate is laminated on the carrier film And effectively transports the substrate for a flexible organic electronic device in a roll-to-roll process for one purpose, particularly as a carrier film, and also effectively after the vapor deposition and heat treatment process of the substrate , It is possible to achieve effectively to minimize the surface residues.

In another example, the carrier film of the present application may have a P ₂ -P ₁ value in the above formula 1 of 0.4 N / cm or less, 0.3 N / cm or less, 0.2 N / cm or 0.16 N / cm or less. The lower limit of the P ₂ -P ₁ value in the above-mentioned formula (1) means that the change of the adhesive force is small before and after the heat treatment process. The lower limit of the P ₂ -P ₁ value is not particularly restricted but may be 0.05 N / cm or more, cm or greater or 0.10 N / cm or greater.

In Equation 1, P ₁ represents the peeling force of the carrier film on the substrate for flexible organic electronic devices before a predetermined heat treatment process. For example, P ₁ is in the range of 0.05 N / cm to 0.2 N / cm Lt; / RTI > Within this range, the carrier film is effectively attached to the substrate for flexible organic electronic devices, and a roll-to-roll process can be performed.

In another example, P ₁ in Equation 1 may be in the range of 0.08 N / cm to 0.16 N / cm or 0.084 N / cm to 0.13 N / cm.

In Equation 1, P ₂ means the peeling force of the carrier film on the substrate for flexible organic electronic devices after a predetermined heat treatment process. For example, P ₂ is in the range of 0.2 N / cm to 0.4 N / cm Lt; / RTI > Within this range, the carrier film can be peeled off from the substrate for a flexible organic electronic device without residue after the heat treatment process. In another example, P ₂ of the above formula 1 may be in the range of 0.15 N / cm to 0.25 N / cm or 0.18 N / cm to 0.245 N / cm.

The carrier film of the present application may also include a second pressure-sensitive adhesive layer which is present on the opposite surface of the base layer on which the first pressure-sensitive adhesive layer is formed. In addition, the second pressure sensitive adhesive layer may have a larger adhesive force than the first pressure sensitive adhesive layer.

2, the carrier film 1000 of the present application includes a first pressure-sensitive adhesive layer 200 on one surface of the base layer 100 and a second pressure-sensitive adhesive layer 300 on the other surface, . ≪ / RTI > In this case, the first pressure-sensitive adhesive layer 200 is a portion adhered to the substrate 2000 for a flexible organic electronic device, and the second pressure-sensitive adhesive layer 300 may be a portion adhered to the carrier glass 3000.

The second pressure-sensitive adhesive layer of the carrier film is adhered to the carrier glass, so that it can have a relatively strong adhesive force with respect to the first pressure-sensitive adhesive layer.

The second pressure sensitive adhesive layer may include an acrylic copolymer, and may include a multifunctional crosslinking agent including a crosslinkable functional group capable of crosslinking the acrylic copolymer, like the first pressure sensitive adhesive layer. The kind of the acrylic copolymer and the multifunctional crosslinking agent can be used without limitation of the kind mentioned in the first pressure sensitive adhesive layer.

In one example, the second pressure sensitive adhesive layer may comprise 100 parts by weight of an acrylic copolymer and 5 to 50 parts by weight of a multifunctional crosslinking agent comprising a crosslinkable functional group. In another example, the second pressure sensitive adhesive layer may comprise 100 parts by weight of the acrylic copolymer and 10 to 50 parts by weight, 15 to 50 parts by weight or 20 to 50 parts by weight of the multifunctional crosslinking agent containing a crosslinkable functional group.

The content of the polyfunctional crosslinking agent can be freely changed within the above-described range provided that the second pressure-sensitive adhesive layer is of such a degree as to assure a relatively strong adhesion force than the first pressure-sensitive adhesive layer.

The thickness of the second pressure sensitive adhesive layer may also have a range similar to that of the first pressure sensitive adhesive layer. For example, the second pressure-sensitive adhesive layer may be in the range of 2 탆 to 100 탆, 5 탆 to 50 탆, or 10 탆 to 40 탆.

The carrier film of the present application may further comprise a protective film for protecting the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer.

3, the carrier film 1000 of the present application has a protective film 400a, a first pressure-sensitive adhesive layer 200, a base layer 100, and a second pressure-sensitive adhesive layer 300 and a protective film 400b. In the roll-to-roll process, as shown in FIG. 4, the upper protective film 400a of the carrier film is removed, and the first pressure sensitive adhesive layer 200 and the flexible organic electronic device The carrier glass 2000 can be attached to the second adhesive layer 300 and the lower protective film 400b can be removed and the carrier glass 3000 can be attached to the second adhesive layer 300. [

As the protective film, a general film or sheet known in this field can be used. For example, a polyester film such as polyethylene terephthalate or polybutylene terephthalate, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a poly (vinyl chloride) film or a polyimide film And the like. Such a film may be composed of a single layer, or two or more layers may be laminated, and in some cases, a functional layer such as an antifouling layer may be further included. The thickness of the protective film is not particularly limited, and may be generally formed to a thickness of 5 to 500 탆 or 10 to 100 탆.

The carrier film of the present application is used for roll-to-roll of a flexible organic electronic device, and the substrate which can be adhered on the carrier film is, for example, 0.05 MPa to 5,000 MPa or And may be a flexible substrate having an elastic modulus ranging from 0.5 MPa to 2,500 MPa.

The carrier film of the present application can be effectively removed after the substrate for flexible organic electronic devices is effectively adhered and further subjected to processes such as vapor deposition and heat treatment, thereby minimizing surface residues.

The carrier film of the present application has an adequate adhesion force enough to be effectively adhered to a substrate for a flexible organic electronic device and can effectively control the adhesive force which can be increased after the vapor deposition or heat treatment process so that the carrier film can be peeled off without surface residues You can have a property.

Figures 1 to 3 illustrate the structure of the carrier film according to the present application.
Fig. 4 is a schematic view of the protective film of the carrier film of the present application being removed, and a substrate for a flexible organic electronic device and a carrier glass adhered thereto.

Hereinafter, the carrier film of the present application will be described in more detail with reference to examples and comparative examples, but it should be noted that the following examples are merely examples according to the present application and are not intended to limit the technical idea of the present application. Be self - evident to a person with knowledge.

One. Peel force  Test

In order to measure the peeling force of the carrier film before and after the heat treatment, the carrier film according to the examples and the comparative examples was cut to a size of 20 mm x 100 mm, and the surface on which the first pressure sensitive adhesive layer was placed was adhered to the flexible substrate. The peel strength (unit, N / cm) was measured at 180 ° peeling angle and 0.3m / min peeling rate using a texture analyzer (TA) After performing the heat treatment for 2 hours, the peeling force (unit, N / cm) was measured under the same conditions.

2. Surface when peeling after heat treatment Residue  Whether

When the carrier film is adhered to the flexible substrate and heat treatment is performed and the carrier film is peeled off from the flexible substrate, whether the adhesive residue is left on the surface of the flexible substrate is visually checked. If the residue is excessive, , And X if there is no residue.

[ Example  One]

1st The pressure-  Produce

90 parts by weight of ethylhexyl acrylate (EHA) and 10 parts by weight of hydroxyethylacrylate (HEA) were added to a 2 L reactor equipped with a cooling device so that nitrogen gas was refluxed therein to facilitate temperature control. Subsequently, 149.1 parts by weight of ethyl acetate (EAc) was poured into the reactor, nitrogen gas was purged for oxygen removal for 60 minutes, and azobisisobutyronitrile ( 0.0 > AIBN) < / RTI > was added thereto and reacted for 3 hours. The reacted reaction product was diluted with ethyl acetate (EAc) to prepare an acrylic copolymer (A1) having a solid concentration of 28% and a molecular weight of 700,000.

A cross-linking agent (hexamethylene diisocyanate adduct, HMDI (trade name, available from Dainippon Ink and Chemicals, Incorporated), which is capable of providing 1.2 equivalents of functional groups per equivalent of the crosslinkable functional group contained in the adhesive resin, Adducts were uniformly mixed to prepare a pressure-sensitive adhesive composition.

The pressure-sensitive adhesive composition was coated on a 125 占 퐉 A4300 (polyethylene terephthalate (PET) film, Toyobo Co.) with 20 占 퐉 and dried at 120 占 폚 for 3 minutes to form a first pressure-sensitive adhesive layer having a thickness of 20 占 퐉.

Second The pressure-  Produce

100 parts by weight of the acrylic copolymer (A2) formed by using 55 parts by weight of butyl acrylate (BA), 30 parts by weight of isobornyl acrylate (IBOA) and 15 parts by weight of hydroxyethyl acrylate (HEA) and 25 parts by weight of a crosslinking agent , A second pressure sensitive adhesive layer was formed on the opposite side of the surface of the PET film on which the first pressure sensitive adhesive layer was formed, in the same manner as the method of forming the first pressure sensitive adhesive layer.

carrier  Production of film

A protective film was laminated on the surface of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer on which the base layer was not formed, to produce a carrier film having the structure shown in Fig. The evaluation of the peel strength of the carrier film according to Example 1 and the surface residue upon peeling after heat treatment are shown in Table 1 below.

Example  2

A carrier film was prepared in the same manner as in Example 1, except that the first pressure-sensitive adhesive layer was formed using a composition obtained by changing the equivalent weight of the crosslinking agent to 0.9 equivalent to 1 equivalent of the crosslinkable functional group contained in the pressure-sensitive adhesive resin. Evaluation of peel strength of the carrier film according to Example 2 and surface residue upon peeling after heat treatment are shown in Table 1 below.

Example  3

A carrier film was prepared in the same manner as in Example 1, except that the first pressure-sensitive adhesive layer was formed using a composition obtained by changing the equivalent weight of the crosslinking agent to 0.6 equivalent to 1 equivalent of the crosslinkable functional group contained in the pressure-sensitive adhesive resin. The evaluation of the peel strength of the carrier film according to Example 3 and the surface residue upon peeling after heat treatment are shown in Table 1 below.

Example  4

A carrier film was prepared in the same manner as in Example 1, except that the first pressure-sensitive adhesive layer was formed using a composition obtained by changing the equivalent weight of the crosslinking agent to 0.3 equivalent to 1 equivalent of the crosslinkable functional group contained in the pressure-sensitive adhesive resin. The evaluation of the peel strength of the carrier film according to Example 1 and the surface residue upon peeling after heat treatment are shown in Table 1 below.

Comparative Example  One

A carrier film was prepared in the same manner as in Example 1, except that a known PSA was used as a pressure-sensitive adhesive resin and the content of the crosslinking agent was adjusted to 25 parts by weight to form a first pressure-sensitive adhesive layer. Evaluation of the peeling force of the carrier film according to Comparative Example 1 and the surface residue upon peeling after heat treatment are shown in Table 1 below

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Peel force before heat treatment (N / cm) 0.085 0.099 0.125 0.180 0.049 Peel force after heat treatment (N / cm) 0.211 0.222 0.245 0.357 0.084 Surface residue when peeling after heat treatment X X X X O

100: substrate layer
200: first pressure-sensitive adhesive layer
300: second pressure-sensitive adhesive layer
400a, b: protective film
1000: carrier film
2000: Flexible organic electronic device substrate
3000: Carrier glass

Claims (15)

A base layer; And
A carrier film for a flexible organic electronic device having a first pressure-sensitive adhesive layer formed on one surface of the substrate layer and comprising an acrylic copolymer,
[Equation 1]
P ₂ -P _1? 0.5 N / cm
P ₁ is the peeling force (N / cm ₂ ) of the first pressure-sensitive adhesive layer on the flexible substrate measured at a peeling speed of 0.3 m / min and a peeling angle of 180 degrees before heat treatment, P ₂ is 150 ° C (N / cm) of the first pressure-sensitive adhesive layer to the flexible substrate measured at a peeling speed of 0.3 m / min and a peeling angle of 180 degrees after the heat treatment for 2 hours in the second pressure-sensitive adhesive layer. The method according to claim 1,
Acrylic copolymer comprises 70 to 97 parts by weight of a (meth) acrylic acid ester monomer and 3 to 30 parts by weight of a monomer containing a crosslinkable functional group. 3. The method of claim 2,
(Meth) acrylic acid ester monomer is an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms. 3. The method of claim 2,
The crosslinkable functional group is any one or more selected from the group consisting of a hydroxyl group, an isocyanate group, a glycidyl group, an epoxy group, an amine group and a carboxyl group. The method according to claim 1,
Wherein the first pressure-sensitive adhesive layer further comprises a multifunctional crosslinking agent comprising a crosslinkable functional group for crosslinking the acrylic copolymer. 6. The method of claim 5,
Wherein the multifunctional crosslinking agent is contained in the first pressure sensitive adhesive layer in a range of 1 to 50 parts by weight based on 100 parts by weight of the acrylic copolymer. 6. The method of claim 5,
Wherein the equivalent of the crosslinkable functional group contained in the polyfunctional crosslinking agent is in the range of 0.3 to 1.5 equivalents relative to 1 equivalent of the crosslinkable functional group contained in the acrylic copolymer. 6. The method of claim 5,
The crosslinkable functional group of the polyfunctional crosslinking agent is selected from the group consisting of alkoxysilane group, carboxyl group, acid anhydride group, vinyl ether group, amine group, carbonyl group, isocyanate group, epoxy group, aziridinyl group, carbodiimide group and oxazoline group A carrier film for at least one flexible organic electronic device. 6. The method of claim 5,
The multi-functional crosslinking agent comprises an aliphatic cyclic diisocyanate compound and an aliphatic acyclic diisocyanate compound. The method according to claim 1,
Wherein the thickness of the first pressure-sensitive adhesive layer is in the range of 2 占 퐉 to 100 占 퐉. The method according to claim 1,
The carrier film for a flexible organic electronic device according to claim 1, wherein P ₁ is in the range of 0.05 N / cm to 0.20 N / cm. The method according to claim 1,
The carrier film for a flexible organic electronic device according to claim 1, wherein P ₂ is in the range of 0.2 N / cm to 0.4 N / cm. The method according to claim 1,
And a second pressure-sensitive adhesive layer which is present on a surface of the base layer opposite to the surface on which the first pressure-sensitive adhesive layer is formed and has an adhesive strength stronger than that of the first pressure-sensitive adhesive layer. 14. The method of claim 13,
And the second pressure-sensitive adhesive layer comprises 100 parts by weight of an acrylic copolymer and 5 to 50 parts by weight of a multifunctional crosslinking agent containing a crosslinkable functional group. The method according to claim 1,
And further comprising a protective film formed on the first pressure-sensitive adhesive layer.

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