KR102308357B1 - Adhesive protective film, composition for adhesive sheet for the same and optical member comprising the same - Google Patents

Abstract

A base film and a pressure-sensitive adhesive sheet formed on the base film, wherein the pressure-sensitive adhesive sheet is formed of a pressure-sensitive adhesive sheet composition comprising a hydroxyl group-containing silicone (meth)acrylic copolymer, a photocurable crosslinking agent, a photoinitiator and a thermosetting crosslinking agent, and the adhesive protection The film has a peeling force of 5 gf/in or less with respect to a glass plate, an adhesive protective film, a pressure-sensitive adhesive sheet composition therefor, and an optical member including the same.

Description

Adhesive protective film, adhesive sheet composition therefor, and optical member comprising the same

The present invention relates to an adhesive protective film, an adhesive sheet composition therefor, and an optical member including the same.

The optical display device includes a display device including an organic light emitting device and the like. A conventional organic light emitting device includes a glass plate as a substrate. However, recently, interest in wearable or foldable devices is increasing. In response to this interest, an attempt is being made to replace the substrate of the organic light emitting diode with a plastic film in a glass plate.

The plastic film is thin and flexible compared to the glass plate. Since the panel of the plastic film substrate has poor mechanical properties, it needs to be protected with a protective film in the optical display device manufacturing process. There was a limit to using a conventional protective film for protecting a glass plate as a protective film for a plastic film. When the protective film protecting the plastic film is removed from the plastic film, if the peeling force is high, the panel including the plastic film may be damaged. In particular, since the plastic film is flexible compared to the glass plate, it is easy to be damaged when the protective film is peeled off. Accordingly, there is a need for a protective film capable of reducing damage or shape change to a panel including a plastic film even when peeled from the plastic film due to low peeling force to the plastic film.

Meanwhile, the protective film may be prepared by coating a composition for a protective film on a base film to a predetermined thickness and curing the composition. However, when the coating layer of the composition for a protective film is thick, there is a problem in that the coating layer is not properly formed on the base film or is peeled off even if it is formed, thereby reducing fairness.

Background art of the present invention is disclosed in Korean Patent Publication No. 2007-0055363 and the like.

SUMMARY OF THE INVENTION It is an object of the present invention to provide an adhesive protective film capable of securing a peeling force capable of suppressing deformation or damage to an adherend during peeling from an adherend while protecting the adherend.

Another object of the present invention is to provide an adhesive protective film having excellent processability due to excellent wettability and scattering properties to an adherend.

Another object of the present invention is to provide an adhesive protective film having excellent adhesion to an adherend in the manufacturing process, but suppressing deformation or damage to the adherend during peeling after the manufacturing process, and excellent adhesion between the adhesive sheet and the base film will be.

The adhesive protective film of the present invention includes a base film and an adhesive sheet formed on the base film, wherein the adhesive sheet comprises a hydroxyl group-containing silicone (meth)acrylic copolymer, a photocurable crosslinking agent, a photoinitiator, and a thermosetting crosslinking agent. is formed, and the adhesive protective film may have a peel force of 5 gf/in or less with respect to the glass plate.

The pressure-sensitive adhesive sheet composition of the present invention includes a hydroxyl group-containing silicone (meth)acrylic copolymer, a photocurable crosslinking agent, a photoinitiator and a thermosetting crosslinking agent, and the thermosetting crosslinking agent is at least one of an isocyanate type crosslinking agent, an epoxy curing agent, and an aziridine based curing agent; and a carboxyl group-containing (meth)acrylate.

The optical member of the present invention may include an optical film and the adhesive protective film of the present invention formed on at least one surface of the optical film.

The present invention provides an adhesive protective film capable of securing a peeling force capable of suppressing deformation or damage to an adherend during peeling from the adherend while protecting the adherend.

The present invention provides an adhesive protective film having excellent processability due to excellent wettability and scattering properties to an adherend.

The present invention provides an adhesive protective film having excellent adhesion to an adherend during the manufacturing process, but suppressing deformation or damage to the adherend during peeling after the manufacturing process, and excellent adhesion between the adhesive sheet and the base film.

1 is a schematic view showing a method for evaluating the scattering properties of the adhesive protective film of Examples and Comparative Examples.
2 is a schematic diagram showing a method for evaluating the wettability of the adhesive protective films of Examples and Comparative Examples.

It will be described in detail so that a person of ordinary skill in the art can easily carry out the present invention by the following examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein.

As used herein, “(meth)acryl” may mean acryl and/or methacrylic. As used herein, "copolymer" may include oligomers, polymers, or resins.

The inventor of the present invention is an adhesive protective film composed of a base film and a pressure-sensitive adhesive sheet, and has excellent adhesion or adhesion between the base film and the pressure-sensitive adhesive sheet, and has excellent wettability and scattering properties to an adherend of the adhesive protective film, resulting in excellent processability As a result of efforts to develop an adhesive protective film that can protect the adherend and secure peeling force that can suppress deformation or damage to the adherend when peeled from the adherend, the adhesive sheet is a hydroxyl group-containing silicone (meth)acrylic-based The present invention was reached by forming a pressure-sensitive adhesive sheet composition comprising a copolymer, a photocurable crosslinking agent, a photoinitiator and a thermosetting crosslinking agent.

In the present specification, the term “adherent” may refer to a plastic film formed of a glass plate, polyimide resin, acrylic resin, or the like.

Hereinafter, an adhesive protective film according to an embodiment of the present invention will be described.

The adhesive protective film may have a peeling force of 5 gf/in or less to a glass plate at 25°C. In the above range, the peeling force to the adherend is low, so that damage to the adherend and/or deformation of the external shape of the adherend can be prevented when the adhesive protective film is peeled from the adherend. Preferably, the peeling force to the glass plate at 25° C. may be 1 gf/in to 5 gf/in, more preferably 3 gf/in to 5 gf/in. The "peel force" may be measured with reference to the peel force evaluation part described in detail below.

The adhesive protective film is a rectangular specimen of width x length (25mm x 100mm), which is adhered to the end width x length (25mm x 10mm) on the acrylic plate, and the other end of the adhesive protective film is positioned at an angle of 20° from the acrylic plate. Then, when the other end is placed in the direction of the acrylic plate, the time for the adhesive protective film to be completely adhered to the acrylic plate may be 7 seconds or less. Within the above range, the wettability of the adhesive protective film to the adherend is good, so that processability can be improved.

The adhesive protective film may include a base film and an adhesive sheet formed on the base film. The pressure-sensitive adhesive protective film may be prepared by coating a pressure-sensitive adhesive sheet composition on a base film to a predetermined coating thickness to form a coating layer, and then thermosetting and photocuring. In this case, if the coating thickness is thick, the adhesion of the pressure-sensitive adhesive sheet to the base film may be lowered, so that the pressure-sensitive adhesive protective film may not be properly formed or the pressure-sensitive adhesive sheet may be peeled off from the base film even if it is formed. On the other hand, although the adhesive protective film of the present invention will be described in detail below, the adhesion or adhesion of the adhesive sheet to the base film is enhanced by including a specific thermosetting crosslinking agent as the thermosetting crosslinking agent. For example, the coating thickness may be 10㎛ to 50㎛, 20㎛ to 30㎛. The adhesive protective film prepared therefrom may have a thickness of 20 μm to 150 μm, 50 μm to 130 μm, and 85 μm to 125 μm. The base film may include a polyester film such as polyethylene terephthalate. The base film may have a thickness of 10 μm to 100 μm, preferably 50 μm to 80 μm.

The adhesive protective film was formed by placing a stainless pencil (diameter of 1 mm) at an angle of 45° to the surface of the adhesive sheet and moving at a load of 1 kg, a speed of 48 mm/min, and at 25° C. When scratched, any particles on the surface of the adhesive sheet It may have good scattering properties because there is no or thin thread-like residue is not formed and it is not scratched. The adhesive protective film is cut to a predetermined size after being adhered to the adherend. In this process, since it has good scattering properties, processability may be improved and additional equipment may not be required.

The adhesive protective film having all of the above-described peeling force range, adhesion, non-acidity, and wettability includes a pressure-sensitive adhesive sheet formed of a pressure-sensitive adhesive sheet composition comprising a hydroxyl group-containing silicone (meth)acrylic copolymer, a photocurable crosslinking agent, a photoinitiator and a thermosetting crosslinking agent It can be formed by

Hereinafter, the pressure-sensitive adhesive sheet composition will be described in detail.

The hydroxyl group-containing silicone (meth)acrylic copolymer forms a matrix of the pressure-sensitive adhesive sheet, and the hydroxyl group reacts with a thermosetting crosslinking agent to secure a peel force in a predetermined range and improve the adhesion or adhesion of the pressure-sensitive adhesive sheet to the base film. In addition, the hydroxyl group-containing silicone (meth)acrylic copolymer can increase the curing rate of the pressure-sensitive adhesive sheet composition by reacting with the photo-curable crosslinking agent and allow the pressure-sensitive adhesive protective film to reach the peel strength range of the present invention.

The hydroxyl group-containing silicone (meth)acrylic copolymer may include a copolymer of a monomer mixture including a hydroxyl group-containing (meth)acrylic monomer, an alkyl group-containing (meth)acrylic monomer, and a silicone-containing (meth)acrylic monomer.

The hydroxyl group-containing (meth)acrylic monomer may provide peeling force to the adhesive protective film. The hydroxyl group-containing (meth)acrylic monomer may be a (meth)acrylate containing at least one hydroxyl group. In one embodiment, the hydroxyl group-containing (meth)acrylate may be a silicone-free non-silicone-based (meth)acrylate. For example, the hydroxyl group-containing (meth)acrylate is 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono (meth)acrylate, 1-chloro-2-hydr Roxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, Neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4- It may be at least one of hydroxycyclopentyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Preferably, the hydroxyl group-containing (meth)acrylate is 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxypropyl It may include at least one of (meth)acrylates.

The hydroxyl group-containing (meth)acrylic monomer may be included in an amount of 5 wt% to 20 wt%, preferably 5 wt% to 10 wt% of the monomer mixture. Within the above range, there may be an effect of improving adhesion to the adherend.

The alkyl group-containing (meth)acrylic monomer may form a matrix of the pressure-sensitive adhesive sheet. The alkyl group-containing (meth)acrylic monomer may include an unsubstituted (meth)acrylate having a linear or branched alkyl group having 1 to 20 carbon atoms. In one embodiment, the (meth)acrylate having an alkyl group may be a non-silicone-based (meth)acrylate that does not contain silicone. For example, (meth)acrylate having an alkyl group is methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylic Rate, iso-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl ( At least one of meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, and ethylhexyl diglycol (meth) acrylate may include.

The alkyl group-containing (meth)acrylic monomer may be included in an amount of 60 wt% to 90 wt%, preferably 70 wt% to 90 wt% of the monomer mixture. In the above range, there may be an effect of imparting adhesive force.

The silicone-containing (meth)acrylic monomer may lower the peel strength of the adhesive protective film. The silicone-containing (meth)acrylic monomer may include monofunctional (meth)acrylate or polyfunctional (meth)acrylate in which the ester moiety of (meth)acrylate is modified with siloxane. Preferably, a monofunctional (meth)acrylate in which the ester moiety of (meth)acrylate is modified with siloxane may be used. In one embodiment, the monofunctional (meth)acrylate modified with siloxane may be a non-particulate compound rather than a particulate. The siloxane-modified monofunctional (meth)acrylate may include a polydialkylsiloxane moiety as the siloxane.

In one embodiment, the monofunctional (meth)acrylate modified with siloxane may be represented by the following Chemical Formula 1:

<Formula 1>

(In Formula 1,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms,

R ₈ is an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms,

R ₉ is hydrogen or a methyl group,

n is an integer from 10 to 100).

Preferably, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are each independently an alkyl group having 1 to 10 carbon atoms, more preferably a methyl group or an ethyl group as an alkyl group having 1 to 5 carbon atoms. , a propyl group, a butyl group, or a pentyl group. Preferably, R ₈ may be an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group, an ethylene group, a propylene group, a butylene group or a pentylene group. Preferably, n may be an integer from 20 to 80, more preferably an integer from 20 to 70.

In one embodiment, the monofunctional (meth)acrylate modified with siloxane may be represented by the following Chemical Formula 1-1:

<Formula 1-1>

(In Formula 1-1,

R ₂ is an alkyl group having 1 to 10 carbon atoms,

R ₈ is an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms,

R ₉ is hydrogen or a methyl group, n is an integer from 10 to 100).

The silicone-containing (meth)acrylic monomer may have a weight average molecular weight of 1000 to 6000, preferably 3000 to 6000. The silicone-containing (meth)acrylic monomer may have a glass transition temperature of -150°C to -10°C, preferably -100°C to -20°C, of the homopolymer. Within the above range, there may be a good effect of wettability and adhesion to the adherend surface.

The silicone-containing (meth)acrylic monomer may be included in an amount of 5 wt% to 20 wt%, preferably 5 wt% to 15 wt% of the monomer mixture. Within the above range, there may be a good effect of wettability and adhesion to an adherend.

The monomer mixture may include a copolymerizable (meth)acrylic monomer in addition to a hydroxyl group-containing (meth)acrylic monomer, an alkyl group-containing (meth)acrylic monomer, and a silicone-containing (meth)acrylic monomer. The copolymerizable (meth)acrylic monomer is a non-silicone-based monomer that does not contain silicone, and is a (meth)acrylate having an alicyclic group, (meth)acrylate having a heteroalicyclic group, (meth)acrylate having an aromatic group, carboxylic acid It may include, but is not limited to, at least one of (meth)acrylic monomers having a group.

The hydroxyl group-containing silicone (meth)acrylic copolymer may be prepared by polymerizing the (meth)acrylic monomer mixture by a conventional method, and the polymerization method may be according to a conventional method known to those skilled in the art.

The hydroxyl group-containing silicone (meth)acrylic copolymer may have a weight average molecular weight of 1 million to 2 million, preferably 1.3 million to 1.7 million. In the above range, there may be an effect of lowering the peeling force and improving the wettability.

The hydroxyl group-containing silicone (meth)acrylic copolymer is 80 parts by weight to 99.9 parts by weight, preferably 85 parts by weight to 99 parts by weight, more preferably from 100 parts by weight of the total of 100 parts by weight of the hydroxyl group-containing silicone (meth)acrylic copolymer and the photocurable crosslinking agent. It may be included in an amount of 90 parts by weight to 99 parts by weight. In the above range, lowering the peel force and improving the wettability It may work.

The photocurable crosslinking agent may react with a curing reaction product of the hydroxyl group-containing silicone (meth)acrylic copolymer and the thermosetting crosslinking agent to increase the curing rate of the pressure-sensitive adhesive sheet and to reach the peel strength range of the present invention.

The photocurable crosslinking agent may include a (meth)acrylate having a function of 2 to 6 functions. For example, the photocurable crosslinking agent is di(meth)acryl having an unsubstituted C1 to C10 alkylene group such as 1,4-butanediol di(meth)acrylate or 1,6-hexanediol di(meth)acrylate. Late, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having a C1 to C3 alkyleneoxy group, including a C1 to C10 alkylene group having an alkylene group di (meth) acrylate, neopentyl Glycol di(meth)acrylate, neopentylglycol adipate di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone modified dicyclopentenyl di(meth)acrylate, ethylene oxide modified di( Meth)acrylate, di(meth)acryloxy ethyl isocyanurate, allylated cyclohexyl di(meth)acrylate, tricyclodecanedimethanol (meth)acrylate, dimethylol dicyclopentanedi(meth)acrylate , Ethylene oxide-modified hexahydrophthalic acid di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, neopentyl glycol-modified trimethylpropane di (meth) acrylate, adamantane di (meth) acrylic bifunctional acrylates such as late or 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene; Trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide trifunctional acrylates such as modified trimethylolpropane tri(meth)acrylate, trifunctional urethane (meth)acrylate, or tris(meth)acryloxyethyl isocyanurate; tetrafunctional acrylates such as diglycerin tetra(meth)acrylate or pentaerythritol tetra(meth)acrylate; 5-functional acrylates, such as dipentaerythritol penta (meth)acrylate; and dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate or urethane (meth)acrylate (ex. isocyanate monomer and trimethylolpropane tri(meth)acrylate) 6-functional acrylate as a reactant, etc., but is not limited thereto.They may be used alone or in combination of two or more types. In one embodiment, the photocurable crosslinking agent without a carboxyl group may be used as the photocurable crosslinking agent. Preferably, the photocurable crosslinking agent may use di(meth)acrylate having an unsubstituted C1 to C10 alkylene group.

The photocurable crosslinking agent is 0.1 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the total of 100 parts by weight of the hydroxyl group-containing silicone (meth)acrylic copolymer and the photocurable crosslinking agent. It may be included in 10 parts by weight. In the above range, it is possible to reach the peel force range of the present invention by adjusting the peel force, and there may be an effect excellent in aging property.

The thermosetting crosslinking agent is at least one selected from an isocyanate-type crosslinking agent, an epoxy-based curing agent, and an aziridine-based curing agent; and a carboxyl group-containing (meth)acrylate.

At least one of an isocyanate-type crosslinking agent, an epoxy-based curing agent, and an aziridine-based curing agent is cross-linked with a hydroxyl group-containing silicone (meth)acrylic copolymer to thermoset the pressure-sensitive adhesive sheet composition to form a matrix of the pressure-sensitive adhesive sheet, and part of the peeling force of the present invention It is possible to secure the peeling force of Preferably, an isocyanate-type crosslinking agent may be included.

The isocyanate-type crosslinking agent may include a conventional isocyanate-type crosslinking agent having two or more isocyanate groups. For example, the isocyanate type crosslinking agent includes xylene diisocyanate (XDI) containing m-xylene diisocyanate, etc., methylenebis (phenyl isocyanate) (MDI) containing 4,4'-methylenebis (phenyl isocyanate), naphthalene at least one of diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, or at least one of adducts thereof.

At least one of an isocyanate-type crosslinking agent, an epoxy-based curing agent, and an aziridine-based curing agent may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the total of the hydroxyl group-containing silicone (meth)acrylic copolymer and the photocurable crosslinking agent. Within the above range, there may be an effect of enhancing adhesion and improving degree of curing. Preferably, at least one of an isocyanate-type crosslinking agent, an epoxy-based curing agent, and an aziridine-based curing agent may be included in an amount of 0.1 parts by weight to 3 parts by weight, and 0.1 parts by weight to 1 part by weight.

The carboxyl group-containing (meth)acrylate may increase adhesion and adhesion between the coating layer and the base film even if the coating thickness is thick when the pressure-sensitive adhesive sheet composition is coated on the base film. The carboxyl group-containing (meth)acrylate may include, but is not limited to, betacarboxylethyl (meth)acrylate.

The carboxyl group-containing (meth)acrylate may be included in an amount of 0.001 parts by weight to 5 parts by weight based on 100 parts by weight of the total of the hydroxyl group-containing silicone (meth)acrylic copolymer and the photocurable crosslinking agent. In the above range, there may be an effect of improving adhesion and scattering properties of the pressure-sensitive adhesive sheet to the base film. Preferably, the carboxyl group-containing (meth)acrylate may be included in an amount of 0.01 parts by weight to 3 parts by weight, or 0.1 parts by weight to 1 part by weight.

at least one of a thermosetting crosslinking agent, that is, an isocyanate-type crosslinking agent, an epoxy-based curing agent, and an aziridine-based curing agent; And the whole of the carboxyl group-containing (meth)acrylate may be included in an amount of 0.001 parts by weight to 10 parts by weight based on 100 parts by weight of the total of the hydroxyl group-containing silicone (meth)acrylic copolymer and the photocurable crosslinking agent. In the above range, there may be an effect of enhancing the adhesion of the pressure-sensitive adhesive sheet. Preferably, the thermosetting crosslinking agent may be included in an amount of 0.01 parts by weight to 5 parts by weight, 0.1 parts by weight to 3 parts by weight, and 0.5 parts by weight to 3 parts by weight.

The photoinitiator may catalyze a curing reaction between a curing reaction product of the hydroxyl group-containing silicone (meth)acrylic copolymer and the thermosetting crosslinking agent and the photocurable crosslinking agent. The photoinitiator may include a commonly known photo-radical initiator. For example, the photoinitiator may be a benzoin-based, hydroxy ketone-based, aminoketone-based or phosphine oxide-based photoinitiator, but is not limited thereto.

The photoinitiator may be included in an amount of 0.001 parts by weight to 5 parts by weight based on 100 parts by weight of the total of the hydroxyl group-containing silicone (meth)acrylic copolymer and the photocurable crosslinking agent. Within the above range, the above-described photocuring may be sufficiently carried out and the remaining amount of the photoinitiator may be effective in preventing the transparency of the adhesive protective film from being lowered. Preferably, the photoinitiator may be included in an amount of 0.01 parts by weight to 5 parts by weight, 0.01 parts by weight to 1 part by weight.

The adhesive sheet composition includes an antistatic agent, a surfactant, a curing accelerator, an ionic liquid, a lithium salt, an inorganic filler, a softener, a molecular weight regulator, an antioxidant, an anti-aging agent, a stabilizer, a tackifying resin, a modified resin (polyol resin, phenol resin, acrylic resin, polyester resin, polyolefin resin, epoxy resin, epoxidized polybutadiene resin, etc.), leveling agent, defoaming agent, plasticizer, dye, pigment (color pigment, extender pigment, etc.), processing agent, sunscreen agent, optical brightener, Conventional additives such as dispersants, heat stabilizers, light stabilizers, ultraviolet absorbers, coagulants, lubricants and solvents may be further included. The additive is included in an amount of 0.001 to 1 part by weight, specifically 0.003 to 1 part by weight, specifically 0.005 to 1 part by weight, based on 100 parts by weight of the total of 100 parts by weight of the hydroxyl group-containing silicone (meth)acrylic copolymer and the photocurable crosslinking agent. can Within the above range, it is possible to produce an additive effect without affecting the peeling force and reliability of the adhesive protective film.

The pressure-sensitive adhesive sheet composition may further include a solvent. A solvent can improve the applicability|paintability of an adhesive sheet composition. As the solvent, a conventional solvent known to those skilled in the art including methyl ethyl ketone and the like may be used. The solvent may be included in the balance excluding the solid content in the pressure-sensitive adhesive sheet composition.

The adhesive protective film may have a total light transmittance of 90% or more, specifically 95% or more in a visible light region (eg, a wavelength of 380 nm to 780 nm). In the above range, the optical transparency is good, so that it can be used in an optical display device.

The pressure-sensitive adhesive protective film may be prepared by coating the pressure-sensitive adhesive sheet composition on a base film to a predetermined thickness, heat curing, and photocuring.

The optical member according to an embodiment of the present invention may include an optical film and an adhesive protective film formed on at least one surface of the optical film, and the adhesive protective film may include the adhesive protective film according to embodiments of the present invention. .

The optical film may include a polyimide film as a display panel. In one embodiment, the optical film may be composed of a light emitting device layer and a polyimide film formed on at least one surface of the light emitting device layer. An organic insulating film or an inorganic insulating film may be further formed between the optical film and the adhesive protective film. The optical member may further include a release film (liner) on the other surface of the adhesive protective film. The release film can prevent the adhesive protective film from being contaminated by foreign substances. As the release film, an optical film formed of the same or different material as the above-described optical film may be used. For example, the release film may be a film formed of at least one of a polyethylene terephthalate resin, a polycarbonate resin, a polyimide resin, a poly(meth)acrylate resin, a cyclic olefin polymer resin, and an acrylic resin. The release film may have a thickness of 10 μm to 100 μm, preferably 10 μm to 50 μm. In the above range, it is possible to support an adhesive protective film.

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, these are presented as preferred examples of the present invention and should not be construed as limiting the present invention in any sense.

Example One

2-ethylhexyl acrylate 80 parts by weight, 2-hydroxyethyl acrylate 10 parts by weight, silicone-containing methacrylate KF2012 (Shinyetsu Corporation, in Formula 1-1, R ² is a methyl group, R ⁸ is an n-propylene group, R ⁹ is a methyl group) by polymerizing a monomer mixture mixed with 10 parts by weight of a hydroxyl group-containing silicone (meth)acrylic copolymer B was prepared.

Based on the solid content, 99 parts by weight of the hydroxyl group-containing silicone (meth)acrylic copolymer B prepared above, 1 part by weight of hexanediol diacrylate (HDDA, ENTIS) as a photocurable crosslinking agent, 0.1 parts by weight of photoinitiator IRGACURE 184 (BASF) , 0.5 parts by weight of beta carboxyethyl acrylate (βCEA, ENTIS) as a thermosetting crosslinking agent and 0.5 parts by weight of an isocyanate-based crosslinking agent L-45 (SOKEN, trifunctional isocyanate crosslinking agent) were mixed to prepare a pressure-sensitive adhesive sheet composition.

Methyl ethyl ketone was added to the prepared pressure-sensitive adhesive sheet composition to make it 70% solid, and then defoamed, and applied to one side of a base film, PET (polyethylene terephthalate) film (thickness: 75 μm, SKC) to a thickness of 25 μm, It was heat-cured by drying at 80° C. for 2 minutes. Then, on the application layer, a PET (polyethylene terephthalate) film (thickness: 25㎛, Toray advanced material), which is a release film, is again laminated on the coating layer, and then the adhesive sheet (thickness) is irradiated with a ^{metal halide lamp at 400mJ/cm 2 .} : 25 μm), to prepare an adhesive protective film composed of a base film/adhesive sheet.

Example 2 to Example 3

A base film/adhesive protective film of the pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1, except that the composition of the pressure-sensitive adhesive sheet composition was changed as shown in Table 1 (unit: parts by weight).

comparative example One

80 parts by weight of 2-ethylhexyl acrylate, 10 parts by weight of isobornyl acrylate, and 10 parts by weight of silicone-containing methacrylate KF2012 (Shinyetsu Co., Ltd.) are mixed and polymerized to form a hydroxyl group-free silicone (meth)acrylic copolymer that does not contain a hydroxyl group Synthesis A was prepared.

99 parts by weight of the silicone (meth)acrylic copolymer A prepared above, 1 part by weight of hexanediol diacrylate (ENTIS) as a photocurable crosslinking agent, 0.1 parts by weight of IRGACURE 184 (BASF) as a photoinitiator, and beta carboxyethyl acrylic as a thermosetting crosslinking agent A pressure-sensitive adhesive sheet composition was prepared by mixing 0.5 parts by weight of Late (ENTIS) and 0.5 parts by weight of an isocyanate-based crosslinking agent L-45 (SOKEN, a trifunctional isocyanate crosslinking agent). A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 using the prepared pressure-sensitive adhesive sheet composition.

comparative example 2 to comparative example 7

A pressure-sensitive adhesive protective film was prepared in the same manner as in Example 1 and Comparative Example 1, except that the composition of the pressure-sensitive adhesive sheet composition was changed as shown in Table 1 (unit: parts by weight).

Hydroxyl group-free silicone (meth)acrylic copolymer
A Hydroxyl group-containing silicone (meth)acrylic copolymer
B photocurable crosslinking agent photoinitiator thermosetting crosslinking agent HDDA IRGACURE 184 βCEA L-45 Example 1 0 99 One 0.1 0.5 0.5 Example 2 0 97 3 0.1 0.5 0.5 Example 3 0 95 5 0.1 0.5 0.5 Comparative Example 1 99 0 One 0.1 0.5 0.5 Comparative Example 2 0 99 One 0.1 0 0 Comparative Example 3 97 0 3 0.1 0.5 0.5 Comparative Example 4 95 0 5 0.1 0.5 0.5 Comparative Example 5 93 0 7 0.1 0.5 0.5 Comparative Example 6 0 99.5 0.5 0.5 0 0.3 Comparative Example 7 0 100 0 0 0.5 0.5

The physical properties of the adhesive sheets prepared in Examples and Comparative Examples were evaluated in Table 2 below, and the results are shown in Table 2 below.

(1) Peel force (unit: gf / in): The adhesive protective film of the base film / adhesive sheet obtained in Examples and Comparative Examples was cut into a rectangle with a width x length of 2.5 cm x 10 cm to prepare a section of an adhesive protective film, A piece of the adhesive protective film was adhered to the glass plate in the order of the adhesive sheet and the base film from the glass plate to prepare a specimen. The specimen was attached to a TA (Texture Analyzer) device, and the peel force was measured when the adhesive protective film section from the specimen was peeled 180° from the glass plate at 25° C. at a peeling rate of 2400 mm/min.

(2) Fragility: A piece of the adhesive protective film was obtained in the same manner as in (1). Referring to FIG. 1 , a piece of the adhesive protective film 2 was adhered to the glass plate 1 using a separate tape (not shown in FIG. 1 ). At this time, it was fixed so that the base film of the adhesive protective film fragment (2) might contact with the glass plate (1). Among the pieces of the adhesive protective film (2), a stainless pencil (diameter 1mm) (3) used for measuring pencil hardness on one side of the adhesive sheet was placed at an angle of 45° to the surface of the adhesive sheet, a load of 1 kg, a speed of 48 mm/min, When scratching while moving at 25°C, if there are no random particles on the surface of the adhesive sheet or if a thin thread-like residue is not formed and is scratched, '○', particles are formed in irregular shapes and sizes on the surface of the adhesive layer. When the adhesive layer was scratched, it was evaluated as 'x'.

(3) Adhesion: The adhesion of the pressure-sensitive adhesive sheet to the base film was evaluated. In the adhesive protective films of Examples and Comparative Examples, place the base film side on the bottom surface, place a cross-cutter or ruler on the film, and then scrape 10 horizontal and vertical lines at 1 mm intervals with a knife. After attaching 3M milky tape to the adhesive sheet surface of the 100 square-spaced cutting coating film, remove it strongly to check the degree of detachment of the coating film. If the coating film of the adhesive sheet remaining on the base film is 95 or more out of 100, it is evaluated as OK, and when the coating film of the adhesive sheet remaining on the base film is less than 95 out of 100, it is evaluated as NG.

(4) Wettability (unit: seconds): The wettability of the adhesive protective film to the acrylic plate was evaluated. Specimens were prepared by cutting the adhesive protective film composed of the base film/adhesive sheet of Examples and Comparative Examples in width x length (25 mm x 100 mm). 2, the end end 5-1 of the adhesive protective film specimen 5 is attached to one side of the acrylic plate 4 so that the width x length (25mm x 10mm) is in contact with the end end and the The adjacent other end end (5-2) was raised at an angle (θ) of 20° to maintain a certain distance. At this time, the adhesive protective film specimen (5) was such that the adhesive sheet was adhered to the acrylic plate (4). Then, when the other end end (5-2) of the adhesive protective film specimen (5) was placed in the direction of the acrylic plate (4) (indicated by the arrow direction in Fig. 2) (referred to as 0 seconds), the adhesive protective film specimen The time until (5) was completely adhered to the acrylic plate (4) was measured.

peel force fugitive adherence wettability Example 1 3.4 ○ OK 4.2 Example 2 3.2 ○ OK 5.1 Example 3 3.0 ○ OK 6.1 Comparative Example 1 3.4 ○ NG 4.7 Comparative Example 2 3.5 ○ NG 3.5 Comparative Example 3 3.1 ○ NG 5.5 Comparative Example 4 2.9 ○ NG 8.7 Comparative Example 5 2.4 x NG 10.0 Comparative Example 6 5.4 ○ NG 4.1 Comparative Example 7 9.8 ○ NG 3.7

As shown in Table 2, the adhesive protective film of the present invention has a peeling force of 5 gf/in or less to the glass plate, and while protecting the adherend, it has a peeling force that can suppress deformation or damage to the adherend when peeling from the adherend. It can be secured, and the wettability and scattering property to the adherend are excellent, so that the processability is excellent, and the adhesion between the pressure-sensitive adhesive sheet and the base film is excellent.

On the other hand, Comparative Examples 1 and 3 to 5, which did not include the hydroxyl group-containing silicone (meth)acrylic copolymer, had poor adhesion, and Comparative Example 5 had poor acidity and wettability. Comparative Example 2 not including the thermosetting crosslinking agent had poor adhesion. Comparative Example 7, which did not include a photocurable crosslinking agent and a photoinitiator, had too high peel strength and poor adhesion. Comparative Example 6 did not have good adhesion and did not satisfy desired physical properties due to increased peeling force.

Simple modifications or changes of the present invention can be easily carried out by those of ordinary skill in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (17)

A pressure-sensitive adhesive protective film comprising a base film and an adhesive sheet formed on the base film,
The pressure-sensitive adhesive sheet is formed of a pressure-sensitive adhesive sheet composition comprising a hydroxyl group-containing silicone (meth)acrylic copolymer, a photocurable crosslinking agent, a photoinitiator and a thermosetting crosslinking agent,
The adhesive protective film will have a peeling force of 5 gf/in or less with respect to the glass plate, the adhesive protective film.
According to claim 1, wherein the adhesive protective film is a rectangular specimen of width x length (25mm x 100mm), the end width x length (25mm x 10mm) is adhered to the acrylic plate, and the other end of the adhesive protective film is attached to the acrylic When the other end is placed at an angle of 20° from the plate and then placed in the direction of the acrylic plate, the time for the adhesive protective film to completely adhere to the acrylic plate is 7 seconds or less.
The adhesive protective film of claim 1, wherein the adhesive protective film has a thickness of 85 μm to 125 μm.
According to claim 1, wherein the hydroxyl group-containing silicone (meth)acrylic copolymer is a copolymer of a monomer mixture comprising a hydroxyl group-containing (meth)acrylic monomer, an alkyl group-containing (meth)acrylic monomer, and a silicone-containing (meth)acrylic monomer It will contain, an adhesive protective film.
The adhesive protective film according to claim 4, wherein the hydroxyl group-containing (meth)acrylic monomer is included in an amount of 5 wt% to 20 wt% of the monomer mixture.
The adhesive protective film according to claim 4, wherein the silicone-containing (meth)acrylic monomer is included in an amount of 5 wt% to 20 wt% of the monomer mixture.
The adhesive protective film according to claim 4, wherein the silicone-containing (meth)acrylic monomer is represented by the following formula (1):
<Formula 1>

(In Formula 1,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms,
R ₈ is an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms,
R ₉ is hydrogen or a methyl group,
n is an integer from 10 to 100).
The adhesive protective film according to claim 1, wherein the photocurable crosslinking agent comprises a (meth)acrylate having a bifunctional to hexafunctional function.
The method of claim 1, wherein the thermosetting crosslinking agent is at least one of an isocyanate-type crosslinking agent, an epoxy-based curing agent, and an aziridine-based curing agent; and a carboxyl group-containing (meth)acrylate.
The adhesive protective film according to claim 9, wherein the carboxyl group-containing (meth)acrylate includes betacarboxylethyl (meth)acrylate.
The adhesiveness of claim 9, wherein the carboxyl group-containing (meth)acrylate is included in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the total of the hydroxyl group-containing silicone (meth)acrylic copolymer and the photocurable crosslinking agent. protective film.
The adhesive protective film according to claim 9, wherein the thermosetting crosslinking agent is included in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the total of the hydroxyl group-containing silicone (meth)acrylic copolymer and the photocurable crosslinking agent.
According to claim 1, wherein the pressure-sensitive adhesive sheet composition
80 parts by weight to 99.9 parts by weight of the hydroxyl group-containing silicone (meth)acrylic copolymer;
0.1 parts by weight to 20 parts by weight of the photocurable crosslinking agent;
Based on 100 parts by weight of the total of the hydroxyl group-containing silicone (meth)acrylic copolymer and the photocurable crosslinking agent,
0.001 parts by weight to 5 parts by weight of the photoinitiator;
The adhesive protective film comprising 0.001 parts by weight to 10 parts by weight of the thermosetting crosslinking agent.
Contains a hydroxyl group-containing silicone (meth)acrylic copolymer, a photocurable crosslinking agent, a photoinitiator and a thermosetting crosslinking agent,
The thermosetting crosslinking agent is at least one of an isocyanate-type crosslinking agent, an epoxy-based curing agent, and an aziridine-based curing agent; And as a pressure-sensitive adhesive sheet composition comprising a carboxyl group-containing (meth) acrylate,
The pressure-sensitive adhesive protective film formed on the base film and the pressure-sensitive adhesive sheet formed on the base film and the pressure-sensitive adhesive sheet composition has a peel force of 5 gf / in or less to a glass plate, the pressure-sensitive adhesive sheet composition.
15. The method of claim 14, wherein the pressure-sensitive adhesive sheet composition
80 parts by weight to 99.9 parts by weight of the hydroxyl group-containing silicone (meth)acrylic copolymer;
0.1 parts by weight to 20 parts by weight of the photocurable crosslinking agent;
Based on 100 parts by weight of the total of the hydroxyl group-containing silicone (meth)acrylic copolymer and the photocurable crosslinking agent,
0.001 parts by weight to 5 parts by weight of the photoinitiator,
The pressure-sensitive adhesive sheet composition comprising 0.001 parts by weight to 10 parts by weight of the thermosetting crosslinking agent.
optical film; And, the optical member comprising the adhesive protective film of any one of claims 1 to 13 formed on one surface of the optical film.
The optical member of claim 16 , wherein the optical film comprises a polyethylene terephthalate-based film.

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