KR20210056593A - Release film for ultra-light release - Google Patents

Abstract

The present invention relates to an ultralight release film and, more specifically, to an ultralight release film which employs a polyester binder resin and an oxazoline group-containing resin which are low in reactivity with polysiloxane, so that the ultralight release film is excellent in terms of substrate adhesion and solvent resistance and capable of achieving ultralight release leading to the minimization of a high temperature temporal change in a releasing region.

Description

Ultra-light peeling release film {RELEASE FILM FOR ULTRA-LIGHT RELEASE}

The present invention relates to an ultra-hard release film capable of implementing ultra-hard peeling that can minimize high temperature aging changes of the release area even when forming a release area having a high thickness for realization of super-hard peeling and excellent adhesion to a substrate and solvent resistance.

In general, in the field of a release film used for a function of protecting an adhesive layer, a release film having excellent solvent resistance is required for various solvents used in the adhesive.

To this end, a general method of improving the degree of crosslinking using a platinum catalyst or a hydrolyzed silane oligomer having a reactive group is used to improve the degree of crosslinking of the polysiloxane itself. However, as the polysiloxane participates in the additive reaction, the peeling force of the release film is reduced. Problems such as a change or a decrease in residual adhesion rate occur.

In addition, there is a method of improving the adhesion of the substrate by adding a binder such as urethane, polyester, acrylic, etc. to the coating solution (Korean Patent Laid-Open Publication No. 10-2017-0099980). Since it must be used by excluding a chemical functional group, there is a problem that some loss in mold release properties occurs.

In particular, in the recent release film market, the need for ultra-hard peelable release films with very low peel strength is accelerating, and for ultra-hard peeling, it is necessary to increase the thickness of the release layer or use a material with very low peeling force to realize ultra-hard peelability. It may be (Korean Patent Laid-Open Publication No. 10-2017-0067067), in this case, there is a problem such as a change in peeling force due to a change over time at a high temperature.

Therefore, in order to realize ultra-light peeling, it is urgent to develop a release film that has excellent solvent resistance and adhesion to the substrate and has less change over time.

Korean Patent Publication 10-2017-0099980 Korean Patent Publication 10-2017-0067067

The present invention has been devised to solve the above problems and meet the requirements of the prior art, and an object of the present invention is to provide a super-hard release film having high adhesion to a substrate and high solvent resistance.

Another object of the present invention is to provide an ultra-hard release film capable of minimizing the change over time of high temperature in the release region even when forming a release region having a high thickness for realization of ultra-hard peeling.

The above and other objects and advantages of the present invention will become more apparent from the following description of preferred embodiments.

The above object is a release film comprising a substrate and a coating layer located on at least one side of the substrate, the coating layer is made of a water-based release coating liquid, and is achieved by a super-hard peeling release film comprising an anchor region and a release region.

Here, the aqueous release coating solution may include vinyl polysiloxane, hydroelectric polysiloxane, polyester resin, oxazoline group-containing resin, platinum catalyst, surfactant, and solvent.

Preferably, the anchor region may be formed of a polyester resin and an oxazoline group-containing resin.

Preferably, it may include 0.1 to 10 parts by weight of an oxazoline group-containing resin relative to 100 parts by weight of the polyester resin.

Preferably, the release region may be one formed of vinyl polysiloxane and hydroelectric polysiloxane.

Preferably, it may include 110 to 200 parts by weight of hydroelectric polysiloxane based on 100 parts by weight of vinyl polysiloxane.

Preferably, the solvent may include 80% to 99% by weight of water and 1% to 20% by weight of ethylene glycol.

Preferably, the aqueous release coating liquid may further include an antistatic agent.

Preferably, the thickness of the coating layer after drying may be 0.01 to 2.0 μm.

More preferably, the thickness of the coating layer after drying may be 0.5 to 1.0 μm.

Preferably, the ultra-hard peeling release film may be aged at 60°C and 90% RH for 1 day and then aging at high temperature and at room temperature for 1 day, and then at room temperature and peeling strength of 15 gf/in or less, respectively.

Preferably, the ultra-hard peeling release film may have a difference between a high-temperature peeling force and a normal-temperature peeling force after aging for one day at 60° C. and 90% RH for one day and then aging at room temperature for one day.

Preferably, the super-hard peeling release film may have a residual adhesion rate of 90% or more.

Preferably, the super-hard peeling release film may be one that does not peel off the coating layer after being wiped by reciprocating three times with a bastion immersed in isopropyl alcohol (IPA).

According to the present invention, there are effects such as excellent adhesion to a substrate and excellent solvent resistance.

Furthermore, the present invention has an effect of minimizing high temperature changes in the release region over time even when forming a release region having a high thickness for realization of ultra-light peeling.

However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

1 is a schematic cross-sectional view of a super-hard peeling release film according to an embodiment of the present invention.
2 is a schematic cross-sectional view of a super-hard peeling release film according to another embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to embodiments of the present invention and drawings. These examples are only illustratively presented to explain the present invention in more detail, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited by these examples. .

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. Also, although methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present invention, suitable methods and materials are described herein.

As used herein, "comprise", "comprising", "include", "including", "containing", "~ The terms characterized by", "has", "having" or any other variation thereof are intended to cover inclusions that are not exclusive. For example, a process, method, article, or apparatus comprising a list of elements is not necessarily limited to those elements, and may include other elements not explicitly listed or inherent to such process, method, article, or apparatus. May be. Also, unless expressly stated to the contrary, "or" refers to an inclusive'or' and not an exclusive'or'.

First, a super-hard release film according to an embodiment of the present invention will be described in detail with reference to FIGS. 1 and 2, which are cross-sectional schematic diagrams of an ultra-hard release film according to a preferred embodiment and another embodiment of the present invention.

Referring to FIG. 1, an ultra-hard release film 100 according to an embodiment of the present invention is a release film including a substrate 10 and a coating layer 20 positioned on at least one side of the substrate, and the coating layer 20 ) Is formed by applying an aqueous release coating liquid, and may have a structure in which the anchor regions 21 and the release regions 22 of the coating layer 20 alternate from side to side.

In addition, referring to FIG. 2, the ultra-hard release film 100 according to another embodiment of the present invention may have a structure in which the anchor region 21 and the release region 22 of the coating layer 20 contact vertically. .

However, in FIGS. 1 and 2, the anchor region 21 and the release region 22 are shown in a state that is physically completely separated, but this is only for convenience of explanation and may be formed when the coating layer is coated once. It shows the structure. In addition, the boundary between the anchor region 21 and the release region 22 may not be clear from each other, and the states of FIGS. 1 and 2 may be mixed, and probabilistically, the state of FIG. 2 may be more than that of FIG. 1. This is high.

Although there is no particular limitation as the substrate 10, it is preferable to use a polyethylene terephthalate film having excellent heat resistance, chemical resistance, and mechanical strength, and economic feasibility. In particular, it is preferably a film having a thickness of 10 to 200 µm.

In one embodiment, the aqueous release coating liquid forming the coating layer 20 includes vinyl polysiloxane, hydroelectric polysiloxane, polyester resin, oxazoline group-containing resin, platinum catalyst, surfactant, and solvent, and The coating layer is formed by heating and curing after coating on one or both sides.

In one embodiment, the anchor region 21 is formed by a polyester resin as a binder resin and an oxazoline group-containing resin as a curing agent in the aqueous release coating solution.

In addition, the polyester resin and the oxazoline group-containing resin forming the anchor region 21 are not particularly limited, and commercialized products widely used in the art may be used.

In the present invention, by using a polyester resin and an oxazoline group-containing resin forming the anchor region 21, the reaction with polysiloxane, which is a composition of the coating liquid, can be minimized, so that a release film having high adhesion to the substrate and solvent resistance can be provided. have. In addition, even when a high-thick release region is formed to implement ultra-light peeling, due to the anchor region 21, it is possible to minimize the change over time of the high temperature of the release region. That is, by using a polyester resin and an oxazoline group-containing resin to preferentially induce crosslinking of carboxylic acids in the polyester resin, solvent resistance can be sufficiently secured even though the degree of silicone crosslinking is not high. The release area is not hard and is maintained soft, so that it is possible to implement ultra-light peeling while having excellent solvent resistance.

In one embodiment, it is preferable to include 0.1 to 10 parts by weight of the oxazoline group-containing resin relative to 100 parts by weight of the polyester resin. This is because when the oxazoline group-containing resin is less than 0.1 parts by weight, the solvent resistance is deteriorated, whereas when it exceeds 10 parts by weight, silicone curing is inhibited, resulting in insufficient releasability of the film.

In one embodiment, the release region 22 is formed by vinyl polysiloxane and hydropre-polysiloxane in the aqueous release coating solution.

In the aqueous release coating liquid, vinyl polysiloxane emulsion and hydroelectric polysiloxane emulsion are not subject to any special restrictions, and silicone emulsion products commonly used in the art can be used.

In one embodiment, it is preferable to include 110 to 200 parts by weight of hydroelectric polysiloxane based on 100 parts by weight of vinyl polysiloxane. This is because if the amount of the hydropolysiloxane is less than 110 parts by weight, the silicon transfer rate is high, whereas if it exceeds 200 parts by weight, stability over time at high temperatures is insufficient.

As described above, the ultra-hard release film according to the present invention can secure excellent properties of silicone curing even at a coating drying condition temperature of 130° C. to 150° C. by adjusting the ratio of vinyl polysiloxane and hydroelectric polysiloxane.

In addition, platinum catalysts do not have any special restrictions, and commercial products widely used in the industry can be used.

In one embodiment, the solvent of the aqueous release coating solution is preferably 80% by weight of water based on the total weight of the coating solution, and 80% to 99% by weight of water and 1% by weight to ensure stability of the coating solution. It is preferable to use a solvent in which to 20% by weight of ethylene glycol (co-solvent) is mixed. As described above, the coating layer according to an embodiment of the present invention may provide a release film that uses 80% by weight or more of water as a solvent and exhibits the same level as the appearance and adhesion of the substrate of the organic solvent. As a result, it is an eco-friendly material with a small amount of VOC emissions, and can be used not only in the field of electronic and electrical materials, but also in various uses such as food.

In one embodiment, in order to impart antistatic properties, a conductive polymer resin may be further included as an antistatic agent in the water-based release coating liquid which further comprises one antistatic layer on the coating layer 20 or forms the coating layer 20. I can. The conductive polymer resin is preferably an aqueous dispersion containing polyanions and polythiophene or an aqueous dispersion containing polyanions and polythiophene derivatives. Polyanions are acidic polymers, such as high molecular carboxylic acid, high molecular weight sulfonic acid, polyvinyl sulfonic acid, or the like. Examples of the polymeric carboxylic acid include polyacrylic acid, polymethacrylic acid, and polymaleic acid, and examples of the polymeric sulfonic acid include polystyrenesulfonic acid, but are not limited thereto. In the embodiment of the present invention, a conductive polymer PEDOT aqueous solution was used as the conductive polymer resin.

At this time, the conductive polymer resin may exhibit stable antistatic performance by using an aqueous dispersion having an average particle diameter of 10 to 90 nm. If the average particle diameter of the conductive polymer resin exceeds 90 nm, the deviation of the surface resistance becomes very large because it is not uniformly distributed inside the coating layer, so that the antistatic performance cannot be properly implemented.If the average particle diameter of the conductive polymer resin is less than 10 nm, the molecular weight is reduced. As it becomes smaller, it becomes farther than a certain distance between molecules, so that the antistatic performance cannot be realized. In the case of stretching in-line, the smaller the average particle diameter, the lower the antistatic performance.

In addition, the water-based release coating liquid forming the coating layer 20 can be heated and cured at a drying temperature of 130° C. to 280° C. to form an excellent coating layer, more preferably having a drying temperature of 130° C. to 150° C. The effect is even greater in offline processing.

In one embodiment, the coating thickness of the coating layer 20 is preferably 0.01 to 2.0 μm in dry thickness. If the coating thickness of the coating layer is less than 0.01 µm, the effect of reducing the peeling force is insignificant and thus the peeling force at low speed is increased, and when it exceeds 2.0 µm, the thickness of the coating layer is too high, resulting in a problem in high-speed productivity.

In addition, it is more preferable that the thickness of the coating layer after drying is 0.5 μm to 1.0 μm. When the thickness is less than 0.5 μm after drying, it is difficult to implement ultra-hard peeling, and when it exceeds 1.0 μm, there is a problem that blocking occurs.

There is no particular restriction on the method of applying the coating liquid forming the coating layer 20, and bar coating, gravure coating, comma coating, or die coating may be applied. The aqueous release coating liquid applied in a liquid state can be heated and cured in a hot air dryer at a temperature of 150° C. for about 30 seconds to obtain a cured release area and an anchor area.

In one embodiment, the ultra-hard peeling release film is preferably aged at 60° C. and 90% RH for 1 day and then aged at high temperature and at room temperature for 1 day, and then the peeling force at room temperature is preferably 15 gf/in or less.

In one embodiment, the ultra-hard release film is preferably aged at 60° C. and 90% RH for 1 day, and then the difference between the high temperature peeling force and the normal temperature peeling force after aging at room temperature for 1 day is less than 10%.

In one embodiment, it is preferable that the super-hard peeling release film has a residual adhesion of 90% or more.

In one embodiment, it is preferable that the coating layer is not peeled off after the ultra-hard release release film is wiped by reciprocating three times with a bastion immersed in isopropyl alcohol (IPA).

Hereinafter, the configuration of the present invention and effects thereof will be described in more detail through examples and comparative examples. However, the present examples are for explaining the present invention in more detail, and the scope of the present invention is not limited to these examples.

[Example]

[Example 1]

1. Base film

A polyethylene terephthalate film with a thickness of 50 μm (manufacturer: Toray Advanced Materials, product name: XD500) was used as a base film.

2. Coating layer

Silicone emulsion resin composed of vinyl polysiloxane emulsion and hydroelectric polysiloxane emulsion (manufacturer: Dow Chemical, product name: SYL-OFF 7920, vinylsiloxane 100 parts by weight: hydroelectric polysiloxane 140 parts by weight) 5 parts by weight, platinum catalyst (manufacturer: Dow Chemical, product name: SYL-OFF 7924) 0.5 parts by weight, polyester binder resin (manufacturer: Base Korea, product name: EW-210S) 10 parts by weight, oxazoline group-containing resin (manufacturer: Japan catalyst, product name: WS-700) 0.1 parts by weight of surfactant (manufacturer: BYK, product name: BYK348) 0.1 parts by weight of water, 95 parts by weight of water, and 4 parts by weight of ethylene glycol were applied to the base film using a bar coater, and then in a hot air dryer. A release film was prepared by heating and curing at a temperature of 140° C. for 30 seconds to form a coating layer having a dry thickness of 0.5 μm.

[Example 2]

A release film was prepared in the same manner as in Example 1, except that 20 parts by weight of a silicone emulsion resin and 2 parts by weight of a platinum catalyst were used in the aqueous release coating solution, and a dry thickness of 1 µm was applied.

[Example 3]

A release film was prepared in the same manner as in Example 1, except that 20 parts by weight of a conductive polymer PEDOT aqueous solution (manufacturer: Heraus: product name Clevious PT) was applied to the aqueous release coating solution.

[Comparative Example 1]

Silicone emulsion resin composed of vinyl silicone emulsion and hydropolysiloxane emulsion (manufacturer: Dow Chemical, product name: SYL-OFF 7920) 5 parts by weight, platinum catalyst (manufacturer: Dow Chemical, product name: SYL-OFF 7924) 0.5 parts by weight, A release film was prepared in the same manner as in Example 1, except that an aqueous release coating solution containing 0.1 parts by weight of a surfactant (manufacturer: BYK, product name: BYK348) and 95 parts by weight of water and 4 parts by weight of ethylene glycol was used. .

[Comparative Example 2]

A release film was prepared in the same manner as in Comparative Example 1, except that 5 parts by weight of a polyester resin were further included in the aqueous release coating solution.

[Comparative Example 3]

A release film was prepared in the same manner as in Comparative Example 1, except that 1 part by weight of a silane coupling agent (manufacturer: Dow Chemical, product name: Z-6043) was further included in the aqueous release coating solution.

[Comparative Example 4]

A release film was prepared in the same manner as in Comparative Example 1, except that 10 parts by weight of a urethane binder (manufacturer: ARAKAWA, product name: UREARNO W321) was further included in the aqueous release coating solution.

[Comparative Example 5]

A release film was prepared in the same manner as in Comparative Example 1, except that the dry thickness was 1 μm.

Using the release films according to Examples 1 to 3 and Comparative Examples 1 to 5, physical properties were measured through the following experimental examples, and the results are shown in Table 1 below.

[Experimental Example]

1. Solvent resistance

After wiping the release film three times by reciprocating it with a sconce (a cloth with large surface roughness) immersed in isopropyl alcohol (IPA), the presence or absence of the coating layer was checked and evaluated according to the following criteria.

○: good solvent resistance (no coating layer falling off)

△: Insufficient solvent resistance (partial damage to the coating layer)

X: No solvent resistance (most of the coating layer is damaged)

2. Appearance

It was evaluated based on the following criteria according to the condition of the lower limbs and stain mura of the coated A4 size release film.

○: The appearance is clean without any spots or spots.

△: Some lower extremities and spots (less than 10 in A4 size) occurred

X: Poor wettability and poor coating appearance

3. Substrate adhesion

The release coating layer was rubbed back and forth 10 times by hand (Rubbing TEST) and evaluated according to the following criteria according to the degree of peeling of the release coating layer.

○: The release coating layer is not peeled off

△: Part of the release coating layer is peeled off

X: The release coating layer comes off a lot

4. High-temperature substrate adhesion

The prepared release film was aged for 1 day in a thermo-hygrostat of 60°C and 90% RH, and then the release coating layer was rubbed back and forth 10 times by hand to evaluate the degree of peeling of the release coating layer according to the following criteria.

○: The release coating layer is not peeled off

△: Part of the release coating layer is peeled off

X: The release coating layer comes off a lot

5. Room temperature peeling force

The peel strength of the release films according to Examples and Comparative Examples was evaluated using TESA7475 tape, which is a standard tape widely used in the art.

First, the tape was attached to the release coating surface of the release area with a 2kg roller, aged at room temperature for 1 day, and then the peeling force at the time of peeling was measured, and the peeling force at the time of peeling at a 180° angle using Cheminstrument's AR-1000 equipment. Measured, but the peeling rate is 0.3mpm and the unit is gf/in.

6. High temperature peeling force

The prepared release film was aged for 1 day in a thermo-hygrostat of 60°C and 90% RH, and then after a rubbing test, peeling force was measured in the same manner as in Experimental Example 5 above.

7. Check the difference in peel strength

The difference between the room-temperature peeling force and the high-temperature peeling force measured in Experimental Examples 5 and 6 above was calculated by the following Equation 1 as the peeling force difference.

(Equation 1)

Peel force difference (%) = (high temperature peel force-room temperature peel force)/high temperature peel force * 100 (%)

8. Measurement of residual adhesion rate

After the release-coated measurement sample was stored at 25°C and 65%RH for 24 hours, a standard adhesive tape (Nitto 31B) was attached to the release-coated surface, and the sample was compressed at room temperature for 24 hours with a load of ^{20 g/cm 2.} The tape that had been adhered to the release coated surface was collected without contamination, and then adhered to a clean PET film surface with a flat surface, and then reciprocated once with a 2 kg tape roller (ASTMD-1000-55T). The peel force was measured as follows, and the residual adhesion rate was calculated by Equation 2.

Measuring instrument: chem-[0149] instrument AR-1000

Measurement method: 180° peeling angle, peeling speed 0.3 m/min

(Equation 2)

Residual adhesion rate (%) = [Peeling force of the adhesive tape that was adhered to the coated surface and peeled off / the peeling force of the adhesive tape not in contact with the coated surface] X 100 (%)

9. Antistatic properties

After installing the sample in an environment at a temperature of 23°C and a humidity of 50%RH using an antistatic meter (Mitsubishi Corporation; model name MCP-T600), the surface resistance was measured according to JIS K7194 standard.

Solvent resistance Exterior materials
Adhesion High temperature material
Adhesion Room temperature peeling force
(gf/in) High temperature peeling force
(gf/in) Peel force difference
(%) Residual
Adhesion rate (%) Surface resistance
(Ω/sq) Example 1 ○ ○ ○ ○ 12.1 12.4 2.4 91 8.1x10 ¹² Example 2 ○ ○ ○ ○ 5.0 5.5 9.1 90 1.7x10 ¹² Example 3 ○ ○ ○ ○ 13.4 13.9 3.6 92 2.6x10 ⁶ Comparative Example 1 X ○ X X 14.1 28.4 50.4 89 1.8x10 ¹² Comparative Example 2 △ ○ ○ X 16.7 29.6 43.6 91 3.4x10 ¹² Comparative Example 3 △ △ ○ △ 11.2 21.9 48.9 82 5.1x10 ¹² Comparative Example 4 ○ ○ ○ △ 16.4 23.5 30.2 61 5.9x10 ¹² Comparative Example 5 X ○ ○ X 5.4 35.7 84.9 88 6.3x10 ¹²

As can be seen from Table 1, the release film according to Example 1 of the present invention has excellent solvent resistance, adhesion to the substrate at room temperature and high temperature, and the difference between the room temperature peeling force and the high temperature peeling force is 2.4%. It can be seen that it is excellent. In addition, it can be seen that the release film according to Example 2 has excellent aging stability under high temperature and high humidity conditions even though the dry thickness of the coating layer is 1 μm in order to implement ultra-hard peeling. In particular, it can be seen that the release film according to Example 3 including an antistatic agent can obtain a release film having excellent surface resistance values while having excellent other physical properties.

On the other hand, it can be seen that the conventional release film of Comparative Example 1 has poor solvent resistance and poor adhesion to substrates and high temperature substrates.In particular, since the difference between normal temperature peeling force and high temperature peeling force occurs by 50% or more, high temperature and high humidity It can be seen that the stability over time under the conditions is remarkably deteriorated.

In addition, it can be seen that the release film of Comparative Example 2 is poor in solvent resistance and poor adhesion to high-temperature substrates when only a polyester binder resin is used without an oxazoline group.

In addition, it was found that the release film of Comparative Example 3 showed significantly lower physical properties than the release films according to Examples 1 to 3 of the present invention despite the addition of the silane coupling agent, which is commonly used as a method of improving adhesion to the substrate and solvent resistance. I can.

In addition, it can be seen that the release film of Comparative Example 4, when using a urethane binder, lacks silicone curing due to the catalyst poison, and thus the residual adhesion rate is significantly lowered.

In addition, it can be seen that the release film of Comparative Example 5 has poor adhesion to a high-temperature substrate and remarkably deteriorates solvent resistance even when only the thickness of the coating layer is thickened to implement ultra-light peeling.

As described above, the release film according to an embodiment of the present invention is not only excellent in solvent resistance and adhesion to the substrate, but also has excellent stability with time at high temperature, so that there is little change even under high temperature and high humidity conditions at 60°C and 90%RH. Therefore, it is easy to implement ultra-light peeling.

In addition, if the coating thickness is simply improved to implement ultra-light peeling, adhesion between the thick coating layer and the substrate is insufficient, and thus, peeling force is increased under high temperature and high humidity conditions, which may lead to process accidents, but according to an embodiment of the present invention It can be seen that the release film has excellent aging stability under high temperature and high humidity conditions even if the dry thickness of the coating layer is increased in order to realize super-hard peeling.

In addition, the release film according to an embodiment of the present invention provides a release film that uses 80% by weight or more of water as a solvent and exhibits the same level as the appearance and substrate adhesion of an organic solvent. It can be seen that it can be used not only in the field of electronic and electrical materials, but also in various uses such as food, and it has antistatic properties, which is suitable for solving problems such as dust or contamination that may occur during the process.

In the present specification, only a few examples of various embodiments performed by the present inventors will be described, but the technical idea of the present invention is not limited or limited thereto, and may be modified and variously implemented by those skilled in the art.

10: description
20: coating layer
21: anchor area
22: release area
100: ultra-hard peeling release film

Claims (14)

Description and
As a release film comprising a coating layer located on at least one side of the substrate,
The coating layer is made of an aqueous release coating liquid, and includes an anchor region and a release region, a super-hard release film. The method of claim 1,
The water-based release coating solution is a vinyl polysiloxane, a hydroelectric polysiloxane, a polyester resin, an oxazoline group-containing resin, a platinum catalyst, a surfactant and a solvent containing, ultra-hard release film. The method of claim 1,
The anchor region is formed of a polyester resin and an oxazoline group-containing resin, a super-hard release film. The method of claim 3,
An ultra-hard release film comprising 0.1 to 10 parts by weight of the oxazoline group-containing resin relative to 100 parts by weight of the polyester resin. The method of claim 1,
The release region is formed of vinyl polysiloxane and hydroelectric polysiloxane, ultra-hard release film. The method of claim 5,
An ultra-hard release film comprising 110 to 200 parts by weight of the hydroelectric polysiloxane based on 100 parts by weight of the vinyl polysiloxane. The method of claim 2,
The solvent comprises 80% to 99% by weight of water and 1% to 20% by weight of ethylene glycol, ultra-hard release film. The method of claim 2,
The water-based release coating liquid further comprises an antistatic agent, ultra-hard release film. The method of claim 1,
The thickness of the coating layer after drying is 0.01 to 2.0 ㎛, ultra-hard release film. The method of claim 9,
The thickness of the coating layer after drying is 0.5 to 1.0 ㎛, ultra-hard release film. The method according to any one of claims 1 to 10,
The ultra-hard release film is aged at 60° C., 90% RH for 1 day, and then aged at high temperature and at room temperature for 1 day, and then the peel strength at room temperature is 15 gf/in or less, respectively. The method of claim 11,
The ultra-hard release film is aged at 60° C., 90% RH for 1 day, and then aged at room temperature for 1 day, and then the difference between the peel strength at room temperature is less than 10%. The method according to any one of claims 1 to 10,
The super-hard peeling release film has a residual adhesion of 90% or more, a super-hard peeling release film. The method according to any one of claims 1 to 10,
The ultra-hard release film is a super-hard release film that does not peel off the coating layer after wiping by reciprocating three times with a bastion immersed in isopropyl alcohol (IPA).

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