KR20200068292A - Adhesive composition, surface protective film and method for manufacturing organic light emitting electronic device - Google Patents

Abstract

The present invention relates to an adhesive composition comprising: a urethane polymer; an acrylic polymer; and a curing agent, to a surface protection film, and to a manufacturing method of an organic light emitting electronic device. According to the present invention, provided is an adhesive layer with little damage or contamination on a surface of an adherend.

Description

Manufacturing method of adhesive composition, surface protection film and organic light emitting electronic device {ADHESIVE COMPOSITION, SURFACE PROTECTIVE FILM AND METHOD FOR MANUFACTURING ORGANIC LIGHT EMITTING ELECTRONIC DEVICE}

The present application relates to a pressure-sensitive adhesive composition, a surface protection film and a method for manufacturing an organic light emitting electronic device using the surface protection film.

The plastic substrate used as the substrate material of the flexible display has a problem that gas barrier properties such as moisture and oxygen are remarkably low. Accordingly, in the related art, a barrier film to which various materials and structures are applied is formed on the substrate to improve the problem of the plastic substrate.

However, recently, as the existing barrier film is not used, the development of a surface protection film for a process capable of protecting a thin film encapsulation (TFE) layer during the manufacturing process of a flexible optical device is required. The surface protective film for the process is a film that temporarily protects the thin film encapsulation layer and is attached to the thin film encapsulation layer during the process to prevent contamination or damage to the surface of the thin film encapsulation layer during the process, and is removed when the process ends.

First, the physical properties required for the surface protection film should adhere well to the surface of the adherend provided on the surface protection film, and must be able to be removed with a low peel force in the step of being removed to prevent damage to the adherend. . Second, after removing the surface protection film, there should be little residue of the pressure-sensitive adhesive to be able to prevent contamination of the adherend.

Registered Patent Publication No. 10-1756828

Conventionally, as a urethane-based adhesive, a plasticizer was added to control the adhesive strength to reduce the adhesive strength. However, in the case of adding a plasticizer, it is possible to realize low adhesion, but since the plasticizer diffuses and is lost to other substances in contact with the product surface, surface contamination occurs and it is difficult to realize low residue properties. . An object of the present invention is to provide an adhesive layer in which a low adhesive force and a low residual amount are realized without including a plasticizer.

One embodiment of the present specification is a urethane polymer; Acrylic polymers; And a curing agent,

The acrylic polymer provides a pressure-sensitive adhesive composition comprising a (meth)acrylate monomer containing silicone as a monomer unit.

Another embodiment of the present specification is an adhesive layer comprising an acrylic polymer,

The acrylic polymer provides a pressure-sensitive adhesive layer comprising a (meth)acrylate monomer containing silicon as a monomer unit.

An exemplary embodiment of the present specification includes a base film and a base layer including a first anti-static layer and a second anti-static layer provided on both sides of the base film; And

A surface protection film comprising an adhesive layer provided on the opposite side of the surface of the second antistatic layer provided with the base film,

The pressure-sensitive adhesive layer provides a surface protection film that is the above-described pressure-sensitive adhesive layer.

Another exemplary embodiment of the present specification provides a method of manufacturing an organic light emitting electronic device including the step of attaching the pressure-sensitive adhesive layer of the above-described surface protection film on the encapsulation layer of the organic light emitting device.

According to the present invention, it is possible to remove the surface protection film with a low peeling force due to low adhesion to the surface of the adherend, but after removal, the adhesive layer having little damage or contamination on the surface of the adherend after desorption due to a small amount of adhesive on the surface of the adherend Can provide.

1 is a substrate layer 110; Pressure-sensitive adhesive layer 124; And it shows a surface protective film consisting of a protective layer 130.
2 is an adhesive layer 124; And it shows a surface protective film consisting of a protective layer 130.
FIG. 3 shows a form in which the surface protection film of FIG. 2 is attached to the adherend 140.
FIG. 4 shows a state in which the adherend of FIG. 3 is an organic light emitting device 510.

Before describing the present invention, some terms are defined.

When a part is referred to as "comprising" a component in the present specification, it means that other components may be further included rather than excluding other components, unless specifically stated to the contrary.

In the present specification,'p to q'means a range of'p or more and q or less'.

In the present specification, (meth)acrylate includes both acrylate and methacrylate.

In the present specification, the meaning that the polymer includes a monomer as a monomer unit means that the monomer participates in a polymerization reaction and is included as a repeating unit in the polymer. In the present specification, when it is said that the polymer includes a monomer, this is interpreted in the same way that the polymer includes a monomer as a monomer unit.

In the present specification, the term "polymer" is understood to be used in a broad sense including a copolymer unless specified as "homopolymer."

In the present specification, "a unit derived from a compound" means a state in which the compound is polymerized and bonded to the polymer, and accordingly, all or part of two or more substituents in the structure of the compound are eliminated, and the polymer is in its position. Radicals for bonding with other units of may be located.

In the present specification, "monomer unit" means a state in which the compound is polymerized and bound in the polymer.

In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are monodisperse polystyrene polymers (standard samples) of various degrees of polymerization commercially available for molecular weight measurement, and gel permeation chromatography (Gel Permeation) It is a molecular weight in terms of polystyrene measured by Chromatography (GPC). In this specification, molecular weight means a weight average molecular weight unless otherwise specified.

Hereinafter, the present invention will be described in detail with reference to the drawings so that those skilled in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the following description.

One embodiment of the present specification provides an adhesive composition.

The pressure-sensitive adhesive composition is a urethane polymer; Acrylic polymers; And curing agents.

The pressure-sensitive adhesive composition according to an exemplary embodiment of the present invention includes a urethane polymer and an acrylic polymer, so that it can be peeled from the adherend with a low peel force, and after the pressure-sensitive adhesive layer is peeled from the adherend, the pressure-sensitive adhesive layer having a small amount of residue on the adherend surface You can implement

In one embodiment of the present invention, as the urethane polymer, a known urethane polymer can be appropriately selected and used within a range that does not degrade the effect of the present invention.

In one embodiment of the present invention, the urethane polymer means a polymer obtained by curing a urethane composition containing a polyol and a polyfunctional isocyanate compound.

As a polyol included in the urethane composition, any suitable polyol may be used as long as it is a compound containing two or more OH groups. In one embodiment, the polyol may include 2 to 6 OH groups, but is not limited thereto.

The polyol included in the urethane composition may be one or two or more. When using two or more types of polyols, the mixing ratio can be appropriately selected.

The number average molecular weight of the polyol contained in the urethane composition may be appropriately selected. In one embodiment, the number average molecular weight of the polyol may be suitably 100 g/mol to 20,000 g/mol, but is not limited thereto.

In one embodiment, the polyol included in the urethane composition may include a bifunctional polyol and a trifunctional polyol. In one embodiment, the proportion of the trifunctional polyol among the polyols included in the urethane composition is 70% to 100% by weight; 80% to 100% by weight; Or 90% to 100% by weight, and the proportion of the bifunctional polyol is 0% to 30% by weight; 0% to 20% by weight; Or 0% to 10% by weight. In an exemplary embodiment, when the polyol includes a trifunctional polyol, it is advantageous to balance the adhesive strength and removability of the pressure-sensitive adhesive layer.

In one embodiment, when the urethane composition comprises a trifunctional polyol, the trifunctional polyol may have a polyol having a number average molecular weight of 10,000 g/mol to 15,000 g/mol and a number average molecular weight of 1,000 g/mol to 5,000. Polyols of g/mol can be used together.

In one embodiment, when the urethane composition includes a bifunctional polyol, the number average molecular weight of the bifunctional polyol may be 100 g/mol to 3,000 g/mol.

It is preferable that the polyol contained in the urethane composition preferably does not contain an additional functional group reactive with an isocyanate group (NC0).

The polyol included in the urethane composition may be, for example, polyacrylic polyol, polyether polyol, polyester polyol, polycaprolactone polyol, polycarbonate polyol, castor oil-based polyol, and combinations thereof, but is not limited thereto.

In an exemplary embodiment, when two or more types of polyols are mixed and used, molecular weight dispersion is easily adjusted. In one embodiment, the polyol is 50 to 100% by weight of polyether polyol in the polyol; And 0 to 50% by weight of polyester polyol. In one embodiment, the polyol is 75% to 95% by weight of polyether polyol in the polyol; And 5% to 25% by weight of polyester polyol.

As the isocyanate compound included in the urethane composition, any suitable polyfunctional isocytate compound commonly used in the art may be selected and used as long as it is a compound that can be used in the urethanization reaction.

The polyfunctional isocyanate compound includes, for example, polyfunctional aliphatic isocyanate, polyfunctional alicyclic isocyanate, polyfunctional aromatic isocyanate compound, trimethylol propane adduct modified with polyisocyanate by trifunctional isocyanate, poly A biuret body in which isocyanate is reacted with water, a trimer having an isocyanurate ring, and the like can be used, but is not limited thereto.

The polyfunctional aliphatic isocyanate compound is, for example, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dode Camethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.

The polyfunctional alicyclic isocyanate compound is, for example, isophorone diisocyanate (IPDI), 1,4-cyclohexane diisocyanate (CHDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI), bis (isocia Natomethyl) cyclohexane (HXDI), and the like.

The polyfunctional aromatic isocyanate compound is, for example, toluene 2,4-diisocyanate (TDI), toluene 2,6-diisocyanate (TDI), 4,4'-methylene diphenyl diisocyanate (MDI), 2,4 '- methylene diphenyl diisocyanate (MDI), polymeric methylene diphenyl diisocyanate (PMDI), p-phenylene diisocyanate (PDI), m-phenylene diisocyanate (PDI), naphthalene 1,5-diisocyanate ( NDI), naphthalene 2,4-diisocyanate (NDI), p-xylylene diisocyanate (XDI), 1,3-bis(1-isocyanato-1-methylethyl)benzene (TMXDI), and the like. It is not limited.

In one embodiment of the present specification, two or more isocyanate compounds may be mixed and used in the urethane composition, and in this case, the type and content of the two or more isocyanate compounds may be appropriately selected. For example, the isocyanate compound contained in the urethane composition may be used by mixing a polyfunctional aromatic isocyanate compound and a polyfunctional aliphatic isocyanate compound.

In the urethane composition, the equivalent ratio (NCO group/OH group) of the OH group of the polyol and the NCO group of the isocyanate compound is 0.1 or more and less than 1. By satisfying the above ratio, OH groups may be present in the urethane polymer formed from the urethane composition.

In the urethane composition, the mixing ratio of the polyol and the isocyanate compound may be appropriately selected.

In one embodiment, the urethane composition may further include other components within a range that does not degrade the effect of the present invention. For example, the urethane composition may further include a catalyst, a plasticizer, an antioxidant, a leveling agent, a solvent, and the like.

As the polymerization method of the urethane polymer, any suitable method known in the art can be selected, and in one embodiment, a method such as solution polymerization can be used.

In one embodiment, the preferred weight average molecular weight of the urethane polymer may be 60,000g/mol to 160,000g/mol. If the weight average molecular weight of the urethane polymer is less than 60,000 g/mol, the urethane polymer is hard and brittle, and if the weight average molecular weight of the urethane polymer exceeds 160,000 g/mol, the urethane polymer has a problem of gelling.

In one embodiment, the hydroxyl value of the urethane polymer is 3mgKOH/g to 15mgKOH/g.

In the present specification, the hydroxyl value of the compound can be measured by a titration method. The method of measuring the hydroxyl value by titration is as follows. 1 g of the compound to be measured is added to 25.5 g of an acetylation reagent, and stirred for 2 hours in an oil bath at 100°C. After air cooling for 30 minutes, 10 ml of pyridine is added. Thereafter, 50 ml (51 g) of 0.5N KOH, 10 drops of a magnetic bar and a phenolphthalein indicator are added, and 0.5N KOH is titrated until the solution turns pink while stirring on a plate.

Acetylation reagent: a solution of 70 g of phthalic anhydride and 500 g of pyridine mixed

Phenolphthalein indicator: A solution of 0.5 g of phenolphthalein stock solution, 250 g of ethanol and 250 g of distilled water

The hydroxyl value can be calculated by the following equation.

Hydroxyl value = 28.05×(A-B)×F/(sample volume)

A: 0.5N KOH (ml) required for blanking

B: 0.5N KOH (ml) required for this test

F: The amount of KOH (ml) when titrating with 0.5N KOH after adding 10 drops of magnetic bar and phenolphthalein indicator to 10 ml of 1N HCL

The acrylic polymer includes a (meth)acrylate monomer containing silicone as a monomer unit. The pressure-sensitive adhesive composition according to an exemplary embodiment of the present invention can be peeled from the adherend even with a low peel force by including a (meth)acrylate monomer containing silicone, and after peeling the pressure-sensitive adhesive layer from the adherend, on the surface of the adherend It is possible to implement an adhesive layer with a small amount of residue.

In one embodiment of the present specification, the (meth)acrylate monomer containing the silicone is a polyorganosiloxane compound containing an acryloyloxy group.

In one embodiment of the present specification, a unit derived from the (meth)acrylate monomer containing the silicone may be represented by the following Chemical Formula 3.

[Formula 3]

In Chemical Formula 3,

R ₁ to R ₇ are the same as or different from each other, and each independently an alkyl group,

R ₈ is hydrogen or a methyl group,

n is an integer greater than or equal to 0,

L is a divalent saturated hydrocarbon group of straight or branched chain; A divalent monocyclic aliphatic saturated hydrocarbon group; A divalent polycyclic saturated hydrocarbon group; A divalent aromatic hydrocarbon group; A divalent group of a ring in which an aromatic hydrocarbon is condensed with cyclic saturated hydrocarbon; -O-; -C(=O)-; -C(=O)-O-; Or -S-, or two or more of the groups are linked groups.

In one embodiment of the present specification, R ₁ to R ₇ are the same as or different from each other, and each independently an alkyl group of C ₁ to C ₁₀ .

In one embodiment of the present specification, Chemical Formula 3 is represented by the following Chemical Formula 3-1.

[Formula 3-1]

In Chemical Formula 3-1,

R ₄ , R ₈ and n have the same definition as in Formula 3,

m is an integer from 0 to 10.

In one embodiment of the present specification, n is 1 to 500; 10 to 400; 20 to 350; Or an integer from 30 to 300.

In one embodiment of the present specification, the number average molecular weight of the (meth)acrylate monomer containing the silicone is 500 g/mol to 10,000 g/mol.

In one embodiment of the present specification, the number average molecular weight of the (meth)acrylate monomer containing the silicone is 10,000 g/mol or less; 9,000 g/mol or less; Or 8,000 g/mol or less. If the number average molecular weight of the (meth)acrylate monomer containing silicone is greater than 10,000 g/mol, there may be limitations in the compatibility between the acrylic polymer and the urethane polymer.

In one embodiment of the present specification, a commercially available monomer may be used as the (meth)acrylate monomer containing the silicone. For example, X-24-8201, X-22-174DX, X-22-2426, X-22-2404, X-22-164A, X-22-164C, FA-4001, manufactured by Shin-Etsu Chemical Industry Co., Ltd., FA-4002 and FA-4003, Tore Dow Corning Corporation BY16-152D, BY16-152, BY16-152C and CHISSO FM-0711, FM-0721 and FM-0725, Shinetsu KP-541, KP-578 , KP-543 and KP-549.

In one embodiment of the present specification, the (meth)acrylate monomer containing the silicone is included in an amount of 0.1% by weight or more based on the total amount of the monomer units included in the acrylic polymer. When the (meth)acrylate monomer containing the silicone is included in an amount of less than 0.1% by weight, the effect of reducing the adhesive strength of the pressure-sensitive adhesive layer may be low.

In one embodiment of the present specification, the (meth)acrylate monomer containing the silicone is included in an amount of 15% by weight or less based on the total amount of monomer units included in the acrylic polymer. When the (meth)acrylate containing the silicone is included in an amount of more than 15% by weight, the compatibility between the acrylic polymer and the urethane polymer is low, and haze may be caused in the adhesive layer.

In one embodiment of the present specification, the acrylic polymer other than the (meth)acrylate monomer containing the silicone, other monomer components polymerizable with the (meth)acrylate monomer in a range that does not inhibit the effect of the present invention (other Monomer).

In one embodiment of the present specification, the acrylic polymer further includes (meth)acrylate monomers such as alkyl (meth)acrylate, cyclohexyl (meth)acrylate, and aromatic (meth)acrylate having less than 8 carbon atoms. However, it is not limited thereto.

Examples of the alkyl (meth)acrylate having less than 8 carbon atoms are methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl ( Meth)acrylate, t-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, and the like, but are not limited thereto.

Examples of the aromatic (meth)acrylate is orthobiphenyl (meth)acrylate, metabiphenyl (meth)acrylate, parabiphenyl (meth)acrylate, 2,6-terphenyl (meth)acrylate, Olsoterphenyl (meth)acrylate, metaterphenyl (meth)acrylate, paraterphenyl (meth)acrylate, 4-(4-methylphenyl)phenyl (meth)acrylate, 4-(2-methylphenyl)phenyl ( Meth)acrylate, 2-(4-methylphenyl)phenyl(meth)acrylate, 2-(2-methylphenyl)phenyl(meth)acrylate, 4-(4-ethylphenyl)phenyl(meth)acrylate, 4- (2-ethylphenyl)phenyl (meth)acrylate, 2-(4-ethylphenyl)phenyl (meth)acrylate, 2-(2-ethylphenyl)phenyl (meth)acrylate, and the like, but are not limited thereto. .

Other (meth)acrylate monomers that may be included in the acrylic polymer include, for example, cyclohexyl (meth)acrylate, phenoxy (meth)acrylate, 2-ethylphenoxy (meth)acrylate, and benzyl (meth). Acrylate, phenyl (meth)acrylate, 2-ethylthiophenyl (meth)acrylate, 2-phenylethyl (meth)acrylate, 3-phenylpropyl (meth)acrylate, 4-phenylbutyl (meth)acrylate , 2,2-methylphenylethyl (meth)acrylate, 2,3-methylphenylethyl (meth)acrylate, 2,4-methylphenylethyl (meth)acrylate, 2-(4-propylphenyl)ethyl (meth)acrylic Late, 2-(4-(1-methylethyl)phenyl)ethyl (meth)acrylate, 2-(4-methoxyphenyl)ethyl (meth)acrylate, 2-(4-cyclohexylphenyl)ethyl (meth )Acrylate, 2-(2-chlorophenyl)ethyl (meth)acrylate, 2-(3-chlorophenyl)ethyl (meth)acrylate, 2-(4-chlorophenyl)ethyl (meth)acrylate, 2 -(4-bromophenyl)ethyl (meth)acrylate, 2-(3-phenylphenyl)ethyl (meth)acrylate, and 2-(4-benzylphenyl)ethyl (meth)acrylate, etc. It is not limited.

In one embodiment, the acrylic polymer is an alkyl (meth) acrylate monomer having less than 8 carbons; And (meth)acrylates containing silicone.

In the present specification, alkyl (meth)acrylate means CH ₂ CR ₃₁ COOR ₃₂ , and R ₃₁ is hydrogen; Or a methyl group, R ₃₂ means an alkyl group. In one embodiment, alkyl (meth)acrylates having less than 8 carbon atoms mean that R ₃₂ has less than 8 carbon atoms.

In one embodiment, the acrylic polymer is 85 to 99.9% by weight of an alkyl (meth)acrylate monomer having less than 8 carbons; And 0.1% to 15% by weight of a (meth)acrylate containing silicone.

In one embodiment of the present specification, the acrylic polymer may be polymerized using various polymerization methods commonly used, such as solution polymerization, peracid polymerization, suspension polymerization, emulsion polymerization, and radiation curing polymerization.

In the present specification, the acrylic polymer is a random copolymer (Random Copolymer) having a form in which monomers are mixed with each other without rules, a block copolymer (Block Copolymer) in which blocks arranged in a certain section are repeated, or a monomer is alternately repeated and polymerized. It may be an alternating copolymer (Alternating Copolymer) having a form.

In one embodiment, the hydroxyl value of the acrylic polymer is 0mmKOH/g.

In one embodiment of the present specification, the weight average molecular weight of the acrylic polymer is 10,000 g/mol or more; 15,000 g/mol or more; Or 20,000 g/mol or more.

In one embodiment of the present specification, the weight average molecular weight of the acrylic polymer is 70,000 g/mol or less; 60,000 g/mol or less; 55,000 g/mol or less; 50,000 g/mol or less; Or 40,000 g/mol or less.

When the molecular weight of the acrylic polymer is less than 10,000 g/mol, the adhesive may migrate from the pressure sensitive adhesive layer to the surface of the adherend to cause problems such as contamination, and if the molecular weight of the acrylic polymer is 70,000 g/mol or less, the urethane polymer It is preferable to satisfy the above range, since compatibility with and the haze generation of the adhesive layer can be minimized.

In one embodiment of the present specification, the curing agent is an isocyanate-based curing agent.

In one embodiment of the present specification, the isocyanate-based curing agent may be selected from oligomers of diisocyanate compounds, polymers, cyclic monomers, or conventional aliphatic or aromatic diisocyanate compounds, and oligomers of commercialized diisocyanate compounds. It can be obtained and used.

In one embodiment of the present specification, the isocyanate-based curing agent includes 2,4- or 2,6-toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), and xylene diisocyanate (XDI). ), an aromatic cyclic diisocyanate compound having a benzene ring such as 1,5-naphthalene diisocyanate; Aliphatic acyclic diisocyanates such as hexamethylene diisocyanate (HDI), propylene diisocyanate, lysine diisocyanate, 2,2,4- or 2,4,4-trimethylhexamerenediisocyanate; Aliphatic cyclic diisocyanate compounds such as 1,4-cyclohexane diisocyanate, isophorone diisocyanate (IPDI), and 4,4'-dicyclohexylmethane diisocyanate (H12MDI); And combinations thereof, but is not limited thereto.

In one embodiment of the present specification, the isocyanate-based curing agent includes at least one of an aliphatic cyclic isocyanate compound and an aliphatic acyclic isocyanate compound.

In one embodiment of the present specification, the pressure-sensitive adhesive composition may be used by mixing two or more isocyanate-based curing agents, and the ratio may be appropriately selected and used.

In one embodiment of the present specification, the pressure-sensitive adhesive composition further includes a solvent. As the solvent, a suitable known solvent may be used, for example, ketone-based, acetate-based, toluene-based, etc., but is not limited thereto.

In one embodiment of the present specification, the catalyst may be appropriately selected in consideration of the purpose of the present application, and may be included, for example, 10 ppm to 500 ppm compared to the urethane polymer.

As the catalyst, a tin-based catalyst such as dibutyl tin dilaurate (DBTDL), a lead-based catalyst, salts of organic and inorganic acids, organometallic derivatives, amine-based catalysts, and diazabicycloundecene-based catalysts may be used, but are not limited thereto.

In one embodiment of the present specification, the pressure-sensitive adhesive composition may further include a curing retarder. Any suitable material known may be used as the curing retardant, and the content of the curing retardant may be appropriately selected. In one embodiment, acetyl acetone may be used as the curing retarder.

In one embodiment of the present specification, the pressure-sensitive adhesive composition may further include various general additives.

In one embodiment of the present specification, the acrylic polymer is 1 part by weight or more compared to 100 parts by weight of the urethane polymer; Or 3 parts by weight or more.

In one embodiment of the present specification, the acrylic polymer is contained in 10 parts by weight or less compared to 100 parts by weight of the urethane polymer.

If the acrylic polymer is included below the above range, the effect of reducing the adhesive strength of the pressure-sensitive adhesive layer may be incomplete, and when it is included above the above range, it is preferable to satisfy the above-mentioned range since it may cause haze of the pressure-sensitive adhesive layer.

In one embodiment of the present specification, the curing agent is 1 part by weight or more compared to 100 parts by weight of the urethane polymer; 5 parts by weight or more; Or 10 parts by weight or more.

In one embodiment of the present specification, the curing agent is 25 parts by weight or less compared to 100 parts by weight of the urethane polymer; Or 20 parts by weight or less.

If the curing agent is included in the above range, there is a problem that the adhesive strength is increased due to the presence of an isocyanate group in the formed adhesive layer, and when included below the above range, the crosslinking reaction is insufficient, so that the adhesive strength of the adhesive layer at elevated temperatures may increase. have.

This specification is also an adhesive layer comprising an acrylic polymer,

The acrylic polymer provides a pressure-sensitive adhesive layer comprising a (meth)acrylate monomer containing silicon as a monomer unit.

The acrylic polymer contained in the pressure-sensitive adhesive layer may be applied to the content of the acrylic polymer contained in the pressure-sensitive adhesive composition.

In one embodiment of the present specification, the acrylic polymer contained in the pressure-sensitive adhesive layer further includes an alkyl (meth)acrylate monomer having less than 8 carbon atoms.

In one embodiment of the present specification, the pressure-sensitive adhesive layer further includes a cured product of a urethane polymer and a curing agent. Here, the contents of the urethane polymer and the curing agent included in the pressure-sensitive adhesive composition may be applied to the urethane polymer and the curing agent.

In one embodiment, the curing agent is an isocyanate-based curing agent, and the cured product of the urethane polymer and the curing agent may mean a material formed by crosslinking the OH group of the urethane polymer and the NCO group of the curing agent.

An exemplary embodiment of the present specification includes a base film and a base layer including a first anti-static layer and a second anti-static layer provided on both sides of the base film; And

A surface protection film comprising an adhesive layer provided on the opposite side of the surface of the second antistatic layer provided with the base film,

The pressure-sensitive adhesive layer includes an acrylic polymer,

The acrylic polymer provides a surface protection film comprising a (meth)acrylate monomer containing silicone as a monomer unit.

An exemplary embodiment of the present specification includes a base film and a base layer including a first anti-static layer and a second anti-static layer provided on both sides of the base film; And

A surface protection film comprising an adhesive layer provided on the opposite side of the surface of the second antistatic layer provided with the base film,

The pressure-sensitive adhesive layer provides a surface protection film that includes a cured product of the pressure-sensitive adhesive composition.

In one embodiment of the present specification, the surface protective film is a protective film, a third antistatic layer and a fourth antistatic layer provided on both sides of the protective film, and a surface provided with the protective film of the third antistatic layer Further comprising a protective layer comprising a release layer provided on the opposite side,

The protective layer may be provided so that the release layer faces the pressure-sensitive adhesive layer.

1 is a cross-sectional view of a surface protection film according to an exemplary embodiment of the present invention. The surface protection film illustrated in FIG. 1 includes a first antistatic layer 11A, a base film 111, a second antistatic layer 11B, an adhesive layer 124, a release layer 123, and a third antistatic layer 11C. , A protective film 131 and a fourth antistatic layer 11D are provided in order.

In one embodiment, the surface protection film is a surface protection film for surface protection of an organic light emitting device during an organic light emitting electronic device manufacturing process.

The pressure-sensitive adhesive layer of the present invention according to one embodiment is provided on one surface of the second antistatic layer, so that the accumulated amount of static electricity can be reduced. In addition, since the surface resistance of the pressure-sensitive adhesive layer is reduced, the generation of static electricity on the surface of the pressure-sensitive adhesive layer is reduced when the protective layer is peeled off the surface protective film.

Accordingly, when the protective layer is removed from the surface protective film in order to attach the pressure-sensitive adhesive layer to the surface of the adherend, or when the surface protective film is peeled off the surface of the adherend, foreign substances that may adhere to the pressure-sensitive adhesive layer or adherend are prevented by static electricity. can do. In addition, it is possible to prevent contamination of the surface of the adherend during the process, thereby preventing degradation of the properties of the adherend surface.

In one embodiment, the surface protection film may be used by removing the protective layer from the surface protection film and attaching the pressure-sensitive adhesive layer to the surface of the device to protect the surface. FIG. 2 shows a state in which the protective layer is removed from the surface protective film of FIG. 1.

Referring to FIG. 2, the surface protective film from which the protective layer has been removed includes the first antistatic layer 11A, the base film 111, the second antistatic layer 11B, and the adhesive layer 124 in order.

FIG. 3 illustrates a form in which the surface protection film of FIG. 2 is attached to the surface of the adherend 140 to protect the surface of the adherend.

In the present specification, the adherend means a material to which the pressure-sensitive adhesive layer can be adhered. In one embodiment, the adherend includes, but is not limited to, an encapsulation layer of an organic light emitting device and a plastic substrate applied to the device.

The type of the base film is not particularly limited. The base film is, for example, polyethylene terephthalate film, polytetrafluoroethylene film, polyethylene film, polypropylene film, polybutene film, polybutadiene film, vinyl chloride copolymer film, polyurethane film, ethylene-vinyl acetate film , Ethylene-propylene copolymer film, ethylene-acrylic acid ethyl copolymer film, ethylene-acrylic acid methyl copolymer film or polyimide film may be used, but is not limited thereto. In one embodiment of the present invention, the base film may be a polyethylene terephthalate (PET) film.

The thickness of the base film may be appropriately selected in consideration of the purpose of the present application. For example, the thickness of the base film is 25 μm or more and 150 μm or less; 50 µm or more and 125 µm or less; Or it may be 50 μm or more and 100 μm or less. When attaching the surface protective film to the encapsulation layer of the organic light emitting device, when the range of the base film is less than the above thickness range, deformation of the base film may easily occur, and when the range of the base film exceeds the above thickness range, adhesion defects may occur. Can occur.

The base film may be, for example, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment or sputter etching treatment, etc. may be performed with appropriate adhesion treatment, but is not limited thereto.

In one embodiment, the base film may be directly attached to the first and/or second antistatic layer. In another exemplary embodiment, when the base film is surface-treated, first and/or second anti-static layers may be attached to the surface-treated base film.

As used herein, the term'anti-static layer' means a layer intended to suppress the generation of static electricity.

The first to fourth antistatic layers may be formed by a known method to achieve the desired effect. For example, the first to fourth antistatic layers may be formed on both sides of the base film and both sides of the protective film by an inline coating method.

In the present invention, the first to fourth antistatic layers may be formed of an appropriate antistatic composition in consideration of the purpose of the present application. For example, the first to fourth antistatic layers are one selected from the group consisting of acrylic resins, urethane resins, urethane-acrylic copolymers, ester resins, ether resins, amide resins, epoxy resins, and melamine resins, or Mixtures of these may be included, but are not limited thereto.

In one example, the first to fourth antistatic layers may include a conductive material. The conductive material may include a conductive polymer or carbon nanotube, but is not limited thereto.

The conductive polymer may be composed of, for example, polyaniline, polypyrrole, polythiophene series, derivatives and copolymers thereof, but is not limited thereto.

The carbon nanotube may have a tube shape formed by rolling a graphite plate shape formed by connecting hexagonal rings made of 6 carbons to each other. The carbon nanotubes are excellent in stiffness and electrical conductivity, and when used as an antistatic layer of a surface protection film, the hardness of the antistatic layer increases, and an antistatic function may be improved.

The thickness of the first to fourth antistatic layers may be appropriately selected in consideration of the purpose of the present application, and the thickness of each antistatic layer may be the same or different.

In one embodiment, the thicknesses of the first to fourth antistatic layers may be independently 10 nm or more and less than 400 nm, and preferably 20 nm or more and 300 nm or less; Or it may be 20 nm or more and 100 nm or less. Since the first to fourth antistatic layers have a thickness within the above-described range, it is possible to have excellent coating properties on both sides of the base film or both sides of the protective film.

In one embodiment, the surface resistance of the first to fourth antistatic layers may be appropriately selected in consideration of the purpose of the present application. For example, the surface resistances of the first to fourth antistatic layers are each independently 10 ⁴ Pa/sq or more; 10 ⁵ Ω/sq or more; 10 ⁶ Ω/sq or more; 10 ⁷ Ω/sq or more; 10 ⁸ Ω/sq or more; Or 10 ⁹ Ω/sq or more. For example, the surface resistances of the first to fourth antistatic layers are each independently 5×10 ¹² Pa/sq or less; Or 10 ¹¹ Ω/sq or less. When the first to fourth antistatic layers have a surface resistance within the above-described range, the surface protection film may have an excellent antistatic function.

In one embodiment, the first and second antistatic layers are in direct contact with both sides of the base film, respectively. In one embodiment, the third and fourth antistatic layers are in direct contact with both sides of the protective film, respectively.

In the present invention, the thickness of the pressure-sensitive adhesive layer may be appropriately selected in consideration of the purpose of the present application. For example, the thickness of the pressure-sensitive adhesive layer is 10㎛ or more; 30 μm or more; Or 45 μm or more. For example, the thickness of the pressure-sensitive adhesive layer is 200 μm or less; 150 μm or less; 100 μm or less; Or 90 μm or less.

By setting the thickness of the pressure-sensitive adhesive layer in the above range, the pressure-sensitive adhesive and the wetting property of the pressure-sensitive adhesive layer to the adherend surface can be improved.

In the present invention, the protective layer is a protective film; And a third antistatic layer and a fourth antistatic layer provided on both sides of the protective film. A release layer is provided on a surface opposite to the surface of the third antistatic layer provided with the protective film.

The protective film is, for example, polyethylene terephthalate; Polytetrafluoroethylene; Polyethylene; Polypropylene; Polybutene; Polybutadiene; Vinyl chloride copolymer; Polyurethane; Ethylene-vinyl acetate; Ethylene-propylene copolymers; Ethylene-acrylic acid ethyl copolymer; Ethylene-methyl acrylate copolymer; Polyimide; nylon; Styrene-based resins or elastomers; Polyolefin-based resins or elastomers; Other elastomers; Polyoxyalkylene resins or elastomers; Polyester resins or elastomers; Polyvinyl chloride-based resins or elastomers; Polycarbonate-based resins or elastomers; Polyphenylene sulfide resins or elastomers; Mixtures of hydrocarbons; Polyamide-based resins or elastomers; Acrylate resins or elastomers; Epoxy resins or elastomers; Silicone-based resins or elastomers; And it may include one or more selected from the group consisting of a liquid crystal polymer, but is not limited thereto.

The thickness of the protective film may be appropriately selected in consideration of the purpose of the present application. For example, 25 μm or more and 150 μm or less; 25 µm or more and 125 µm or less; Or it may be 25 μm or more and 100 μm or less. When the thickness of the protective film is less than the above range, when the surface protective film having the pressure-sensitive adhesive layer formed on the encapsulation layer of the organic light-emitting device is bonded, there is a possibility that deformation of the protective film may occur easily. Can occur.

The material of the release layer can be appropriately selected according to the purpose of the present invention. As the material of the release layer, for example, a silicone-based release agent, a fluorine-based release agent, a long-chain alkyl-based release agent, and a fatty acid amide-based release material may be used, but are not limited thereto. In one embodiment, a silicone-based release agent may be used as a material for the release layer.

As the silicone-based release agent, for example, an addition-reactive silicone polymer can be used.

The release layer may be formed by applying the release layer material to, for example, a protective layer and drying it. Any suitable coating method may be appropriately used as the coating and drying method of the release layer material.

The thickness of the release layer may be appropriately selected in consideration of the purpose of the present application. For example, the thickness of the release layer is 10 nm or more and 500 nm or less; 10 nm or more and 300 nm or less; Or it may be 10 nm or more and 200 nm or less. If the release layer does not have the aforementioned thickness, defects in the film may occur during the process.

In the present specification, unless otherwise specified,'glass' may mean an alkali-free glass (NEG, OA-21).

In the surface protection film according to the exemplary embodiment of the present specification, peeling when peeling the opposite surface of the surface of the pressure-sensitive adhesive layer provided with the base layer at a peeling speed of 1.8 m/min and a peeling angle of 180° from glass The force is more than 0.5gf/in.

In the surface protection film according to the exemplary embodiment of the present specification, peeling when peeling the opposite surface of the surface of the pressure-sensitive adhesive layer provided with the base layer at a peeling speed of 1.8 m/min and a peeling angle of 180° from glass Force is less than 10gf/in; 7 gf/in or less; 5 gf/in or less; Or 4.5 gf/in or less.

In one embodiment, the peeling force when peeling the opposite side of the surface of the pressure-sensitive adhesive layer provided with the base layer from the glass at a peeling rate of 1.8 m/min and a peeling angle of 180° widens the surface protective film. After cutting to 25 mm and a length of 150 mm, the pressure-sensitive adhesive layer of the surface protection film was attached to the glass with a roller of 2 kg, and stored at a temperature of 25° C. and 50% relative humidity for 24 hours, and then a material property analyzer ( Texture Analyzer, manufactured by Stable Microsystems, UK), which is the peeling force when the surface protective film is peeled from the glass at a peeling rate of 1.8 m/min and a peeling angle of 180°.

In one embodiment, the peeling force when the surface protective film is peeled from the glass at a peeling rate of 1.8 m/min and a peeling angle of 180° is a value measured under a temperature of 25° C. and a relative humidity of 50%. .

In the surface protection film according to an exemplary embodiment of the present specification, the residual ratio of the surface opposite to the surface provided with the base layer of the pressure-sensitive adhesive layer is 80% or more; 85% or more; over 90; Or 92% or more.

In the surface protection film according to the exemplary embodiment of the present specification, a residual ratio of a surface opposite to a surface provided with the base layer of the pressure-sensitive adhesive layer is 100% or less. A residual ratio of 100% means that there is no residual amount of the pressure-sensitive adhesive layer.

In one embodiment of the present specification, the residual ratio of the surface opposite to the surface of the pressure-sensitive adhesive layer provided with the base layer has a peeling force when peeling from the glass at a peeling rate of 1.8 m/min and a peeling angle of 180°. After preparing an adhesive (Ref.) of 1,800±100gf/in, and measuring adhesive strengths (A) and (B) as follows, it can be obtained by calculating the following formula (4)

The adhesive strength (B) is after attaching the pressure-sensitive adhesive layer of the surface protection film to the glass and storing for 10 days at a temperature of 60° C. and a relative humidity of 90%, the surface protection film is removed from the glass, and the surface It is the peeling force when attaching the adhesive (Ref.) to the glass surface from which the protective film has been removed, and peeling the adhesive (Ref.) from the glass at a peeling rate of 1.8 m/min and a peeling angle of 180°. ,

The adhesive force (A) is the peel force when the adhesive (Ref.) is peeled from the glass at a peel rate of 1.8 m/min and a peel angle of 180°.

[Formula 4]

Residue (%) = (Adhesive Force (B)/Adhesive Force (A))×100

In one embodiment, as a pressure-sensitive adhesive (Ref.) having a peeling force of 1,800±100 gf/in when peeling from a glass at a peeling rate of 1.8 m/min and a peeling angle of 180°, 9002D products of LG Chem. However, it is not limited thereto.

In one embodiment, the peel strength when peeling the pressure-sensitive adhesive (Ref.) from the glass at a peel rate of 1.8 m/min and a peel angle of 180° was measured under a temperature of 25° C. and a relative humidity of 50%. Is the value.

Another exemplary embodiment of the present specification provides a method of manufacturing a surface protection film. The said manufacturing method relates to the manufacturing method of the surface protection film mentioned above, for example. Therefore, the contents of the above-described surface protection film may be equally applied to the surface protection film formed by the method for manufacturing a surface protection film described below.

In one example, the method of manufacturing the surface protection film includes forming a base film, and a base layer including a first antistatic layer and a second antistatic layer provided on both sides of the base film, respectively; A protective layer comprising a protective film, a third antistatic layer and a fourth antistatic layer provided on both sides of the protective film, and a release layer provided on a surface opposite to the surface of the third antistatic layer provided with the protective film To do; And bonding the base layer and the protective layer by an adhesive layer so that the second antistatic layer and the release layer face each other.

In one embodiment, the method for manufacturing a surface protective film comprises forming an adhesive layer on one surface of the second antistatic layer of the base layer before the step of bonding the base layer and the protective layer by the adhesive layer. It may further include. In this case, the step of bonding the base layer and the protective layer may be a step of bonding the base layer and the protective layer so that the pressure-sensitive adhesive layer and the release layer face each other.

The step of forming an adhesive layer on one surface of the second antistatic layer of the base layer may include coating the adhesive composition on the opposite side of the surface on which the base film of the second antistatic layer is provided; And curing the coated adhesive composition.

As a method of coating the pressure-sensitive adhesive composition, a known coating method such as a reverse coating method, a gravure coating method, a spin coating method, a screen coating method, a fountain coating method, a dipping method, or a spray method can be used, but is not limited thereto.

Curing of the coated pressure-sensitive adhesive composition may be performed at an appropriate temperature and time. In one embodiment, curing of the coated pressure-sensitive adhesive composition may be performed through aging for 3 days or more in an oven at 40° C., but is not limited thereto.

In one embodiment, the base film and a base layer comprising a first antistatic layer and a second antistatic layer, respectively provided on both sides of the base film; And the pressure-sensitive adhesive layer provided on the opposite side of the surface opposite to the base film of the second antistatic layer can be prepared by peeling the protective layer from the surface protection film including the above-described protective layer and release layer. have.

An exemplary embodiment of the present specification provides a method of manufacturing an organic light emitting electronic device.

In one embodiment of the present specification, the method of manufacturing an organic light emitting electronic device includes attaching the pressure-sensitive adhesive layer of the above-described surface protective film on the encapsulation layer of the organic light emitting element.

In one embodiment, when the surface protective film further includes a protective layer, the method of manufacturing the organic light emitting electronic device removes the protective layer from the surface protective film before the step of attaching the pressure-sensitive adhesive layer on the encapsulation layer. Further comprising steps.

In one embodiment of the present specification, the organic light emitting device sequentially includes a back plate, a plastic substrate, a thin film transistor, an organic light emitting diode, and an encapsulation layer.

4 is a view exemplarily showing a state in which a surface protective film according to an embodiment of the present invention is attached to an encapsulation layer during an organic light emitting electronic device manufacturing process. Referring to FIG. 4, the surface protection film of FIG. 2 according to an exemplary embodiment of the present invention includes a back plate 511, a plastic substrate 512, a thin film transistor 513, an organic light emitting diode 514 and an encapsulation layer 515 ) Is sequentially attached to the sealing layer 515 of the organic light emitting device 510 including the pressure-sensitive adhesive layer and the sealing layer.

The encapsulation layer may exhibit excellent moisture barrier properties and optical properties in the organic light emitting electronic device. In addition, the encapsulation layer may be formed of a stable encapsulation layer regardless of the form of an organic light emitting electronic device such as top emission or bottom emission.

In one embodiment, the encapsulation layer may include a single layer or a multi-layered inorganic material layer. As a method of forming the encapsulation layer, a method of forming a conventional encapsulation layer known in the art may be applied.

The single or multi-layered inorganic material layer may include, for example, an aluminum oxide system, a silicon-nitride compound system, a silicon oxide oxynitride system, or the like.

A method of manufacturing an organic light emitting electronic device of the present application includes the steps of peeling the surface protective film from the encapsulation layer; And laminating a touch screen panel and a cover window on the encapsulation layer. Since the surface protection film exhibits an excellent antistatic function to the encapsulation layer when peeled from the encapsulation layer, when attaching a touch screen panel on the encapsulation layer, it prevents foreign matter from adhering between the encapsulation layer and the touch screen, thereby preventing device defects. Can be prevented.

Hereinafter, the present application will be described in more detail through examples according to the present application and comparative examples not according to the present application, but the scope of the present application is not limited by the examples presented below.

Preparation Example 1-Preparation of pressure-sensitive adhesive composition 1

<Preparation of urethane polymer>

80 parts by weight of trifunctional preminol (polyether polyol, S 4013F, ASAHI GLASS CO. LTD., Mn=12,000 g/mol) in a three-necked flask filled with nitrogen gas, bifunctional polyol (polypropylene glycol, PPG-1000d, Kumho Petrochemical, Mn=1,000g/mol) 5 parts by weight and a mixture of trifunctional MPD/TMPT-based polyol (MPD(3-methyl-1,5-pentanediol) and TMPT (trimethylol propane adipate), Polyol F-3010, Kuraray, Mn=3,000 g/mol) 15 parts by weight and ethyl acetate were added and stirred at a high speed for 15 minutes under a catalyst (DBTDL). Next, 18 parts by weight of the polyfunctional alicyclic isocyanate compound (MHG-80B, ASAHI KASEI) compared to 100 parts by weight of the preminol, polyol, and MPD/TMPT-based polyol was slowly added dropwise and heated at 90±5° C. for 3 hours and isocyanate The reaction was performed until the (NCO) peak disappeared to prepare a urethane polymer having a weight average molecular weight of 110,000 g/mol.

<Preparation of acrylic polymer (D1)>

Acrylate FM-0721 containing 98 parts by weight of butyl methacrylate (BMA) and silicone in a 1L reactor in which a nitrogen gas is refluxed and a cooling device is installed to facilitate temperature control, and Mn=5,000 g/mol by CHISSO 2 After adding the monomer mixture composed of parts by weight, ethyl acetate was added as a solvent. Then, nitrogen gas was purged for about 1 hour to remove oxygen, and then the reactor temperature was maintained at 62°C. After homogenizing the mixture, 400 ppm of azobisisobutylnitrile (AIBN) as a reaction initiator and 400 ppm of n-dodecylmercaptan (n-DDM) were added as a chain transfer agent, and the mixture was reacted. After the reaction, it was diluted with toluene to prepare an acrylic polymer (D1) having a weight average molecular weight of 32,000 g/mol.

<Preparation of adhesive composition 1>

100 parts by weight of the prepared urethane polymer, 15 parts by weight of HDI Trimer-based curing agent (TKA-100, ASAHI KASEI), 100 parts by weight of the urethane polymer, 7.5 parts by weight of the acrylic polymer, 0.005 parts by weight of catalyst (DBTDL) and curing delay Mixing 3 parts by weight of the agent (acetyl acetone), a toluene solvent was added so that the solid content concentration was 48 wt%, and the mixture was stirred with a disper to prepare an adhesive composition 1.

Preparation Example 2-Preparation of pressure-sensitive adhesive composition 2

An acrylic polymer (D2) having a weight average molecular weight of 35,000 g/mol was prepared in the same manner as the method for preparing an acrylic polymer (D1), except that the weight ratio of BMA and FM-0721 was 95:5 instead of 98:2.

The pressure-sensitive adhesive composition 2 was prepared in the same manner as the method for preparing the pressure-sensitive adhesive composition 1, except that the acrylic polymer (D2) was used instead of the acrylic polymer (D1).

Preparation Example 3-Preparation of pressure-sensitive adhesive composition 3

An acrylic polymer (D3) having a weight average molecular weight of 30,000 g/mol was prepared in the same manner as the method for preparing an acrylic polymer (D1), except that the weight ratio of BMA and FM-0721 was 92.5:7.5 instead of 98:2.

The pressure-sensitive adhesive composition 3 was prepared in the same manner as in the pressure-sensitive adhesive composition 1, except that the acrylic polymer (D3) instead of the acrylic polymer (D1) was used in an amount of 9 parts by weight compared to 100 parts by weight of the urethane polymer.

Preparation Example 4-Preparation of pressure-sensitive adhesive composition 4

An acrylic polymer (D4) having a weight average molecular weight of 28,000 g/mol was prepared in the same manner as the method for preparing an acrylic polymer (D1), except that the weight ratio of BMA and FM-0721 was 90:10 instead of 98:2.

The pressure-sensitive adhesive composition 4 was prepared in the same manner as in the pressure-sensitive adhesive composition 1, except that the acrylic polymer (D4) was used instead of the acrylic polymer (D1).

Preparation Example 5-Preparation of adhesive composition 5

An acrylic polymer (D5) having a weight average molecular weight of 33,000 g/mol was prepared in the same manner as the method for preparing an acrylic polymer (D1), except that the weight ratio of BMA and FM-0721 was 87.5:12.5 instead of 98:2.

The pressure-sensitive adhesive composition 5 was prepared in the same manner as in the pressure-sensitive adhesive composition 1, except that the acrylic polymer (D5) instead of the acrylic polymer (D1) was used in an amount of 5 parts by weight compared to 100 parts by weight of the urethane polymer.

Comparative Preparation Example 1-Preparation of Comparative Composition 1

Comparative composition 1 was prepared in the same manner as in the method of preparing the adhesive composition 1, except that the acrylic polymer (D1) was not used.

Comparative Preparation Example 2- Preparation of Comparative Composition 2

Comparative composition 2 was prepared in the same manner as in the method of preparing the pressure-sensitive adhesive composition 1, except that isopropyl myristate (IPMS) was used in an amount of 20 parts by weight compared to 100 parts by weight of the urethane polymer instead of the acrylic polymer (D1).

Comparative Preparation Example 3-Preparation of Comparative Composition 3

Comparative composition 3 was prepared in the same manner as in the method of preparing the pressure-sensitive adhesive composition 1, except that isopropyl myristate (IPMS) was used in an amount of 40 parts by weight compared to 100 parts by weight of the urethane polymer instead of the acrylic polymer (D1).

Comparative Preparation Example 4-Preparation of Comparative Composition 4

An acrylic polymer (D6) having a weight average molecular weight of 36,000 g/mol was prepared in the same manner as the method for preparing an acrylic polymer (D1), except that only BMA was used instead of BMA and FM-0721.

The pressure-sensitive adhesive composition 5 was prepared in the same manner as in the pressure-sensitive adhesive composition 1, except that the acrylic polymer (D6) was used instead of the acrylic polymer (D1).

Preparation of surface protection film

As a base layer, a polyethylene terephthalate (PET) film (H330, Kolon Corporation) having a thickness of 75 µm coated with an antistatic layer of 50 nm on both sides of the base film was prepared. As a protective layer, an antistatic layer is formed on both sides of a 50 µm thick polyethylene terephthalate (PET) film (XD510P, TAK), and a release layer coated film (12ASW, SKC) is prepared on one antistatic layer. Did. Next, after comma coating the pressure-sensitive adhesive composition on one surface of the substrate layer to a thickness of 75 μm and drying with hot air, the protective layer is laminated on the pressure-sensitive adhesive composition so that the substrate layer and the release layer face each other, and aged at 40° C. for 5 days. After that, a surface protection film was prepared.

The surface protective films of Examples 1 to 5 and Comparative Examples 1 to 4 were prepared in the same manner as the method of manufacturing the surface protective film, except that the pressure-sensitive adhesive composition was set to the pressure-sensitive adhesive composition 1 to 5 and Comparative Compositions 1 to 4. Table 1 below briefly compares the configurations of Examples 1 to 5 and Comparative Examples 1 to 4.

The physical properties of the pressure-sensitive adhesive layer in Examples and Comparative Examples of the present application were evaluated in the following manner, and the results are shown in Table 2 below.

Measurement of peel force

The surface protective films of Examples 1 to 5 and Comparative Examples 1 to 4 were cut to have a width of 25 mm and a length of 150 mm. Subsequently, the pressure-sensitive adhesive layer of the surface protection film was attached to the glass using a 2 kg roller, and stored at room temperature for about 24 hours. Subsequently, using a device (Texture Analyzer, manufactured by Stable Micro Systems, UK), the base film on which the pressure-sensitive adhesive layer was formed was peeled from the glass at a peeling rate of 1.8 m/min and a peeling angle of 180° to evaluate a low-speed peeling force. . The peel force was measured for two identical specimens, and the average value was employed.

Residual rate measurement

An adhesive (Ref.) having a peeling force of 1,800±100 gf/in when peeling from a glass at a peeling speed of 1.8 m/min and a peeling angle of 180° is prepared.

Measurement of adhesive force (B): After attaching the pressure-sensitive adhesive layer of the prepared surface protection film to the glass and storing for 10 days at a temperature of 60° C. and a relative humidity of 90%, the surface protection film is removed from the glass. The pressure-sensitive adhesive (Ref.) was attached to the glass surface from which the surface protection film had been removed, and peeling force was evaluated while peeling at a peeling rate of 1.8 m/min and a peeling angle of 180°. Let this be the adhesive force (B).

Measurement of adhesive force (A): The adhesive force when attaching the adhesive (Ref.) to the glass, and peeling the adhesive (Ref.) from the glass at a peeling rate of 1.8 m/min and a peeling angle of 180° Was evaluated. Let this be the adhesive force (A).

The adhesive force (A) and (B) were substituted into the following formula to obtain a residual ratio.

Residue (%) = (Adhesive Force (B)/Adhesive Force (A))×100

Acrylic polymer molecular weight
(g/mol) Monomer type (weight ratio) Acrylic polymer
Content (Middle Rangbu) Plasticizer type
(Parts by weight) Example 1 3.2 million BMA/FM-0721
(98:2) 7.5 - Example 2 3.5 million BMA/FM-0721 (95:5) 7.5 - Example 3 3.0 million BMA/FM-0721 (92.5:7.5) 9 - Example 4 2.8 million BMA/FM-0721 (90:10) 7.5 - Example 5 3.3 million BMA/FM-0721 (87.5:12.5) 5 - Comparative Example 1 - - - - Comparative Example 2 - - - IPMS(20) Comparative Example 3 - - - IPMS(40) Comparative Example 4 3.6 million BMA
(100) 7.5 -

Peeling force (gf/in) Residual rate (%) Example 1 2.5 93 Example 2 4.2 94 Example 3 2.4 92 Example 4 2.1 95 Example 5 3.0 92 Comparative Example 1 14 92 Comparative Example 2 6.2 78 Comparative Example 3 4.3 68 Comparative Example 4 13 88

When the surface protection film of the present invention is used from Table 2, the adhesive strength between the pressure-sensitive adhesive layer and the adherend is low, so that the film can be peeled with low peel strength, and there is little residue from the pressure-sensitive adhesive layer after peeling, so that contamination of the adherend surface is small. Can be confirmed.

11A: first antistatic layer
11B: second antistatic layer
11C: Third antistatic layer
11D: 4th antistatic layer
110: base layer
111: base film
123: release layer
124: adhesive layer
130: protective layer
131: protective film
140: adherend
510: organic light emitting device
511: back plate
512: plastic substrate
513: thin film transistor
514: organic light emitting diode
515: sealing layer

Claims (17)

Urethane polymers; Acrylic polymers; And a curing agent,
The acrylic polymer is a pressure-sensitive adhesive composition comprising a silicone (meth) acrylate monomer as a monomer unit. The method according to claim 1, The unit derived from the (meth) acrylate monomer containing the silicone is a pressure-sensitive adhesive composition represented by the formula (3):
[Formula 3]

In Chemical Formula 3,
R ₁ to R ₇ are the same as or different from each other, and each independently an alkyl group,
R ₈ is hydrogen or a methyl group,
n is an integer greater than or equal to 0,
L is a divalent saturated hydrocarbon group of straight or branched chain; A divalent monocyclic aliphatic saturated hydrocarbon group; A divalent polycyclic saturated hydrocarbon group; A divalent aromatic hydrocarbon group; A bivalent group of a ring in which an aromatic hydrocarbon is condensed with cyclic saturated hydrocarbon; -O-; -C(=O)-; -C(=O)-O-; Or -S-, or two or more of the groups are linked groups. The method according to claim 1, the number average molecular weight of the (meth) acrylate monomer containing the silicone is a pressure-sensitive adhesive composition will be from 500g / mol to 10,000g / mol. The method according to claim 1, wherein the (meth) acrylate monomer containing the silicone is a pressure-sensitive adhesive composition that is contained in an amount of 0.1 to 15% by weight relative to the total amount of monomer units contained in the acrylic polymer. The method according to claim 1, wherein the weight average molecular weight of the acrylic polymer is 10,000g / mol to 70,000g / mol pressure-sensitive adhesive composition. The method according to claim 1, wherein the weight average molecular weight of the urethane polymer is 60,000g / mol to 160,000g / mol pressure-sensitive adhesive composition. The method according to claim 1, wherein the acrylic polymer is a pressure-sensitive adhesive composition that is contained in 1 part by weight to 10 parts by weight relative to 100 parts by weight of the urethane polymer. The method according to claim 1, wherein the curing agent is a pressure-sensitive adhesive composition that is contained in 1 part by weight to 25 parts by weight relative to 100 parts by weight of the urethane polymer. As an adhesive layer comprising an acrylic polymer,
The acrylic polymer is a pressure-sensitive adhesive layer comprising a (meth)acrylate monomer containing silicon as a monomer unit. The pressure-sensitive adhesive layer of claim 9, wherein the pressure-sensitive adhesive layer further comprises a cured product of a urethane polymer and a curing agent. A base layer comprising a base film and a first antistatic layer and a second antistatic layer provided on both sides of the base film; And
As a surface protection film comprising an adhesive layer provided on the opposite surface of the surface of the second anti-static layer provided with the base film,
The pressure-sensitive adhesive layer is a surface protective film that is the pressure-sensitive adhesive layer according to claim 9. The method according to claim 11, A protective film, a third anti-static layer and a fourth anti-static layer provided on both sides of the protective film, and a release layer provided on the opposite side of the surface provided with the protective film of the third anti-static layer And further comprising a protective layer,
The protective layer is a surface protection film that the release layer is provided to face the pressure-sensitive adhesive layer. The method according to claim 11, Peeling force when peeling the opposite side of the surface of the pressure-sensitive adhesive layer provided with the base layer from the glass at a peeling rate of 1.8 m / min and a peeling angle of 180 ° is 0.5gf / in or more 10gf / In or less surface protection film. The surface protection film according to claim 11, wherein a residual ratio of a surface opposite to a surface provided with the base layer of the pressure-sensitive adhesive layer is 80% or more. A method of manufacturing an organic light emitting electronic device comprising the step of attaching the pressure-sensitive adhesive layer of the surface protection film according to claim 11 on an encapsulation layer of an organic light emitting device. 16. The method of claim 15, wherein the organic light emitting device sequentially comprises a back plate, a plastic substrate, a thin film transistor, an organic light emitting diode, and an encapsulation layer. The method according to claim 15, Peeling the surface protective film from the sealing layer; And laminating a touch screen panel and a cover window on the encapsulation layer.

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