KR20190019408A - Adhesive Composition and Adhesive Film Using the Same - Google Patents

Abstract

The present invention provides an adhesive composition comprising an antistatic agent, a silicone urethane (meth) acrylate resin, a (meth) acrylate ester monomer and a photoinitiator, and an adhesive film using the same. The adhesive film according to the present invention is excellent in antistatic properties and durability and has small peeling force.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a pressure-sensitive adhesive composition,

The present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive film using the pressure-sensitive adhesive composition, and more particularly, to a pressure-sensitive adhesive composition having excellent antistatic properties and durability and a small peeling force.

An organic light-emitting diode (OLED), which is attracting attention as a next-generation flat panel display, is a diode-type device formed by depositing an organic material between an anode and a cathode or by forming a film through a solution process and laminating . Since OLEDs are self-emissive, they have excellent viewing angle and contrast ratio and can simplify the process, making them lightweight and thin.

A protective film is attached to the surface of the OLED through a pressure-sensitive adhesive layer in order to prevent scratches or contamination on the surface during transportation or manufacturing processes. The protective film is peeled off when the protective film is finished. At this time, since the protective film is made of a plastic material, static electricity is generated at the time of peeling. The generated static electricity may adsorb foreign matter on the surface of the OLED to contaminate its surface or damage the internal circuit of the OLED. Accordingly, there is an increasing interest in a protective film having a pressure-sensitive adhesive layer having a small peeling force while exhibiting antistatic properties.

For example, Korean Patent Registration No. 10-0926022 discloses a protective film comprising a pressure-sensitive adhesive layer containing an ionic antistatic agent. The protective film is obtained by applying a pressure-sensitive adhesive composition containing a solvent to form a pressure-sensitive adhesive layer on a substrate. However, the pressure-sensitive adhesive composition containing such a solvent has a problem in that it is difficult to obtain the thickness of the pressure-sensitive adhesive layer at a level of several tens of micrometers. In addition, the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition has a problem of poor durability.

Therefore, there is a demand for development of a pressure-sensitive adhesive composition of a solvent-free type having excellent antistatic property and durability and a small peeling force.

Korean Patent Registration No. 10-0926022

An object of the present invention is to provide a pressure-sensitive adhesive composition of a solvent-free type having excellent antistatic property and durability and a small peeling force.

Another object of the present invention is to provide a pressure-sensitive adhesive film formed using the pressure-sensitive adhesive composition.

On the other hand, the present invention provides a pressure-sensitive adhesive composition comprising an antistatic agent, a silicone urethane (meth) acrylate resin, a (meth) acrylate ester monomer and a photoinitiator.

In one embodiment of the present invention, the silicone urethane (meth) acrylate resin may be a reaction product of (meth) acrylate having a hydroxyl group at both ends with polysilicon having a hydroxyl group, a polyisocyanate, and a hydroxyl group.

On the other hand, the present invention provides a pressure-sensitive adhesive film comprising a base film and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition on the base film.

The pressure-sensitive adhesive composition according to the present invention includes an antistatic agent and a silicone urethane (meth) acrylate resin, and has excellent antistatic property and durability and a small peel force. Also, since the pressure-sensitive adhesive composition according to the present invention is a solventless type, it is advantageous to form a pressure-sensitive adhesive layer having a thickness of several tens of micrometers.

Hereinafter, the present invention will be described in more detail.

An embodiment of the present invention relates to a pressure-sensitive adhesive composition comprising an antistatic agent (A), a silicone urethane (meth) acrylate resin (B), a (meth) acrylate ester monomer (C) and a photoinitiator (D).

The antistatic agent (A)

In one embodiment of the present invention, the kind of the antistatic agent (A) is not particularly limited, and examples thereof include 1-hexyl-4-methylpyridinium hexafluorophosphate, dodecylpyridinium hexafluorophosphate, fluorinated organic A metal oxide such as indium-doped tin oxide (ITO), a metal compound (e.g., HQ-115 of 3M Company), an alkali metal salt, an alkaline earth metal salt, a conductive polymer (e.g., polythiophene (PEDOT of Bayer), polyaniline, ), Quaternary ammonium salts (e.g., poly (acrylamide-co-diallyldimethylammonium chloride) solution of Sigma-Aldrich), antioxidants such as antimony doped tin oxide (ATO), tin oxide, zinc oxide, antimony oxide, indium oxide, Butyl-3-methylimidazolium hexafluorophosphate [BMIM] [PF ₆ ], 1-butyl-3- (2-hydroxyethyl) imidazolium bis (trifluoromethanesulfonyl) imide [ BHEIM] [NTf _2], tetra-butyl methyl ammonium bis (trifluoromethyl Tansul sulfonyl) already and the like de [TBMA] [NTf _2], these may be used alone or in mixture of two or more.

In particular, in consideration of compatibility with the resin, the antistatic agent (A) may include an alkali metal salt or an alkaline earth metal salt.

Examples of the alkali metal salt or alkaline earth metal salt include compounds represented by the following general formula (1).

[Chemical Formula 1]

_{M [(FSO 2) 2 N} ] p

In this formula,

M is an alkali metal or an alkaline earth metal,

p is an integer of 1 to 2;

The alkali metal used in the present invention refers to an element other than hydrogen among the group 1 of the periodic table and includes, but is not limited to, lithium (Li), sodium (Na), potassium (K) and the like.

The alkaline earth metal used in the present invention refers to a Group 2 element of the periodic table and includes, but is not limited to, magnesium (Mg) and calcium (Ca).

Specifically, the compound represented by Formula 1 is _{Li [(FSO 2) 2 N} ], Na [(FSO 2) 2 N], K [(FSO 2) 2 N], Ca [(FSO 2) 2 N] _2, or Mg [(FSO ₂ ) ₂ N] _{2. In} particular, Li [(FSO ₂ ) ₂ N] can be used in consideration of compatibility with resins and antistatic performance. These may be used alone or in combination of two or more.

The antistatic agent (A) may be contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the total amount of the silicone urethane (meth) acrylate resin (B) and the (meth) acrylate ester monomer (C). If the antistatic agent is contained in an amount of less than 1 part by weight, antistatic properties may not be exhibited. If the antistatic agent is contained in an amount of more than 10 parts by weight, stability with time of the pressure-sensitive adhesive composition may deteriorate.

Silicone Urethane ( Meta ) Acrylate  Resin (B)

In one embodiment of the present invention, the silicone urethane (meth) acrylate resin (B) may be a resin having a silicon bond (-Si-O-) and a urethane group in the molecule and a (meth) acryloyloxydiaryl group have.

The silicone urethane (meth) acrylate resin (B) has a silicon bond having a large bonding angle, and thus has a large binding energy. Accordingly, the silicone urethane (meth) acrylate resin (B) can improve the durability of the pressure-sensitive adhesive composition and can advantageously provide low stickiness.

The silicone urethane (meth) acrylate resin (B) may be a reaction product of a polysilicon (b1) having a hydroxyl group at both terminals, a polyisocyanate (b2), and a (meth) acrylate having a hydroxyl group (b3).

The polysilicon (b1) having a hydroxyl group at both terminals may be a compound represented by the following formula (3).

(3)

In this formula,

R ¹ and R ³ are each independently a C ₁ -C ₁₀ alkylene group or a C ₁ -C ₁₀ oxyalkylene group,

R ² is a C ₁ -C ₁₀ alkyl group, a C ₃ -C ₁₀ cycloalkyl group or an aryl group,

n is an integer of 1 to 30;

As used herein, a C ₁ -C ₁₀ alkylene group means a linear or branched divalent hydrocarbon having 1 to 10 carbon atoms and includes, for example, methylene, ethylene, propylene, butylene, pentylene and the like However, the present invention is not limited thereto.

As used herein, a C ₁ -C ₁₀ oxyalkylene group means a functional group in which at least one of the chain carbons in the linear or branched divalent hydrocarbon having 1 to 10 carbon atoms is substituted with oxygen, for example, ethyl Propyloxyethyl, and the like, but is not limited thereto.

As used herein, a C ₁ -C ₁₀ alkyl group means a linear or branched monovalent hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl , i-butyl, t-butyl, n-pentyl, n-hexyl, and the like.

C ₃ -C ₁₀ cycloalkyl group as used herein means a simple or fused ring hydrocarbon having 3 to 10 carbon atoms and includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like, It is not.

As used herein, an aryl group includes both an aromatic group and a heteroaromatic group and a partially reduced derivative thereof. The arromatic group is a simple or fused ring of 5 to 15 members, and the heteroaromatic group means an aromatic group containing at least one of oxygen, sulfur or nitrogen. Exemplary aryl groups include, but are not limited to, phenyl, naphthyl, pyridinyl, furanyl, thiophenyl, indolyl, quinolinyl, imidazolinyl, But are not limited to, oxazolyl, thiazolyl, tetrahydronaphthyl, and the like.

The weight average molecular weight of the polysilicon (b1) having a hydroxyl group at both terminals may be 800 to 2,000. If the weight-average molecular weight of the polysilicon (b1) having a hydroxyl group at both ends is less than 800, the crosslinking density may increase and the adhesive force may be difficult to achieve. If the weight average molecular weight is more than 2,000, unreacted monomers may degrade durability and peeling force have.

As the polyisocyanate (b2), aliphatic diisocyanate, alicyclic diisocyanate and / or aromatic diisocyanate can be used.

Examples of the aliphatic diisocyanate include methyl diisocyanate, 1,2-ethanediyl diisocyanate, 1,3-propanediyl diisocyanate, 1,6-hexanediyl diisocyanate, 3-methyl-octane-1,8-diyl diisocyanate And the like.

Examples of the alicyclic diisocyanate include 1,2-cyclopropanediyl diisocyanate, 1,3-cyclobutanediyl diisocyanate, 1,4-cyclohexanediyl diisocyanate, 1,3-cyclohexanediyl diisocyanate, Isocyanate, 4-methyl-cyclohexane-1,3-diyl diisocyanate, and the like.

Examples of the aromatic diisocyanate include 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 3-chloro-1,2-benzene diisocyanate, , 2-benzene diisocyanate, 5-chloro-1,2-benzene diisocyanate, 2-chloro-1,3-benzene diisocyanate, 4-chloro-1,3-benzene diisocyanate, Benzene diisocyanate, 3-chloro-1,4-benzene diisocyanate, 3-methyl-1,2-benzene diisocyanate, 4-methyl- 1,2-benzene diisocyanate, 2-methyl-1,3-benzene diisocyanate, 4-methyl-1,3-benzene diisocyanate, 5-methyl-1,3-benzene diisocyanate Benzene diisocyanate, 3-methyl-1,4-benzene diisocyanate, 3-methoxy-1,2-benzene diisocyanate, 4-methoxy- Methoxy-1,2-benzene diisocyanate, 2-methoxy-1,3-benzene diisocyanate, 4-methoxy-1,3-benzene diisocyanate, 5-methoxy- Benzene diisocyanate, 3-methoxy-1,4-benzene diisocyanate, 3,4-dimethyl-1,2-benzene diisocyanate, 4,5-dimethyl Benzene diisocyanate, 2,3-dimethyl-1,4-benzene diisocyanate, 3-chloro-4-methyl-1,2-benzene diisocyanate, Benzene diisocyanate, 4-chloro-5-methoxy-1,3-benzene diisocyanate, 3-methyl- Benzene diisocyanate, 5-chloro-2-fluoro-1,3-benzene diisocyanate, 2-chloro-3- 4-benzene diisocyanate, 2,3-diisocyanate pyridine, Diisocyanate-3-methylpyridine, 2,5-diisocyanate-4-methylpyridine, 2, 2-diisocyanate, 5-diisocyanate-6-methylpyridine, and the like.

Particularly, as the polyisocyanate (b2), an alicyclic diisocyanate such as isophorone diisocyanate can be used in consideration of compatibility, durability and peelability.

The (meth) acrylate (b3) having a hydroxy group is used to introduce a (meth) acryloyloxydane group into the silicone urethane (meth) acrylate resin (B).

Examples of the (meth) acrylate (b3) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3- (Meth) acrylic acid alkyl esters having a hydroxyl group such as butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate; Polyfunctional (meth) acrylates having a hydroxyl group such as trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate; Polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, and the like.

In one embodiment of the present invention, the silicone urethane (meth) acrylate resin may be a compound represented by the following formula (2).

(2)

In this formula,

R ¹ and R ³ are each independently a C ₁ -C ₁₀ alkylene group or a C ₁ -C ₁₀ oxyalkylene group,

R ² is a C ₁ -C ₁₀ alkyl group, a C ₃ -C ₁₀ cycloalkyl group or an aryl group,

R < ⁴ > is hydrogen or methyl,

n is an integer of 1 to 30;

In one embodiment of the present invention, R ¹ and R ³ are each independently a C ₁ -C ₁₀ oxyalkylene group, and R ² may be a C ₁ -C ₁₀ alkyl group.

Yi In one embodiment of the present _{^{invention, R 1 - (CH 2)}} 2 -O- (CH 2) 3 - , and, R ³ is _{- (CH 2) 3 -O- (} CH 2) 2 - , and, R ² May be methyl.

The silicone urethane (meth) acrylate resin (B) can be produced, for example, by dissolving the polysilicon (b1) having a hydroxyl group at both ends of the ends and the (meth) acrylate (b3) The polyisocyanate (b2) is fed, mixed and reacted, or the polyisocyanate (b2) having a hydroxy group at both ends is reacted with the polyisocyanate (b2) under a solventless condition to obtain a urethane prepolymer having an isocyanate group (B3) having a hydroxyl group, followed by mixing and reacting the (meth) acrylate (b3). The reaction may be carried out at 20 to 120 ° C for 30 minutes to 24 hours.

In the production of the silicone urethane (meth) acrylate resin (B), a polymerization inhibitor, a urethanization catalyst and the like may be used if necessary.

Examples of the polymerization inhibitor include 3,5-bis-tert-butyl-4-hydroxytoluene, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether (methoquinone), para-tert- butylcatechol methoxyphenol, 6-di-tert-butylcresol, phenothiazine, tetramethylthiuram disulfide, diphenylamine, dinitrobenzene, methoxyhydroquinone and the like can be used.

Examples of the urethanization catalyst include nitrogen-containing compounds such as triethylamine, triethylenediamine and N-methylmorpholine; Metal salts such as potassium acetate, zinc stearate and tin octylate; Organic metal compounds such as dibutyl tin dilaurate and zirconium tetraacetylacetonate can be used.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "weight average molecular weight") of the silicone urethane (meth) acrylate resin (B) measured by gel permeation chromatography (using GPC and tetrahydrofuran as an elution solvent) And may be, for example, 1,500 to 3,000. When the weight average molecular weight is within the above range, the pressure-sensitive adhesive film has excellent durability and peelability.

( Meta ) Acrylate  The ester monomer (C)

In one embodiment of the present invention, the (meth) acrylate ester monomer (C) may include aliphatic (meth) acrylate, alicyclic (meth) acrylate, (meth) acrylate having an ether group, Acrylate, aromatic (meth) acrylate, (meth) acrylamide having a nitrogen atom, and the like. Among them, when aliphatic (meth) acrylates, especially C _{4 -20} alkyl (meth) acrylates, are used, their peelability and adhesion are excellent.

Examples of the aliphatic (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) (Meth) acrylate, isobutyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-pentyl (Meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (Meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl Acrylate, hexadecyl (meth) acrylate There may be mentioned isoamyl (meth) acrylate as an example.

Examples of the alicyclic (meth) acrylate include isobonyl (meth) acrylate, cyclohexyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.

Examples of the (meth) acrylate having an ether group include 3-methoxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) (Meth) acrylate, ethoxy-diethylene glycol (meth) acrylate, and ethyl carbitol (meth) acrylate, which have an addition molar number of oxyethylene in the range of 1 to 15 .

Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.

Examples of the aromatic (meth) acrylate include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol acrylate, phenyl (meth) acrylate, 2-hydroxy- Methacrylate, and the like.

Examples of the (meth) acrylamide having a nitrogen atom include (meth) acrylamide, dimethyl (meth) acrylamide, acryloylmorpholine, dimethylaminopropyl (meth) acrylamide, isopropyl (Meth) acrylamide, hydroxyethyl (meth) acrylamide, diacetone (meth) acrylamide and the like.

The (meth) acrylate ester monomer (C) may be used in an amount of 10 to 200 parts by weight based on 100 parts by weight of the silicone urethane (meth) acrylate resin (B). When the (meth) acrylate ester monomer (C) is used within the above range, the releasability is excellent.

Photoinitiator (D)

In one embodiment of the present invention, the photoinitiator (D) means an initiator that absorbs an active energy ray to generate a radical.

The photoinitiator may comprise a short wavelength photoinitiator and a long wavelength photoinitiator. By including both the short-wavelength photoinitiator and the long-wavelength photoinitiator, the durability can be improved due to the uniform cross-linking of the pressure-sensitive adhesive layer.

The short-wavelength photoinitiator means an initiator that absorbs an active energy ray of a short wavelength to generate radicals, and the absorption wavelength region may be, for example, 370 nm or less.

Specific examples of the short-wavelength photoinitiators include benzoin compounds, benzophenone compounds, thioxanthone compounds, and acetophenone compounds.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, p-phenylbenzophenone, 4,4'-bis (diethylamino) benzophenone (EAB-F), and dichlorobenzophenone.

Examples of the thioxanthone compound include 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone (DETX) 4-isopropylthioxanthone (ITX), and the like.

Specific examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2- 2-methyl-1-propane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2- 2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and the like.

These short-wavelength photoinitiators may be used alone or in combination of two or more.

The long wavelength photoinitiator is an initiator that absorbs an active energy ray of a long wavelength to generate radicals, and the absorption wavelength region thereof may be in a range of, for example, 350 to 450 nm.

Typical examples of the long-wavelength photoinitiators include phosphine oxide compounds.

Examples of the phosphine oxide compound include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, bis (2,4,6- Bis (2,4,6-trimethylbenzoyl) -2-methylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) (2,4,6-trimethylbenzoyl) -2,5-diethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,3,5,6-tetramethylphenylphosphine Oxides, and the like.

In addition to the above-mentioned phosphine oxide compounds, ethyl-2,4,6-trimethylbenzoyl phenylphosphinate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) 2-p-methoxystyryl-4,6-bistricloromethyl-s-triazine, 2, 3-bistricloromethyl-6-p-methoxystyryl- 4-methylnaphthyl-6-triazine, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2 - (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o- 2-methyl-1-phenyl-1-on, dimethoxy-2-phenylacetophenone Can be used as a long-wavelength photopolymerization initiator.

The weight ratio of the short-wavelength photoinitiator and the long-wavelength photoinitiator may be 1 to 5: 1. When the weight ratio is satisfied, the peelability of the pressure-sensitive adhesive film is excellent due to an effective crosslinking reaction.

The photoinitiator (D) may be contained in an amount of 0.01 to 10.0 parts by weight based on 100 parts by weight of the total amount of the silicone urethane (meth) acrylate resin (B) and the (meth) acrylate ester monomer (C). If the amount of the photoinitiator is less than 0.01 part by weight, it may be difficult to effectively initiate the crosslinking reaction. If the amount is more than 10.0 parts by weight, discoloration or the like may occur due to the residual initiator.

The pressure-sensitive adhesive compositions according to one embodiment of the present invention may further contain other additives such as a silane coupling agent, a tackifier resin, an antioxidant, an antioxidant, an antioxidant, an antioxidant, An antioxidant, a corrosion inhibitor, a leveling agent, a surface lubricant, a dye, a pigment, a defoaming agent, a filler, a light stabilizer, and the like.

One embodiment of the present invention relates to a pressure-sensitive adhesive film comprising a base film and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition on the base film.

The pressure-sensitive adhesive film according to one embodiment of the present invention is formed using the above-described pressure-sensitive adhesive composition, so that it has excellent antistatic property and durability and a small peeling force.

Specifically, the adhesive film according to an embodiment of the present invention may have a peeling force of 6 g / 25 mm or less, for example, 2 to 6 g / 25 mm on a glass substrate, and a peel force of 4 g / 25 mm , For example from 0.5 to 3 g / 25 mm.

The pressure-sensitive adhesive film according to an embodiment of the present invention is a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to the present invention on a base film or a pressure-sensitive adhesive layer formed from the pressure- .

As the base film, a polyolefin film, a polyester film, an acrylic film, a styrene film, an amide film, a polyvinyl chloride film, a polyvinylidene chloride film, a polycarbonate film and the like can be used.

The thickness of the base film is preferably 30 to 80 mu m. When the thickness is less than 30 mu m, the substrate film is susceptible to poor adhesion, etc. When the thickness is more than 80 mu m, the shrinkage rate under a severe condition is large and the possibility of flooding is high.

The pressure-sensitive adhesive layer can be formed by coating a pressure-sensitive adhesive composition on one base film. The coating method is not particularly limited as long as it is a method known in the art, and examples of the coating method include a bar coater, an air knife, a gravure, a pressing roll, a reverse roll, a kiss roll, a spray, a blade, a die coater, a casting, Can be used. Specifically, the pressure-sensitive adhesive composition is applied on a single base film to a predetermined thickness, or the pressure-sensitive adhesive composition is sandwiched between two base films, compressed to a predetermined thickness, Preferably 200 to 1500 mJ / cm < 2 >, and curing the composition.

The thickness of the pressure-sensitive adhesive layer may be 5 to 200 占 퐉, preferably 50 to 100 占 퐉. If the thickness of the pressure-sensitive adhesive layer is less than 5 mu m, durability may be poor, and if it is more than 200 mu m, peelability may be deteriorated.

The pressure-sensitive adhesive film according to an embodiment of the present invention may be subjected to a surface treatment of the pressure-sensitive adhesive layer to improve the adhesiveness before bonding.

The surface treatment method is not particularly limited, and the surface of the pressure-sensitive adhesive layer can be activated by a method such as corona discharge treatment, plasma treatment, ultraviolet irradiation, electron beam irradiation, or an anchoring agent application.

The adhesive film according to one embodiment of the present invention can be applied to an organic light emitting diode (OLED), a touch panel, and the like. In particular, the pressure-sensitive adhesive film according to one embodiment of the present invention exhibits excellent antistatic property and durability and has a small peeling force, and can be used as a protective film for OLED and the like.

Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples and Experimental Examples. It should be apparent to those skilled in the art that these examples, comparative examples and experimental examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Manufacturing example  1 to 2: silicone urethane ( Meta ) Acrylate  Manufacture of resin

Polyisocyanate, polysilicon having a hydroxyl group at both terminals and dibutyltin dilaurate as a catalyst were charged into a 2 L three-necked flask equipped with an electronic stirrer, a heating mantle, a cooling tube and a temperature controller under the following composition (unit: parts by weight) And the reaction temperature was raised to 70 DEG C while stirring and the reaction was maintained for 4 hours. Thereafter, (meth) acrylate having a hydroxy group and methoxyhydroquinone as a polymerization inhibitor were dropped and reacted in the composition shown in Table 1, and the reaction was maintained for 2 hours after completion of the addition. When the characteristic peak of NCO of 2260 cm < ^-1 > peak on FT-IR disappeared, the reaction was terminated to obtain a silicone urethane (meth) acrylate resin.

Production Example 1 Production Example 2 Polyisocyanate ¹⁾ 444 444 Polysilicon having a hydroxy group at both ends (b1-1) ²⁾ 933 (b1-2) ³⁾ 1800 Dibutyl tin dilaurate 0.4 0.4 Methoxyhydroquinone 0.3 0.3 (Meth) acrylate having a hydroxy group ⁴⁾ 260 260

1) Isophorone diisocyanate (molecular weight: 222)

2) X-22-160AS (Shin-Etsu, molecular weight 933)

3) KF-6001 (Shinetsu, molecular weight 1800)

4) 2-hydroxyethyl methacrylate (molecular weight: 130)

Example  1 to 3 and Comparative Example  1 to 2: Preparation of pressure-sensitive adhesive composition

The pressure-sensitive adhesive composition was prepared by mixing the respective components in the composition shown in Table 2 below (unit: parts by weight).

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 (Meth) acrylate resin Production Example 1 60 30 Production Example 2 60 30 B3 ¹⁾ 60 B4 ²⁾ 60 (Meth) acrylate ester monomer C1 ³⁾ 20 20 20 20 20 C2 ⁴⁾ 20 20 20 20 20 Antistatic agent A1 ⁵⁾ 3 3 3 3 3 Photoinitiator D1 ⁶⁾ 3 3 3 3 3 D2 ⁷⁾ One One One One One

1) bisphenol A epoxy acrylate

2) Soybean oil-modified polyester acrylate

3) tridecyl acrylate

4) Isodecyl acrylate

5) Lithium bisphosphorosulfonylimide

6) 1-Hydroxycyclohexyl phenyl ketone

7) diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide

Experimental Example  One:

The pressure-sensitive adhesive composition prepared in the above examples and comparative examples was dropped on a polyethylene terephthalate (PET) film of 75 μm, and a 38 μm-thick polyethylene terephthalate film treated with silicone was covered on the upper layer. Followed by laminating using a high speed laminator instrument. The thus treated specimen was cured using a metal halide ultraviolet lamp with an accumulated light quantity of 1000 mJ / cm ² to produce an adhesive film.

The physical properties of the pressure-sensitive adhesive films were measured by the following methods, and the results are shown in Table 3 below.

(1) Glass peel force (g / 25 mm )

The produced adhesive film was cut into a size of 25 mm x 250 mm using a super cutter, and then the release film was peeled off and bonded to a glass plate to prepare a test piece. The prepared specimens were fixed on a universal material testing machine (UTM) and peeled off at 180 ° at a speed of 300 m / min to measure the peeling force against the glass. At this time, the peeling force means the peeling force of the surface irradiated with ultraviolet rays.

(2) Liner ( liner ) Peel force (g / 25 mm )

The prepared adhesive film was cut into a size of 25 mm x 250 mm using a super cutter to produce a specimen. The release film of the prepared specimen was partially peeled off, fixed on a universal testing machine (UTM), peeled off at 180 ° at a speed of 300 m / min, and peel strength was measured. At this time, the peeling force means the peeling force of the surface irradiated with ultraviolet rays.

(3) Surface resistivity (Ω / □)

Three points of the pressure-sensitive adhesive film were measured 10 times each using a surface resistivity meter (MCP-HT450, manufactured by Mitsuishi Chemical Co., Ltd.), and the average value was measured.

(4) Durability (heat resistance)

The durability was evaluated by the following evaluation criteria after observing the occurrence of bubbles or peeling after being left at a temperature of 60 캜 for 500 hours.

<Evaluation Criteria>

Ⓞ: No bubble or peeling

○: Bubbles or peeling <5

?: 5 pieces? Bubbles or peeling <10 pieces

X: 10 pieces &lt; bubble &

Glass peel force (g / 25mm) Liner peel force (g / 25mm) Surface resistivity
(Ω / □) durability Example 1 4.1 2.2 4 x 10 ⁹ Ⓞ Example 2 3.2 2.5 5 x 10 ⁹ Ⓞ Example 3 3.5 1.8 4.5 x 10 ⁹ Ⓞ Comparative Example 1 17.2 3.9 5 x 10 ⁸ × Comparative Example 2 15.2 1.7 5 x 10 ⁹ ×

As can be seen from Table 3, the pressure-sensitive adhesive films prepared from the pressure-sensitive adhesive compositions of Examples 1 to 3 including the antistatic agent and the silicone urethane (meth) acrylate resin were excellent in antistatic property and durability, . On the other hand, it was confirmed that the pressure-sensitive adhesive films prepared from the pressure-sensitive adhesive compositions of Comparative Examples 1 and 2, which did not use the silicone urethane (meth) acrylate resin, had poor durability or high peel strength.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. Do. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Accordingly, the actual scope of the invention is defined by the appended claims and their equivalents.

Claims (12)

An antistatic agent, a silicone urethane (meth) acrylate resin, a (meth) acrylate ester monomer and a photoinitiator. The pressure-sensitive adhesive composition according to claim 1, wherein the antistatic agent comprises an alkali metal salt or an alkaline earth metal salt. The pressure-sensitive adhesive composition according to claim 2, wherein the antistatic agent is a compound represented by the following formula (1):
[Chemical Formula 1]
_{M [(FSO 2) 2 N} ] p
In this formula,
M is an alkali metal or an alkaline earth metal,
p is an integer of 1 to 2; The method of claim 3, wherein the antistatic agent is _{Li [(FSO 2) 2 N} ], Na [(FSO 2) 2 N], K [(FSO 2) 2 N], Ca [(FSO 2) 2 N] 2 And Mg [(FSO ₂ ) ₂ N] ₂ . The pressure-sensitive adhesive composition according to claim 1, wherein the silicone urethane (meth) acrylate resin is a reaction product of (meth) acrylate having polysilicon, polyisocyanate, and hydroxyl group having a hydroxyl group at both terminals. The pressure-sensitive adhesive composition according to claim 5, wherein the silicone urethane (meth) acrylate resin is a compound represented by the following formula (2):
(2)

In this formula,
R ¹ and R ³ are each independently a C ₁ -C ₁₀ alkylene group or a C ₁ -C ₁₀ oxyalkylene group,
R ² is a C ₁ -C ₁₀ alkyl group, a C ₃ -C ₁₀ cycloalkyl group or an aryl group,
R &lt; ⁴ &gt; is hydrogen or methyl,
n is an integer of 1 to 30; The pressure-sensitive adhesive composition according to claim 6, wherein the compound represented by Formula 2 is a compound wherein R ¹ and R ³ are each independently a C ₁ -C ₁₀ oxyalkylene group and R ² is a C ₁ -C ₁₀ alkyl group. The method of claim 7 wherein the compound has R ¹ of the formula _{2 - (CH 2) 2 -O-} (CH 2) 3 - , and the _{^{R 3 - (CH 2) 3}} -O- (CH 2) ₂ - and R ² is methyl. The pressure-sensitive adhesive composition according to claim 1, wherein the (meth) acrylate ester monomer is an aliphatic (meth) acrylate. The pressure-sensitive adhesive composition according to claim 1, wherein the photoinitiator comprises a long-wavelength photoinitiator and a short-wavelength photoinitiator. A pressure-sensitive adhesive film comprising a base film and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of any one of claims 1 to 10 on the base film. The adhesive film according to claim 11, wherein the adhesive film is a protective film of the organic light emitting diode.