KR20200038637A - Protection film for processing - Google Patents

Abstract

The present invention relates to a protective film for a process which is stably attached to a surface of an adherend during a manufacturing process of a display device or a semiconductor device to protect the surface, is simultaneously easy to peel due to a rapid decrease in adhesive strength due to additional photo-curing after processing, and does not generate the contamination by residues after peeling.

Description

PROTECTIVE FILM FOR PROCESSING

The present invention relates to a protective film for a process, and more specifically, it is stably attached to the surface of a display device or a semiconductor device during a manufacturing process, and simultaneously protects the surface. Therefore, it is easy to peel and relates to a protective film for a process that does not cause contamination by residue after peeling.

A display device, such as a flat panel display panel, generally forms a thin film transistor (TFT) circuit on a glass substrate or deposits an organic material layer to form a pixel, and then forms a color filter glass substrate or encapsulation glass thereon. Will be sealed. The display device manufactured as described above performs a slimming process in order to reduce the overall thickness, cuts the cells in units of a predetermined standard, and performs various necessary circuit wiring processes such as attaching a flexible printed circuit board (FPCB) and various other methods. The process of attaching the driving IC to perform the display function is performed. In addition, a number of additional tasks such as inspection processes are performed. When a large number of processes are performed as described above, damage such as scratches may occur on the surface of the display device, and such surface damage may increase the defect rate of the final product.

In order to solve the above-described problem, a protective film that protects the surface of the display device from being damaged during processing is used. The protective film is stably attached to the surface of the display device or the semiconductor device, and must be easily peeled off from the adherend after processing is completed. In particular, when peeling, the display device must be peeled off without any damage or residue.

However, the protective film for the conventional process has a relatively high adhesive strength, so that the peeling was not easy without damaging the surface, and contamination by residues of the adhesive layer after peeling was caused. In particular, in order to increase the productivity and process speed of the display device, if the protective film is peeled at a high speed of 2,000 mm / min or more after processing, the adhesive force of the protective film also increases in proportion to the peeling speed. There was a limit to speed and productivity.

On the other hand, the present inventors have a single layer of adhesive layer containing a thermosetting component and a photocuring component, thereby exhibiting a stable initial adhesive strength due to the thermosetting component, and at the same time, realizing a significant decrease in adhesive strength due to further performing photocuring after processing. It was intended to provide a protective film for a process having excellent peelability.

However, when the adhesive layer is a relatively thick thick film type single layer, the UV light intensity and irradiation amount must be increased in order to exhibit a desired peeling effect, and if insufficient, additional photocuring by UV irradiation is an adhesive layer. Since it does not occur even inside, it was found that it is not only difficult to exert the desired peeling effect, but also lowers the reliability of the final product.

Thus, the present invention is provided with a coating layer of a multi-layered structure comprising a light-transmitting first coating layer containing a thermosetting component; and a heat-sensitive component and a light-curable adhesive second coating layer containing a photo-curing component. By adjusting the thickness and physical properties, it is a technical task to provide a protective film for easy peelability by maximizing the photo-curing efficiency while realizing a low adhesion to an adherend having surface roughness under high-speed peeling conditions.

In order to achieve the above technical problem, the present invention is a first substrate; Second substrate; And at least two or more multi-layer coating layers formed between the first base material and the second base material, wherein the multi-layer coating layer comprises: a first light-transmitting coating layer comprising a thermosetting component; And a thermosetting component and a photocurable adhesive second coating layer including a photocurable component.

According to the exemplary embodiment of the present invention, the light-transmitting first coating layer may have a light transmittance of 80% or more at a wavelength of 380 to 780 nm, and a haze of 0.5 to 3.0%.

According to an embodiment of the present invention, the light-transmitting first coating layer may be a coating layer having a modulus of 100 to 800 MPa and a pencil hardness of 2H to 5H at 25 ° C.

 According to one embodiment of the present invention, the first optically transmissive coating layer may be 0.5 gf / inch or less tack-free.

According to one embodiment of the present invention, the light-transmitting first coating layer includes at least one hydroxyl group (-OH) or carboxyl group (-COOH) in the molecule, and has a glass transition temperature (° C) of -50 ° C to -30 ° C. , And a (meth) acrylate resin having a weight average molecular weight (Mw) of 100,000 to 600,000 g / mol; And it may include a polyfunctional or more polyfunctional epoxy-based thermosetting curing agent or isocyanate-based thermosetting curing agent.

According to an embodiment of the present invention, when peeling at a rate of 1,500 to 3,000 mm / min before photocuring, the adhesive strength to the adherend of the adhesive second coating layer is 20 gf / inch or less, and after photocuring 1,500 to 3,000 mm When peeling at a rate of / min, the adhesive force to the adherend of the adhesive second coating layer may be 2.5 gf / inch or less.

According to one embodiment of the present invention, the adhesive second coating layer may have an adhesive strength reduction rate of Equation 1 below from 80 to 95% due to additional photocuring by light energy of 100 to 800 mJ / cm ² .

[Equation 1]

Adhesion reduction rate (%) = (A ₁ -A ₂ ) / A ₁ × 100

In the above formula, A ₁ is the adhesive strength of the adhesive second coating layer before photocuring, and A ₂ is the adhesive strength of the adhesive second coating layer after photocuring.

According to an embodiment of the present invention, the adhesive second coating layer is a polyol; Thermosetting agent; An epoxy-based (meth) acrylate monomer having at least one epoxy group in the molecule and having two or more functional groups; A silicone-based (meth) acrylate oligomer having at least one silicone in the molecule and having at least five functionalities; And it may include a cured product of the pressure-sensitive adhesive composition containing a photoinitiator.

According to one embodiment of the present invention, the polyol may have a weight average molecular weight (Mw) of 50,000 to 150,000 g / mol.

According to one embodiment of the present invention, the epoxy-based (meth) acrylate monomer has a molecular weight of 100 to 1,000 g / mol, and may have 2 to 6 polymerizable functional groups.

According to one embodiment of the present invention, the silicone-based (meth) acrylate oligomer has a weight average molecular weight (Mw) of 5,000 to 20,000 g / mol, and may have 5 to 15 polymerizable functional groups.

According to one embodiment of the invention, the pressure-sensitive adhesive composition, based on 100 parts by weight of the polyol, respectively, 1 to 10 parts by weight of a heat curing agent; 3 to 20 parts by weight of an epoxy (meth) acrylate monomer; 10 to 30 parts by weight of a silicone-based (meth) acrylate oligomer; And 0.1 to 7 parts by weight of a photoinitiator.

According to an embodiment of the present invention, the first base material and the second base material may be at least one of a protective film and a release film, respectively.

According to an embodiment of the present invention, the thickness of the protective film is 50 to 150 μm, and the thickness of the release film may be 10 to 100 μm.

According to an embodiment of the present invention, the protective film for the process, a protective film; A light transmissive first coating layer; Adhesive second coating layer; And a release film may be sequentially stacked.

According to an embodiment of the present invention, the coating base film; The thickness ratio between the light-transmissive first coating layer and the adhesive second coating layer may be 1: 0.4 to 1.4: 0.05 to 0.7.

According to one embodiment of the present invention, the first base material is a polyethylene terephthalate (PET) film, a polybutylene terephthalate film, a polyethylene naphthalate (PEN) film, a polyethylene film, a polypropylene film, a cellophane, a diacetyl cellulose film , Triacetylcellulose film, acetylcellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film , Polyether ether ketone film, polyether sulfone film, polyetherimide film, polyimide (PI) film, fluorine resin film, polyamide film, acrylic resin film, norbornene resin film, and cycloolefin resin film Can be

According to one embodiment of the present invention, the second base material may be any one of a release paper and a release polymer film.

According to one embodiment of the present invention, the protective film for the process can be used in any one of the manufacturing process of the semiconductor device and the display device.

According to one embodiment of the present invention, the protective film for the process is attached to one side of the adhesive second coating layer and the adherend after detaching the second substrate, the adherend being a cover glass, a cover plastic of a semiconductor device or a display device It may be any one of a film, an organic photosensitive material, an encapsulating material and a polarizing film.

According to the exemplary embodiment of the present invention, the surface of the protective film for the process where the second base material is detached and one surface of the adherend to be attached may be formed with a predetermined surface roughness.

The protective film for a process according to the present invention comprises at least two or more multi-layer coating layers instead of a single-layer adhesive layer in the form of a conventional thick film (50 μm or more), by controlling the composition, thickness and physical properties of each layer constituting the multi-layer coating layer. Under the high-speed peeling condition, it is possible to implement a low adhesive force even to an adherend having roughness.

In addition, through the maximization of the efficiency of photo-curing, it exhibits a rapid drop in adhesive strength according to the additional implementation of photo-curing, so it can realize high detaping characteristics and excellent processability at the same time without leaving surface damage or peeling residue after processing of the display device. You can.

In addition, in the present invention, by optimally blending the composition of the adhesive layer, it is possible to reduce the adhesive force even during high-speed peeling, and at the same time, high light transmittance, low haze characteristics, and surface resistance can be secured.

Accordingly, the protective film for the process of the present invention can be usefully applied to the manufacturing process of display devices in the field, including flat panel displays, and other semiconductor devices and manufacturing processes thereof.

1 is a cross-sectional view showing the structure of a protective film for a process according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below. In addition, embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

In the present specification, “(meth) acrylate” refers to acrylate and / or methacrylate.

In addition, in this specification, "monomer" and "monomer" have the same meaning. The monomer in the present invention is a compound that is distinguished from oligomers and polymers and has a weight average molecular weight (Mw) of 1,000 g / mol or less. In the present specification, "polymerizable functional group" refers to an unsaturated group involved in the polymerization reaction, such as (meth) acrylate group.

In addition, since the size and thickness of each component shown in the drawings are arbitrarily shown for convenience of description, the present invention is not necessarily limited to what is shown. In the drawings, thicknesses are enlarged to clearly represent various layers and regions. In the drawings, thicknesses of some layers and regions are exaggerated for convenience of description.

Also, in the specification, when a part “includes” a certain component, it means that other components may be further included instead of excluding other components, unless otherwise stated. In addition, throughout the specification, "above" or "on" means that not only is located above or below the target part, but also when there is another part in the middle, and the direction of gravity must be determined. It does not mean that it is located above the standard.

<Protective film for process>

1 schematically shows a cross-sectional structure of a protective film for a process according to the present invention.

Referring to Figure 1, the protective film for the process 100, the first base 130; A second substrate 140; And at least two or more multi-layer coating layers formed between the first base 130 and the second base 140, wherein the multi-layer coating layer comprises: a first light-transmitting coating layer 110 including a thermosetting component; And a second coating layer 120 that can be further photocured including a thermosetting component and a photocurable component.

Here, one of the first substrate 130 and the second substrate 140 is a substrate for a protective film (substrate), the other is a substrate for a release film.

Light transmissive first coating layer

In the protective film 100 for the process of the present invention, the light-transmitting first coating layer 110 supports the second adhesive layer 120, which will be described later, and has light transparency, thereby further light curing of the second adhesive layer 120. It serves to make it possible.

The light-transmitting first coating layer 110 is a heat-curing layer comprising a conventional thermosetting resin and a thermosetting agent known in the art. Particularly, the light-transmitting first coating layer 110 uses an acrylic resin having a high hardness and modulus as a main resin, and mixes at least one heat curing agent among epoxy and isocyanate to form an illuminance. It is preferable that it is a hard coating layer in which wettability with an adherend is suppressed.

The (meth) acrylate resin serves to express the hardness and modulus of the coating film by controlling the crosslinking density of the entire coating layer of the light-transmitting first coating layer 110. The (meth) acrylate resin may include, without limitation, acrylic polymer resins known in the art. Specifically, it may be prepared by a conventional solution polymerization method or suspension polymerization method using conventional (meth) acrylic monomers and other known components that can be used in the production of (meth) acrylic resins.

According to an embodiment of the present invention, the (meth) acrylate resin may have a weight average molecular weight (Mw) of 100,000 to 600,000 g / mol, preferably 150,000 to 600,000 g / mol, and more preferably 200,000 to 400,000 g / mol. When it has the above-mentioned weight average molecular weight, cohesive force is secured, and adhesion to the adherend surface having roughness can be maintained without deformation of the coating film. If it is higher than the above-mentioned weight average molecular weight range, the lack of adhesion and light transmittance are inhibited, and if it is low, the cohesive force is lowered to deform by the roughness of the surface to be adhered, thereby exhibiting an effect of increasing adhesion.

According to another embodiment of the present invention, the (meth) acrylate resin may have a glass transition temperature (Tg) of -50 to -30 ℃. In the above range, the coating film of the light-transmitting first coating layer 110 maintains sufficient hardness to prevent the coating film from being damaged or easily broken and peeled off from the substrate by an external impact, and is also too hard to prevent deterioration of workability with other substrates. have. Here, the glass transition temperature of the (meth) acrylate resin can be determined by the calculated value using the FOX equation and the measured value by thermal analysis.

According to another embodiment of the present invention, the (meth) acrylate resin includes at least one hydroxyl group (-OH) or carboxyl group (-COOH) in the molecule for thermal curing reaction with an epoxy-based curing agent or an isocyanate-based curing agent. can do.

In the present invention, the content of the (meth) acrylate resin may be 90 to 99 parts by weight based on the total weight (for example, 100 parts by weight) of the thermosetting composition for forming the light-transmitting first coating layer, more specifically 94 It may be from 98 parts by weight. When the content of the (meth) acrylate resin falls within the above-described range, desired hardness, modulus, and light transmissive effects may be expressed. The remaining amount excluding the content of the (meth) acrylate resin in the total weight of the above-mentioned thermosetting composition for forming the light-transmitting first coating layer may be a content of a curing agent or other additives.

The curing agent is not particularly limited as long as it is a heat curing agent capable of reacting with the aforementioned acrylate resin. As an example, a thermosetting epoxy curing agent and / or an isocyanate curing agent can be used.

The epoxy curing agent can improve the curing rate and improve heat resistance. The epoxy curing agent may be used without limitation an epoxy-based component known in the art. Preferably, a bifunctional or more polyfunctional epoxy-based thermosetting curing agent can be used. Here, the polyfunctional epoxy-based curing agent refers to an epoxy-based curing agent having an average number of epoxy groups in a molecule of 2 or more, preferably 2 to 4.

In addition, the isocyanate curing agent can be used without limitation a conventional curing agent having an isocyanate group (-NCO) contained in the molecule. Non-limiting examples of isocyanate curing agents that can be used include, but are not limited to, methylene diphenyl diisocyanate (MDI), toluene diisocyante (TDI), hexamethylene diisocyanate (HMDI) ), Isoprone diisocyanate (IPDI), meta xylene diisocyanate (MXDI), tetramethylxylene diisocyanate (TMXDI), diisocyanates made by alicyclic by adding hydrogen to the benzene ring of the MDI (H12 MDI), diisocyanate (hydrogenated XDI) made by alicyclic by adding hydrogen to the benzene ring of xylene diisocyanate (XDI). The above-mentioned components may be used alone or in combination of two or more.

In the present invention, the content of the thermosetting agent is not particularly limited, for example, the (meth) acrylate resin may be 0.5 to 5 parts by weight based on 100 parts by weight, preferably 1 to 3 parts by weight.

The present invention, as long as it does not impair the intrinsic properties of the light-transmitting first coating layer 110, various polymers such as flame retardants, conventional thermosetting resins or thermoplastic resins and oligomers thereof, solid ultraviolet rubber particles or ultraviolet rays as necessary. Common additives such as absorbents, antioxidants, polymerization initiators, dyes, pigments, thickeners, leveling agents, antioxidants, concealers, lubricants, process stabilizers, plasticizers, blowing agents, reinforcing agents, colorants, fillers, granules, metal inerts, solvents, etc. And the like.

The light-transmitting first coating layer 110 of the present invention described above, after preparing a thermosetting composition comprising a (meth) acrylate resin and a heat curing agent, and other additives, if necessary, the composition as a first base (130) ) And the second substrate 140, and then dried and heat-cured.

Since the light-transmitting first coating layer 110 manufactured as described above transmits the irradiated UV, an additional photo-curing reaction of the adhesive second coating layer 120 located thereunder must occur, so it must have excellent light transmissivity. . In addition, it can exhibit high hardness and modulus compared to a coating layer containing a conventional acrylic resin.

According to an embodiment of the present invention, the light-transmitting first coating layer 110 may have a light transmittance of 80% or more at a wavelength of 380 to 780 nm, and a haze of 0.5 to 3.0%. In addition, the modulus may be 100 to 800 MPa at 25 ° C, and a hard coating layer having a pencil hardness of 2H to 5H. In addition, the light-transmitting first coating layer 110 of the present invention may have a low adhesive force or may be non-tacky. In one example, the light-transmitting first coating layer 110 may be a tack-free coating layer of 0.5 gf / inch or less.

The thickness of the light-transmitting first coating layer 110 is not particularly limited, and may be 5 to 70 μm, and preferably 5 to 50 μm.

Adhesive second coating layer

In the protective film 100 for the process of the present invention, the adhesive second coating layer 120 is attached to one surface of the display device and / or semiconductor device, which is an adherend, and exhibits stable initial adhesive strength, and at the same time, significantly reduces adhesive strength after photocuring. Due to this, it plays a role in exerting excellent detaping characteristics.

The adhesive second coating layer 120 is a thermosetting adhesive layer that can be further photocured by including a thermosetting component and a photocurable component, for example, primary thermal curing by urethane or acrylic resin and an isocyanate curing agent. Afterwards, it is a second adhesive layer capable of controlling the adhesive strength before and after light irradiation by enabling secondary additional photocuring by UV oligomer and photoinitiator. Specifically, the adhesive second coating layer 120 includes a cured product of a pressure-sensitive adhesive composition in which a thermosetting component containing a polyol and a curing agent is mixed with a photocurable component containing at least two specific photopolymerizable monomers and oligomers.

The thermosetting component constituting the adhesive second coating layer 120 of the present invention includes a polyol and a thermosetting agent.

The polyol can be used without limitation a conventional polyol used in the art of polyurethane synthesis. Non-limiting examples of polyols that can be used include polyether polyols, polyester polyols, polycaprolactone polyols, polytetramethylene ether diols, polybutadiene diols, polytetramethylene ether diols, polypropylene oxide diols, polybutylene oxide diols, Polytetramethylene ether glycol, polypropylene oxide glycol, polypropylene oxide triol, polybutylene oxide glycol, polybutylene oxide triol, triol, and the like. The above-mentioned components may be used alone or in combination of two or more.

According to one embodiment of the invention, the polyol may be a resin having a weight average molecular weight (Mw) of 50,000 to 150,000 g / mol, and preferably 80,000 to 100,000 g / mol. When the weight average molecular weight of the polyol is less than 50,000, the molecular weight is excessively lowered to decrease flexibility, and when it exceeds 150,000, hardness and abrasion resistance of the adhesive layer may be reduced.

The content of the polyol is not particularly limited, and for example, it may be 50 to 60 parts by weight based on the total weight (eg, 100 parts by weight) of the pressure-sensitive adhesive composition. If the content of the polyol is less than 50 parts by weight, the hardness of the urethane composition may be weakened, and when it exceeds 60 parts by weight, stability against impact and tear strength may be weakened.

The curing agent is not particularly limited as long as it is a heat curing agent capable of reacting with the aforementioned polyol to form a urethane resin. As an example, an isocyanate curing agent can be used.

The isocyanate curing agent serves to form a urethane resin by reacting the isocyanate group (-NCO) contained in the molecule with the hydroxy group (-OH) of the polyol described above. Non-limiting examples of isocyanate curing agents that can be used include, but are not limited to, methylene diphenyl diisocyanate (MDI), toluene diisocyante (TDI), hexamethylene diisocyanate (HMDI) ), Isoprone diisocyanate (IPDI), meta xylene diisocyanate (MXDI), tetramethylxylene diisocyanate (TMXDI), diisocyanates made by alicyclic by adding hydrogen to the benzene ring of the MDI (H12 MDI), diisocyanate (hydrogenated XDI) made by alicyclic by adding hydrogen to the benzene ring of xylene diisocyanate (XDI). The above-mentioned components may be used alone or in combination of two or more.

In the present invention, the equivalent ratio between the polyol and the isocyanate curing agent can be appropriately adjusted within a range known in the art, and for example, the use ratio of the polyol and the curing agent may be 1: 0.8 to 1.2 equivalent ratio.

The content of the isocyanate curing agent is not particularly limited, and for example, may be 1 to 10 parts by weight based on 100 parts by weight of the polyol, and preferably 1 to 6 parts by weight. When the content of the isocyanate is less than 1 part by weight, a hydroxyl group may remain in the pressure-sensitive adhesive composition, and thus the hardness and strength of the adhesive layer may be reduced, and when it exceeds 10 parts by weight, an isocyanate group remains, resulting in foaming phenomenon due to bonding with moisture. Cracks may occur.

The photocurable component constituting the adhesive second coating layer 120 of the present invention includes at least two specific photopolymerizable monomers, oligomers, and photoinitiators. Specifically, a polyfunctional epoxy-based (meth) acrylate monomer having at least one epoxy group in the molecule and having at least one functional group; A polyfunctional silicone-based (meth) acrylate oligomer having at least one silicone in the molecule and having at least one functional group; And photoinitiators.

The epoxy-based (meth) acrylate monomer acts as a cross-linking agent for controlling the crosslinking density between polymers after photopolymerization, and assists in curing properties such as hardness, adhesion, and appearance characteristics of the adhesive second coating layer 120. The epoxy-based (meth) acrylate monomer may have two or more, preferably 2 to 6, polymerizable functional groups, such as (meth) acrylate groups, in the molecule, which are polymerizable unsaturated groups. In addition, it may have at least one epoxy group in the molecule, specifically, it is preferable that two or more epoxy groups are present, preferably 2 to 4. In addition, the molecular weight of the epoxy-based (meth) acrylate monomer may be 100 to 1,000 g / mol, and preferably 200 to 700 g / mol.

The content of the epoxy-based (meth) acrylate monomer is not particularly limited, and for example, it may be 3 to 20 parts by weight based on 100 parts by weight of the polyol, and preferably 4 to 20 parts by weight. When the content of the epoxy-based (meth) acrylate monomer falls within the above-described range, an initial adhesive strength increase effect may be exhibited.

In addition, the silicone-based (meth) acrylate oligomer, as a main component for forming a coating film after photopolymerization, controls the crosslinking density of the entire coating film and serves to express adhesive properties.

The silicone-based (meth) acrylate oligomer may include 5 or more polymerizable functional groups in the molecule, preferably 5 to 15, and more preferably 8 to 12. At this time, if the number of polymerizable functional groups in one molecule of the polyfunctional silicone (meth) acrylate oligomer is less than 5, it may be difficult to exhibit desired adhesive properties. In addition, the polyfunctional silicone (meth) acrylate oligomer may have at least one silicone in a molecule, and specifically, it is preferable to include 2 to 4 silicone-containing groups (eg, siloxane groups, etc.). In addition, the weight average molecular weight (Mw) of the silicone (meth) acrylate oligomer may be 5,000 to 20,000 g / mol, and preferably 5,000 to 10,000 g / mol.

The content of the silicone-based (meth) acrylate oligomer is not particularly limited, and for example, it may be 10 to 30 parts by weight based on 100 parts by weight of the polyol, and preferably 10 to 20 parts by weight. When the content of the silicone-based (meth) acrylate oligomer falls within the above-described range, it is possible to exert an effect of lowering the adhesive strength after light irradiation.

The photoinitiator is a component that is excited by light energy such as ultraviolet light (UV) to initiate photopolymerization, and conventional photopolymerization photoinitiators in the field can be used without limitation.

Non-limiting examples of photoinitiators that can be used include Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure 907, Benzionalkylether, Benzophenone, Benzyl dimethyl katal, Hydro Hydroxycyclohexyl phenylacetone, chloroacetophenone, 1,1-dichloro acetophenone, diethoxy acetophenone, hydroxyacetophenone (diethoxyaceto Phenone (Hydroxy Acetophenone), 2-Choro thioxanthone, 2-ETAQ (2-EthylAnthraquinone), 1-hydroxy-cyclohexyl-phenyl-ketone (1-Hydroxy-cyclohexyl-phenyl-ketone) , 2-hydroxy-2-methyl-1-phenyl-1-propanone (2-Hydroxy-2-methyl-1-phenyl-1-propanone), 2-hydroxy-1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-methyl-1-propanone (2-Hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propanone), methylbenzoylpo Mate (methylbenzoylformate), etc. These may be used alone or in combination of two or more.

The content of the photoinitiator is not particularly limited, for example, it may be 0.1 to 7 parts by weight based on 100 parts by weight of the polyol, preferably 0.1 to 5 parts by weight. When the content of the photoinitiator falls within the above-described range, a photopolymerization reaction may be sufficiently performed without deteriorating physical properties.

The pressure-sensitive adhesive composition of the present invention may include a solvent known in the art. Non-limiting examples of solvents that can be used include, N-methylpyrrolidinone (NMP), N, N-dimethylacetamide (DMAc), tetrahydrofuran (THF), And one or more substances selected from the group consisting of N, N-dimethylformamide (DMF: N, N-dimethylformamide), dimethylsulfoxide (DMSO), cyclohexane, and acetonitrile. . The content of the solvent is not particularly limited, and may be a residual amount that satisfies the total weight (eg, 100 parts by weight) of the pressure-sensitive adhesive composition.

The present invention, as long as it does not impair the inherent properties of the adhesive second coating layer 120, flame retardants known in the art as necessary, various polymers such as thermosetting resins or thermoplastic resins and oligomers thereof, solid rubber particles Or conventional additives such as UV absorbers, antioxidants, polymerization initiators, dyes, pigments, thickeners, leveling agents, antioxidants, hiding agents, lubricants, processing stabilizers, plasticizers, foaming agents, reinforcing agents, colorants, fillers, granules, metal inerts, etc. And the like.

The above-mentioned adhesive second coating layer 120 of the present invention includes a thermosetting component containing a polyol and a curing agent, a photocurable component containing at least two specific photopolymerizable monomers and oligomers, and a photoinitiator, and other additives as necessary. After preparing the pressure-sensitive adhesive composition comprising, it may be prepared by applying the composition on the light-transmitting first coating layer 110 and then drying and heat-curing.

The adhesive second coating layer 120 formed through thermosetting has a polyurethane resin derived from a thermosetting component as a main component, and includes a silicone-based (meth) acrylate oligomer, an epoxy-based (meth) acrylate monomer, and a photoinitiator. The chemical component is not polymerized and is present in dispersed form. The photocurable component is further subjected to a photopolymerization reaction through a predetermined light energy irradiation.

The thickness of the adhesive second coating layer 120 is not particularly limited, and may be in the range of 5 to 70 μm, preferably 5 to 50 μm.

Article 1

In the protective film 100 for a process of the present invention, a first base material 130 is disposed on one surface of the light-transmitting first coating layer 110. The first base 130 may be a coating substrate of the light-transmitting first coating layer 110.

The first base 130 is not particularly limited, and a plastic film having transparency known in the art may be used without limitation.

Non-limiting examples of the first base material 130 that can be used include, but are not limited to, polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, polyethylene films, polypropylene films, cellophane, and diacetylcellulose. Film, triacetylcellulose film, acetylcellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone Film, polyether ether ketone film, polyether sulfone film, polyetherimide film, polyimide (PI) film, fluororesin film, polyamide film, acrylic resin film, norbornene resin film, cycloolefin resin film And so on. Specifically, it may be at least one of a polyimide (PI) film, a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, a protective film, and a carrier film.

Here, the protective film and the carrier film may be used conventionally known in the art, for example, may be an adhesive layer formed on one surface of a polyimide film, PET film, PEN film. The adhesive layer may be a component commonly used in the art, and for example, an epoxy-based adhesive, a silicone-based adhesive, an acrylic-based adhesive, and mixed components thereof may be contained. The silicone pressure-sensitive adhesive may be a PSA in the form of a liquid resin using a siloxane polymer as a binder.

The thickness of the first base 130 is not particularly limited, and may be, for example, 50 to 150 μm, and preferably 50 to 100 μm. If necessary, the first substrate 130 may be a surface treatment such as a matte treatment or a corona treatment, or may be an antistatic treatment.

Article 2

In the protective film for the process of the present invention, the first substrate 130 and the substrate 120 for a different purpose than the above-described first substrate 130, for example, the second substrate 140 for release use are disposed on the other surface of the adhesive second coating layer 120. .

The second substrate 140 may be used without limitation, conventionally known in the art, for example, release paper, and release polymer film (eg, release PET film). The second base 140 may be formed by laminating.

The release polymer film may be applied without limitation, such as a conventional plastic film known in the art. Non-limiting examples of plastic films that can be used include polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, polyethylene films, polypropylene films, cellophane, diacetylcellulose films, and triacetylcellulose films. , Acetylcellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether And a turketone film, a polyether sulfone film, a polyetherimide film, a polyimide film, a fluorine resin film, a polyamide film, an acrylic resin film, a norbornene resin film, and a cycloolefin resin film. These plastic films may be either transparent or translucent, and may be colored or non-colored, and may be appropriately selected depending on the application.

The thickness of the second base 140 is not particularly limited, and may be, for example, 10 to 100 μm.

The protective film 100 for a process of the present invention described above may have a total thickness of 100 μm to 300 μm, but is not limited thereto and may have various thicknesses depending on the applied product.

Conventional UV photocuring-related technologies have formed the thickness of the adhesive layer to a thin film level of 10 to 20 μm in order to optimize the photocurability. Particularly, when the adhesive layer in the form of a photocurable single layer is a thick film having a thickness of 50 μm or more, the photocuring reaction inside the thick film due to UV irradiation is unlikely to occur uniformly, so there is a limitation in expanding the variation width of the adhesive force. Accordingly, it was difficult to uniformly lower the adhesive force by UV photocuring as the thickness of the adhesive layer increased.

Thus, in the present invention, instead of a single layer adhesive layer in the form of a conventional thick film (over 50 μm), at least two or more multilayer coating layers are formed, but the light-transmitting first coating layer (thermal curing layer) and the adhesive second coating layer (which form the multilayer coating layer) By adjusting the composition, thickness, and physical properties of the heat / photocurable layer), the modulus, hardness, and photocurable adhesive strength of the adhesive layer are simultaneously controlled. Particularly, in the present invention, by adjusting the thickness of the adhesive second coating layer 120 to be smaller than that of the conventional thick-film single layer adhesive layer, after UV irradiation, the photocuring efficiency is maximized through a uniform curing reaction, resulting in excellent peelability of 2 gf / in or less. Detaping characteristics can be exhibited. In addition, through the high hardness and modulus implementation of the light-transmitting first coating layer 110, it is possible to implement a low adhesion of 20 gf / in level to an adherend having roughness under high-speed peeling conditions.

According to an embodiment of the present invention, the protective film for the process 100 is a protective film 130; Light-transmitting first coating layer 110; Adhesive second coating layer 120; And a release film 140 may be sequentially stacked. Here, the protective film 130; The thickness ratio between the light-transmissive first coating layer 110 and the adhesive second coating layer 120 may be 1: 0.4 to 1.4: 0.05 to 0.7, and preferably 1: 0.5 to 1.2: 0.15 to 0.5. In addition, the overall thickness of the multi-layer coating layer that combines the light-transmitting first coating layer 110 and the adhesive second coating layer 120 is a first base material 130 and a first base material used as a coating substrate for the above-mentioned light-transmitting first coating layer 110. Any one of the two substrates 140, for example, may be adjusted to have the same thickness as the protective film 130.

On the other hand, the protective film for the process is generally not detached from the surface of the display device or the semiconductor device during the processing process, and is easily detached after processing, and it is required that the adhesive layer is not transferred when peeling. very important.

The protective film 100 for a process according to the present invention can control the initial adhesive strength and the adhesive strength after light curing to a predetermined range through optimization of the composition of the adhesive second coating layer 120, and residues before and after UV irradiation are generated. Does not work. Through such adhesion control, it is possible to significantly improve the processability, productivity and economics of the display device.

According to one embodiment of the present invention, the protective film for the process 100 is peeled at a rate of 1,500 ~ 3,000mm / min after photocuring, the adhesive force of the adhesive body of the adhesive second coating layer 120 is 2.5 gf It may be less than / inch, preferably greater than 0, less than 2.0 gf / inch.

According to another embodiment of the present invention, the protective film for the process 100 when peeling at a rate of 1,500 ~ 3,000mm / min before photocuring, the adhesive strength of the adherend of the second adhesive layer 120 is 20 It may be gf / inch or less, preferably 10 to 20 gf / inch. Here, the initial adhesive strength and the adhesive strength after photocuring are measured based on the case where the thickness of the adhesive second coating layer 120 is 50 to 150 μm, preferably 75 to 100 μm, respectively.

The adherend may be a structure of one surface of a display device or a semiconductor device to which the protective film 100 for a process of the present invention is attached, and is not particularly limited. For example, the display device may be any one of a cover glass, an organic photoresist, an encapsulation material, and a polarizing film. The glass may be a general glass substrate or tempered glass.

In general, when the thickness of the adhesive layer is thick, and / or the peeling rate is high, the adhesive strength of the adhesive layer is increased proportionally, and the peeling property is remarkably deteriorated. In addition, as the surface roughness of the adherend to which the adhesive layer adheres increases, the peeling properties significantly decrease. On the other hand, in the present invention, even if the protective film having a thick fim-type multilayer coating layer having a thickness of 50 µm or more is peeled at a high speed at a speed of 1,500 to 3,000 mm / min, the adhesive second coating layer 120 is rapidly exposed after photocuring. Excellent peeling properties can be exhibited due to reduced adhesion. At this time, the surface roughness (Ra) of the adherend is not particularly limited, and may have a range of roughnesses known in the art. For example, it may be 0.5 to 10 μm.

According to another embodiment of the present invention, the adhesive second coating layer 120 may have an adhesive strength reduction rate represented by the following Equation 1 due to additional photo-curing by light energy of 100 to 800 mJ / cm ² , may be 80 to 95%. And preferably 80 to 90%.

[Equation 1]

Adhesion reduction rate (%) = (A ₁ -A ₂ ) / A ₁ × 100

In the above formula, A ₁ is the initial adhesive strength of the adhesive second coating layer before photocuring, and A ₂ is the adhesive strength of the adhesive second coating layer after photocuring.

Meanwhile, in the present invention, the above-described embodiment of FIG. 1 is exemplarily described. However, the present invention is not limited thereto, and it is also within the scope of the present invention to construct a layer having a multilayer structure rather than the structure illustrated by introducing another conventional layer in the art.

<Method of manufacturing protective film for process>

The present invention provides a method of manufacturing a protective film for the above-described process.

Such a protective film can be produced without limitation according to conventional methods known in the art. As an example, the protective film for the process is coated with a first light-transmitting first coating layer (thermosetting) and an adhesive second coating layer (thermal / UV curable) continuously on one of the first and second substrates, and then the second coating layer It can be produced by laminating the other and the other substrate.

For one embodiment of the method of manufacturing a protective film for a process according to the present invention, (i) by applying and curing a composition for forming a light-transmitting first coating layer on one surface of a first substrate to form a light-transmitting first coating layer step; (ii) forming an adhesive second coating layer by applying and drying the composition for forming an adhesive second coating layer on the light-transmitting first coating layer; And (iii) laminating a second base material on the other surface of the adhesive first coating layer.

The light-transmitting first coating layer 110 prepares a thermosetting composition in which the above-mentioned (meth) acrylate resin and a thermosetting agent are mixed at a predetermined mixing ratio, and then applies the thermosetting composition on one surface of the first base 130 After drying / heating can be prepared.

According to one embodiment of the present invention, the composition for forming the light-transmitting first coating layer is (meth) acrylate resin And a heat curing agent, wherein the heat curing agent is compared to 100 parts by weight of the (meth) acrylate resin. It may be a composition containing 0.5 to 5 parts by weight. The composition for forming the light-transmitting first coating layer may further include a residual amount of a solvent satisfying 100 parts by weight of the thermosetting composition.

The method of applying the composition for forming the light-transmitting first coating layer on the first base 130 is not particularly limited, and a conventional coating method known in the art can be used without limitation. As an example, various methods such as a casting method, a dip coating, a die coating, a roll coating, a slot die, a comma coating, or a mixing method thereof may be used. Subsequently, the drying process can be suitably carried out within the usual conditions known in the art. As an example, drying may be performed at 100 to 200 ° C. for 5 minutes to 2 hours.

In addition, after preparing the pressure-sensitive adhesive composition in which the above-described thermosetting component and the photo-curable component are mixed at a predetermined mixing ratio, the second adhesive layer 120 is coated on one surface of the light-transmitting first coating layer 110. It can be prepared by drying / heating.

According to one embodiment of the present invention, the pressure-sensitive adhesive composition for forming the second adhesive layer is 1 to 10 parts by weight of a heat curing agent, respectively, based on 100 parts by weight of the polyol; 3 to 20 parts by weight of an epoxy (meth) acrylate monomer; 10 to 30 parts by weight of a silicone-based (meth) acrylate oligomer; And 0.1 to 7 parts by weight of a photoinitiator. The pressure-sensitive adhesive composition may further include a residual amount of a solvent that satisfies 100 parts by weight of the pressure-sensitive adhesive composition.

The adhesive composition for forming the adhesive second coating layer may also be prepared through the above-described coating method. The drying process can also be carried out properly within the usual conditions known in the art.

The adhesive second coating layer 120 formed through thermal curing may be semi-cured or fully cured. At this time, semi-curing means a state that has already been cured and has been cured for a certain level or more. For example, the degree of cure (D) may be about 40% to 80%.

Subsequently, the adhesive second coating layer 120 may be manufactured by laminating by facing one surface of the second base 140.

Here, the first base 130 and the second base 140 may be sheet-shaped, respectively, or may be wound in a roll shape after being continuously laminated according to a roll-to-roll method. In addition, sheet-to-sheet lamination, roll-to-sheet lamination, and the like can also be used.

The protective film for a process manufactured as described above is then subjected to additional photocuring by irradiating a predetermined light energy. This photocuring method can be performed by methods known in the art. In one example, the additional photo-curing may be performed using a metal halide lamp used in a conventional, e.g., about 100 to 800mJ / cm ^2, preferably UV irradiation of about 300mJ / cm ² to 500mJ / cm ² However, it is not limited thereto.

The above-described protective film for a process of the present invention and its modified examples are applicable to various fields requiring excellent adhesion and peeling properties. In particular, it can be applied without limitation to the manufacturing process of the display device.

In the present invention, the display device refers to a device that displays an image, as well as a flat panel display device (FPD), a curved display device, and a foldable display device. And a flexible display device. Specifically, the display device is a liquid crystal display (Liquid Crystal Display), an electrophoretic display (Electrophoretic Display), an organic light emitting display (Organic Light Emitting Display), an inorganic EL display (Inorganic Light Emitting Display), field emission display The device may be a field emission display, a surface-conduction electron-emitter display, a plasma display, a cathode ray display, or electronic paper. For one embodiment, it may be a flat panel display panel such as LCD, PDP, OLED.

The protective film of the present invention is not limited to the aforementioned use, and is applicable to a conventional semiconductor device known in the art and a manufacturing process thereof. The semiconductor manufacturing process includes all of the conventional processes known in the art, and may be, for example, a semiconductor wafer process.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are only to illustrate the present invention, the present invention is not limited by the following examples.

[Examples 1-4. Manufacturing of protective film for process]

1-1. Preparation of composition for forming light-transmitting first coating layer

The components of the composition for forming the light-transmitting first coating layer were prepared by mixing according to the ratio of the compounding example in [Table 1]. In Table 1, the unit of use of each composition is parts by weight.

1-2. Preparation of an adhesive composition for forming an adhesive second coating layer

The components of the adhesive composition for forming the adhesive second coating layer were prepared by mixing according to the ratio of the compounding example in [Table 1]. In Table 1, the unit of use of each composition is parts by weight.

1-2. Manufacturing of protective film for process

After coating the composition for forming the above-mentioned light-transmitting first coating layer on one surface of a PET film (Gerontech ZR-ASD), it was coated and dried at 120 ° C. for 5 minutes to prepare a light-transmitting first coating layer. Subsequently, on the prepared light-transmitting first coating layer, a pressure-sensitive adhesive composition for forming a pressure-sensitive second coating layer was mixed and coated, followed by coating and drying at 120 ° C. for 5 minutes to prepare an adhesive second coating layer. Thereafter, a release film having a thickness of 25 µm was placed on the other surface of the adhesive second coating layer to prepare a protective film for the process.

The thickness and composition of the protective film for the process thus prepared were measured according to the following measurement method, and the results are shown in Table 1 below.

Example Comparative example One 2 3 4 One 2 Mixing ratio of light-transmitting first coating layer (Meth) acrylate resin ^a)
(Mw: 800,000, Tg: -17 ° C) 100 (Meth) acrylate resin ^b)
(Mw: 400,000, Tg: -36 ° C) 100 100 100 100 (Meth) acrylate resin ^c)
(Mw: 80,000, Tg: -59 ° C) 100 Epoxy curing agent ^d) 2 2 2 Isocyanate curing agent ^e) 2 2 2 Mixing ratio of the adhesive second coating layer Polyol ¹⁾ 100 100 100 100 100 100 Hardener ²⁾ 4 3 4 3 4 3 Photocurable silicone type
Oligomer ³⁾ 10 15 10 15 10 15 Photocurable epoxy system
Monomer ⁴⁾ 20 19 20 19 20 19 Photoinitiator ⁵⁾ 0.5 0.4 0.5 0.4 0.5 0.4 Properties of process protective film Light transmittance (%) 94 96 94 95 73 93 Modulus (Mpa) 600 600 500 500 1,000 300 Hardness 3H 2H 3H 2H 5H N.G Thickness ratio
(Protection film: 1st coating layer: 2nd coating layer) 1: 0.4:
0.35 1: 0.67:
0.33 1: 0.73:
0.27 1: 1.4:
0.1 1: 0.67: 0.33 1: 0.67:
0.33 Initial adhesion
(@ Glass) (gf / inch) 13.68 ± 0.44 11.57 ± 0.10 11.09 ± 0.23 14.6 ± 1.5 7.64 ± 0.68 30.65 ± 4.16 Adhesion after light irradiation (@ Glass) (gf / inch) 1.85 ± 0.10 1.48 ± 0.19 1.46 ± 0.18 1.28 ± 0.40 3.58 ± 0.23 27.53 ± 0.13 Residue O.K O.K O.K O.K N.G N.G

<Light transmissive first coating layer>

(Meta) acrylate resin ^{a) ~ c)} : Doosan Electronics Co., ^Ltd. product (Mw: 800,000 / 400,000 / 80,000)

Epoxy-based curing agent ^d) : Cosmotech, NA-301, 4-functional epoxy

Isocyanate curing agent ^e) : Cosmotech, HDI curing agent

<Adhesive second coating layer>

Polyol ¹⁾ : Samhwa Paint, SERASTER UA5-8 (Mw: 80,000)

Curing agent ²⁾ : Isocyanate type, Samwha Paint Co., SC100I

Photocurable oligomer ³⁾ : Silicone-based oligomer, Miwon Specialty Chemicals, SIU2400 (Number of polymerizable functional groups: 10, Mw: 8,000 g / mol)

Photocurable monomer ⁴⁾ : Epoxy-based oligomer, ENTIS, EB600 (Number of polymerizable functional groups: 2, Molecular weight: 500 g / mol)

Photoinitiator ⁵⁾ : 2,4,6-trimethylbenzoyl-diphenyl phosphine, Ciba Co. Darocur TPO

[Comparative Examples 1 to 2]

The protective films for the processes of Comparative Examples 1 to 2 were prepared in the same manner as in Example 1, except that the composition was changed as shown in Table 1 above.

[Experimental Example 1]

The properties of the protective films for the processes prepared in Examples 1 to 4 and Comparative Examples 1 to 2 were measured according to the following measurement method, and the results are shown in Table 1 above.

(1) 180 ° peel force measurement method (initial adhesion)

A protective film for a process of 2.54 cm x 15 cm (horizontal x vertical) was prepared. After washing the surface of the glass plate to be used as an adherend with acetone, the release sheet of the protective film was detached, the detachable surface of the protective film was opposed to the glass plate, and was rubbed and stacked once using a rubber roller (about 2 kg). After storage at room temperature for 30 minutes, the sample was measured at 180 ° peel force three times at a rate of 3,000 mm / min.

(2) 180 ° peel force measurement method (adhesive power after light irradiation)

After the initial adhesion measurement in (1) above, the laminate of the protective film and the glass plate was irradiated with light energy of 60 mW / cm ² for 5 seconds, then stored at room temperature for 30 minutes and samples were stored at a rate of 3,000 mm / min. The 180 ° peel force was measured three times.

(3) Permeability and haze

The protective film for the prepared process was measured for transmittance and haze using a spectrophotometer (Nippen Denshoku Co., Ltd., NDH2000 model).

(4) Measurement of residue

After the peel strength was measured by the (2) 180 ° peel force measurement method (adhesive power after light irradiation), the glass plate was visually checked to confirm whether any residue remained.

(5) Pencil hardness measurement

Using a pencil hardness meter (Shinto Scientific, Heidon) as a pencil for evaluation of Mitsubishi (UNI), a 500 kg / cm 2 load was drawn at a rate of 0.5 mm / sec, and then the pencil hardness was checked.

(6) Modulus measurement

Storage modulus (G ') when strain is 2% within a range of 0.1 to 10 Hz at 25 ° C using a plate-plate (40 mm diameter) system of a TA rheometer (AR 1000, TA Instruments, USA). ) And viscosity were measured, respectively.

As a result of the experiment, while the thermosetting resin and the two photocurable oligomers were mixed, Examples 1 to 4 satisfying a specific blending ratio exhibited excellent transmittance while exhibiting low initial adhesion and low adhesion after light irradiation, without residue It turns out that it shows light transmittance.

Through the above results, it was confirmed that the protective film according to the present invention can be usefully applied as a film for protecting the display surface during the manufacturing process of the display device.

100: process protective film
110: light-transmitting first coating layer
120: adhesive second coating layer
130: first substrate
140: second substrate

Claims (21)

First substrate;
Second substrate; And
It has at least two or more multi-layer coating layer formed between the first base material and the second base material,
The multilayer coating layer,
A first transmissive coating layer comprising a thermosetting component; And
A protective film for a process comprising a thermosetting component and a photocurable adhesive second coating layer comprising a photocurable component. According to claim 1,
The light-transmitting first coating layer,
At 380 ~ 780nm wavelength, the light transmittance is more than 80%,
Protective film for process with a haze of 0.5 to 3.0%. According to claim 1,
The light-transmitting first coating layer is a hard coating layer having a modulus of 100 to 800 MPa and a pencil hardness of 2H to 5H at 25 ° C, a protective film for a process. According to claim 1,
The light-transmitting first coating layer is 0.5 gf / inch or less tack-free, protective film for processing. According to claim 1,
The light-transmitting first coating layer,
A (meth) acrylate resin containing at least one hydroxyl or carboxyl group in the molecule, having a glass transition temperature (° C) of -50 ° C to -30 ° C, and a weight average molecular weight (Mw) of 100,000 to 600,000 g / mol; And
A protective film for a process comprising a bifunctional or higher epoxy-based thermosetting curing agent or an isocyanate-based thermosetting curing agent. According to claim 1,
When peeling at a rate of 1,500 to 3,000 mm / min before photocuring, the adhesive strength to the adherend of the adhesive second coating layer is 20 gf / inch or less,
When peeling at a rate of 1,500 to 3,000 mm / min after photocuring, the adhesive force for the adherend of the adhesive second coating layer is 2.5 gf / inch or less, a process adhesive film. According to claim 1,
The adhesive second coating layer is a protective film for a process in which the adhesive strength reduction rate of the following Equation 1 is 80 to 95% due to additional photocuring by light energy of 100 to 800 mJ / cm ² .
[Equation 1]
Adhesion reduction rate (%) = (A ₁ -A ₂ ) / A ₁ × 100
In the above formula,
A ₁ is the adhesive strength of the adhesive second coating layer before photocuring,
A ₂ is the adhesive strength of the adhesive second coating layer after photocuring. According to claim 1,
The adhesive second coating layer
Polyol;
Thermosetting agent;
An epoxy-based (meth) acrylate monomer having at least one epoxy group in the molecule and having two or more functional groups;
A silicone-based (meth) acrylate oligomer having at least one silicone in the molecule and having at least five functionalities; And
A protective film for a process comprising a cured product of an adhesive composition containing a photoinitiator. The method of claim 8,
The polyol is a protective film for a process having a weight average molecular weight (Mw) of 50,000 to 150,000 g / mol. The method of claim 8,
The epoxy-based (meth) acrylate monomer has a molecular weight of 100 to 1,000 g / mol, and a protective film for a process having 2 to 6 polymerizable functional groups. The method of claim 8,
The silicone-based (meth) acrylate oligomer has a weight average molecular weight (Mw) of 5,000 to 20,000 g / mol, and a protective film for a process having 5 to 15 polymerizable functional groups. The method of claim 8,
The pressure-sensitive adhesive composition, respectively, based on 100 parts by weight of the polyol,
1 to 10 parts by weight of a heat curing agent;
3 to 20 parts by weight of an epoxy (meth) acrylate monomer;
10 to 30 parts by weight of a silicone-based (meth) acrylate oligomer; And
A protective film for a process comprising 0.1 to 7 parts by weight of a photoinitiator. According to claim 1,
The first base material and the second base material are protective films for a process, which are at least one of a protective film and a release film, respectively. The method of claim 13,
The thickness of the protective film is 50 to 150 ㎛,
The release film has a thickness of 10 to 100 μm, a process protective film. The method of claim 13,
The process protective film, a protective film; A light transmissive first coating layer; Adhesive second coating layer; And a release film are sequentially stacked, a protective film for a process. The method of claim 15,
The protective film; A protective film for a process wherein the thickness ratio between the light-transmissive first coating layer and the adhesive second coating layer is 1: 0.4 to 1.4: 0.05 to 0.7. According to claim 1,
The first base material is polyethylene terephthalate (PET) film, polybutylene terephthalate film, polyethylene naphthalate (PEN) film, polyethylene film, polypropylene film, cellophane, diacetylcellulose film, triacetylcellulose film, acetylcellulose butyrate Film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, A protective film for a process which is one of polyethersulfone film, polyetherimide film, polyimide (PI) film, fluorine resin film, polyamide film, acrylic resin film, norbornene resin film, and cycloolefin resin film. According to claim 1,
The second base material is a protective film for any one of a release paper and a release polymer film. According to claim 1,
A protective film for a process used in any one of a semiconductor device and a display device. According to claim 1,
The protective film for the process is attached to one side of the adhesive second coating layer and the adherend after detaching the second substrate,
The adherend is a protective film for a process which is any one of a cover glass, an organic photosensitive material, a sealing material, and a polarizing film of a semiconductor device or a display device. The method of claim 20,
A protective film for a process in which a predetermined surface roughness is formed on one surface of a protective film for a process to which the second base material is detached and an adherend to be attached.

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