Release film containing fluorine group and method for manufacturing the same

Abstract

The fluorine group-containing release film according to the present application includes: a base film; and a release layer located on at least one surface of the base film and formed by applying a release coating solution containing a fluorine group-containing organopolysiloxane (A) and a non-fluorine group-containing organopolysiloxane (B) on at least one surface of the base film. Wherein the 2θ value of the entire release layer everywhere according to the XRD analysis result is greater than 12.0 degrees and less than 13.5 degrees. Thus, the coating solution can be diluted and coated without using a fluorine-based solvent, which improves the processability and makes the coating uniform, thereby improving the peelability and peel strength variation. Furthermore, the amount of the expensive fluorine group-containing organopolysiloxane used can be minimized, thus a product with excellent physical properties and high cost-effectiveness can be manufactured. When the fluorine group-containing release film according to the present application is applied to an organic silicon-based adhesive treatment process, a cost reduction effect as well as excellent physical properties can be obtained.

Description

TECHNICAL FIELD

[0001] The present application relates to a fluorine group-containing release film and a manufacturing method thereof, and more particularly to a fluorine group-containing release film in which at least one surface of a polyester base film is coated with a fluorine group-containing release coating solution, and which has excellent peelability and residual adhesion rate and an excellent appearance of a release layer by improved coating properties. BACKGROUND

[0002] Generally, silicone-based adhesives have advantages such as heat resistance, friction resistance, and flexibility, and thus have been widely used in flexible displays and the like recently. In addition, silicone-based adhesives are excellent in electrical insulation, low toxicity, and cold resistance, and thus are used in a wide range of applications.

[0003] In order to use such silicone-based adhesives, a fluorine group-containing release film having excellent peelability is required. In the case of a generally known silicone-based release film, since the silicone of the release coating layer is well compatible with the silicone-based adhesive layer, the release coating layer cannot be peeled from the silicone-based adhesive layer when laminated together. For this reason, a film coated with a fluorine-based resin-containing release agent is often used as a release film for use as a silicone-based adhesive.

[0004] However, the fluorine-based resin-containing release agent has low surface energy and is not well compatible with general organic solvents, which can cause coating defects such as pinhole defects, and thus the use of a fluorine-based solvent is required when dissolving or applying the coating solution. In addition, since such a fluorine-based solvent has very high volatility, it is difficult to maintain a constant coating thickness during coating of the film, and thus stains on the coating layer due to poor leveling and changes in peel strength due to coating thickness changes can occur during coating. Therefore, in order to solve the problem of not being able to dissolve fluorine-based polymers with non-fluorine-containing organic solvents, a combination of a phenyl-containing silicone adhesive and an addition reaction type silicone release agent has been proposed to enable peeling, but there are problems such as an increase in peel strength over time.

[0005] In addition, when the crosslinking degree of the fluorine-based resin-containing release agent is evaluated by a rub-off test, physical property changes such as partial reflow, fogging, etc. occur.

[0006] In addition, in the case of a fluorine-based solvent and a fluorine-based resin-containing release agent, it is several tens of times more expensive than general organic solvents and silicone-based release agents, and thus is disadvantageous in terms of productivity. Although the properties of silicone-based adhesives are excellent, due to these disadvantages, the use of release films has not increased exponentially. SUMMARY

[0007] Technical Problem

[0008] The present application has been designed to solve the above problems and meet the conventional needs, and aims to provide a fluorine group-containing release film having excellent peelability and residual adhesion rate and having improved coatability, thereby exhibiting excellent appearance characteristics of a release layer, and a manufacturing method thereof.

[0009] The foregoing and other objects and advantages of the present application will become apparent to those skilled in the art from reading the following description of preferred embodiments thereof, given by way of example.

[0010] Technical Solution

[0011] The above object is achieved by a fluorine group-containing release film including: a base film; and a release layer on at least one surface of the base film and formed by applying a release coating solution containing a fluorine group-containing organopolysiloxane (A) and an organopolysiloxane (B) not containing a fluorine group on at least one surface of the base film, wherein a 2θ value according to an XRD analysis result is greater than 12.0 degrees and less than 13.5 degrees throughout the release layer.

[0012] Preferably, the release film can have a peel strength of 5 gf / inch to 25 gf / inch, which is measured by placing the release film at 25°C and 65% RH for 24 hours, then adhering an organic silicon-based adhesive tape (MY2G, Taiwan) to a surface of the release layer, pressing the tape at 50°C with a load of 20 g / cm 2 for 24 hours, and peeling the tape at a peel angle of 180° and at a peel speed of 0.3 mpm.

[0013] Preferably, the release layer can have a thickness of 100 nm to 300 nm after drying.

[0014] Preferably, the fluorine group-containing release film can have a residual adhesion rate of 90% or more.

[0015] Preferably, the release layer can be divided into a first region adjacent to the base film and containing Si in the release layer, and a second region adjacent to a surface of the release layer not in contact with the base film and containing F.

[0016] Preferably, the first region and the second region can have a contrast difference.

[0017] Preferably, the first region can be black, and the second region can be white.

[0018] Preferably, the second region can have a thickness of 0.001% to 40% of the total thickness of the release layer.

[0019] Preferably, the fluorine group-containing organopolysiloxane A can contain at least one fluorine-containing substituent selected from alkenyl groups having 2 to 10 carbon atoms, and fluoroalkyl or fluoroether groups in one molecule.

[0020] Preferably, the non-fluorine group-containing organopolysiloxane B can be contained in an amount of 50 parts by weight to 2,000 parts by weight, based on 100 parts by weight of the fluorine group-containing organopolysiloxane (A).

[0021] Preferably, the non-fluorine group-containing organopolysilioxane B can contain alkenyl groups having 2 to 10 carbon atoms or alkyl groups in one molecule.

[0022] Preferably, the release coating solution can contain a total amount of 2% to 6% by weight of solid content.

[0023] Further, the above object is achieved by a method of manufacturing a fluorine group-containing release film, the method including preparing a base film, and forming a release layer by applying a release coating solution on at least one surface of the base film and drying the release coating solution, the release coating solution containing a fluorine group-containing organopolysiloxane (A), a non-fluorine group-containing organopolysiloxane (B), a hydrosilicone, and a platinum chelate catalyst, wherein a 2θ value according to an XRD analysis result is greater than 12.0 degrees and less than 13.5 degrees throughout the release layer.

[0024] Advantageous Effects

[0025] The fluorine group-containing release film according to one embodiment of the present application has excellent peelability and residual adhesion rate, and has improved coating properties, so that the release layer has excellent appearance properties.

[0026] Further, in the fluorine group-containing release film according to one embodiment of the present application, the use amount of expensive fluorine group-containing organopolysiloxane can be reduced and an expensive fluorine-based solvent can not be used, thereby improving the cost effectiveness of the product.

[0027] However, the effects of the present application 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. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 is a block diagram of a fluorine group-containing release film according to one embodiment of the present application.

[0029] Figure 2 is a graph showing XRD analysis results of Example 1 and Comparative Examples 1 and 2.

[0030] Figure 3is a TEM image for measuring the thickness of Example 1. DETAILED DESCRIPTION

[0031] Hereinafter, the present application will be described in detail with reference to examples of the present application and the accompanying drawings. These examples are merely exemplary for a more detailed description of the present application, and it will be apparent to those skilled in the art that the scope of the present application is not limited to these examples.

[0032] 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 application belongs. In case of conflict, the present specification, including definitions, will control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application, suitable methods and materials are described herein.

[0033] As used herein, the terms "comprises," "comprising," "includes," "including," "contains," "containing," "characterized by," "has," "having," or "consists of," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or.

[0034] In describing and / or claiming the present application, the term "copolymer" is used to refer to a polymer formed by the copolymerization of two or more monomers. Such copolymers include di-copolymers, tri-copolymers, or higher order copolymers.

[0035] First, a block diagram of a fluorine-containing group-containing release film according to one embodiment of the present application will be described with reference to Figure 1 A fluorine-containing group-containing release film according to one embodiment of the present application will be described in detail.

[0036] Referring to Figure 1 A fluorine-containing group-containing release film 100 according to one embodiment of the present application includes a base film 10 and a release layer 20 located on at least one surface of the base film 10.

[0037] The release layer 20 can be positioned by coating the base film 10 with a release coating solution including the fluorine group-containing organopolysiloxane (A) and the fluorine group-free organopolysiloxane (B) and further including a hydrogen polysiloxane and a platinum chelate catalyst. As a result of efforts to provide a release film based on an organic silicon-based adhesive that can satisfy excellent release characteristics and appearance characteristics, the present invention aims to provide a fluorine group-containing release film that is excellent in release characteristics and coating appearance characteristics and has improved cost effectiveness by forming a release layer 20 through the application of a release coating solution including a fluorine group-containing organopolysiloxane and a fluorine group-free organopolysiloxane on at least one surface of a polyester base film 10. Hereinafter, each component will be described in detail.

[0038] 1. Base film 10

[0039] The base film 10 is a polyester base film, and the polyester resin used thereof can be a well-known base film commonly used in the conventional organic silicon release coating field. In particular, the polyester base film described herein can be the polyester base film disclosed in Korean Patent Registration No. 10-1268584, which is prior art of the applicant of the present invention. However, in the embodiments of the present invention, the polyester base film is not described with particular limitations in order to explain only the technical features of the present invention, but it should be understood that the technical features related to the well-known polyester base film are included.

[0040] Specifically, the base film 10 will be described focusing on polyester-based resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc., but the base film of the organic silicon release coating solution is not limited to a polyester sheet or a polyester film. The polyester resin forming the base film can be a polyester obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic diol. Examples of the aromatic dicarboxylic acid can include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid (e.g., p-hydroxybenzoic acid), etc. Examples of the aliphatic diol can include ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, 1,4-cyclohexane dimethanol, neopentyl glycol, etc. As the polyester-based resin, the dicarboxylic acid component and the diol component can be used in combination of two or more kinds thereof, or a copolymer containing a third component can be used.

[0041] In addition, the polyester base film according to one embodiment of the present invention can be a mono-axially or bi-axially oriented film having high transparency as well as excellent productivity and processability. Representative polyester resins can include polyethylene terephthalate (PET), polyethylene 2,6-naphthalate (PEN), etc.

[0042] Further, the polyester base film 10 according to the present application can contain particles to impart excellent roll-to-roll running characteristics, and the added particles are not particularly limited in type as long as it can exhibit excellent sliding characteristics.

[0043] Specifically, the base film 10 can include particles such as silica, silicon oxide, calcium carbonate, calcium sulfate, calcium phosphate, magnesium carbonate, magnesium phosphate, barium carbonate, kaolin, aluminum oxide, titanium dioxide, or the like. Although the shape of the particles used in the base film is not particularly limited, it can be preferably any one of a spherical shape, a block shape, a rod shape, a plate shape, or the like.

[0044] Further, the hardness, specific gravity, and color of the particles are not particularly limited. If necessary, these particles can be used in combination of any two or more kinds thereof. The average diameter of the particles used is preferably in the range of 0.1 to 5 μm, more preferably 0.1 to 2 μm. If the average diameter of the particles is less than 0.1 μm, aggregation between the particles can occur, thereby resulting in insufficient dispersion. On the other hand, if the average diameter exceeds 5 μm, the surface roughness characteristics of the film are deteriorated, thereby resulting in coating defects during post-processing.

[0045] Further, when the base film 10 as a polyester film includes particles, the content of the particles is preferably in the range of 0.01 to 5% by weight, more preferably 0.01 to 3% by weight. If the content of the particles is less than 0.01% by weight, the sliding characteristics of the polyester film are deteriorated, thereby resulting in deterioration of the roll-to-roll running characteristics. If the content of the particles exceeds 5% by weight, the surface smoothness of the film can be deteriorated.

[0046] The thickness of the base film 10 is not particularly limited, and is preferably in the range of 30 to 125 μm. If the thickness of the base film 10 is less than 30 μm, it is too thin, deformation occurs due to heat treatment, and if the thickness exceeds 125 μm, it is too thick, heat cannot be sufficiently transferred, thereby resulting in problems regarding solidification.

[0047] 2. Release layer 20

[0048] The release layer 20 is located on at least one surface of the base film 10, and can be formed by coating at least one surface of the base film 10 with a release coating solution including an organic polysiloxane A containing a fluorine group and an organic polysiloxane B not containing a fluorine group, and further including a hydrogen polysiloxane and a platinum chelate catalyst.

[0049] The organopolysiloxane A and the organopolysiloxane B are main components of the release coating solution of the present application, and the organopolysiloxane A and the organopolysiloxane B can exist as separate molecules or can be linked as a copolymer. Furthermore, any one of an addition reaction type silicone resin, a condensation reaction type silicone resin, and an ultraviolet curing type silicone resin can be used, and the type used is not particularly limited.

[0050] In one embodiment, the organopolysiloxane A containing a fluorine group preferably contains at least one fluorine-containing substituent selected from an alkenyl group bonded to a silicon atom and having 2 to 10 carbon atoms and a fluoroalkyl group or a fluoroether group bonded to a silicon atom in one molecule.

[0051] Specifically, the organopolysiloxane A containing a fluorine group preferably has a structure represented by Formula 1 shown below.

[0052] (Formula 1)

[0053]

[0054] In Formula 1, Ra is a monovalent hydrocarbon group of 1 to 10 carbon atoms other than an aliphatic unsaturated group, and specifically, can be an alkyl group; an aryl group; and a group in which part or all of the hydrogen atoms of these groups are substituted with a hydroxyl group, a cyano group, or the like or substituted with an alkenyl group having 2 to 10 carbon atoms.

[0055] Rb is a monovalent hydrocarbon group of 1 to 10 carbon atoms other than an aliphatic unsaturated group, and specifically, can be an alkyl group; an aryl group; and a group in which part or all of the hydrogen atoms of these groups are substituted with a hydroxyl group, a cyano group, or the like or substituted with an alkenyl group having 2 to 10 carbon atoms or a hydrogen group.

[0056] Rc has at least one fluorine-containing substituent selected from a fluoroalkyl group or a fluoroether group, and is a monovalent hydrocarbon group of 1 to 10 carbon atoms other than an aliphatic unsaturated group, and specifically, can be an alkyl group; an aryl group; and a group in which part or all of the hydrogen atoms of these groups are substituted with at least one of a hydroxyl group or a cyano group of a hydrocarbon group, an alkenyl group having 2 to 10 carbon atoms, or a hydrogen group.

[0057] Furthermore, X, Y, and Z are each an integer of 1 or more.

[0058] Furthermore, in Formula 1, the fluoroalkyl group preferably has a structure of the following Formula 2.

[0059] (Formula 2)

[0060]

[0061] In Formula 2, n is an integer of 1 to 8, and m is an integer of 1 to 5.

[0062] Further, in Formula 1, the fluoroether group preferably has a structure of the following Formula 3.

[0063] (Formula 3)

[0064]

[0065] In Formula 3, p is an integer of 1 to 5, q is an integer of 0 or 1, r is an integer of 0 to 2, m is an integer of 1 to 5, and X is an oxygen atom or a single bond.

[0066] In one embodiment, in one molecule of the organic polysiloxane B not containing a fluoro group, the alkenyl group bonded to a silicon atom can exist in any portion of the molecule, and preferably contains at least two or more alkenyl groups. Further, the molecular structure is a linear type or a branched type molecular structure, or a combination thereof.

[0067] Specifically, the organic polysiloxane B not containing a fluoro group preferably has a structure represented by Formula 4 shown below.

[0068] (Formula 4)

[0069]

[0070] In Formula 4, Ra is a monovalent hydrocarbon group of 1 to 10 carbon atoms other than an aliphatic unsaturated group, and specifically, can be an alkyl group; an aryl group; and a group in which part or all of the hydrogen atoms of these groups are substituted with a hydroxyl group, a cyano group, or the like, or substituted with an alkenyl group having 2 to 10 carbon atoms. Further, Rb is a monovalent hydrocarbon group of 1 to 10 carbon atoms other than an aliphatic unsaturated group, and specifically, can be an alkyl group; an aryl group; and a group in which part or all of the hydrogen atoms of these groups are substituted with a hydroxyl group, a cyano group, or the like, or substituted with an alkenyl group having 2 to 10 carbon atoms or a hydrogen group. Further, X and Y are each an integer of 1 or more.

[0071] In one embodiment, based on 100 parts by weight of the organic polysiloxane A containing a fluoro group, the organic polysiloxane B not containing a fluoro group is preferably contained in an amount of 50 parts by weight to 2,000 parts by weight. In this case, if the amount is less than 50 parts by weight, the residual adhesion rate decreases, and the 2θ value according to the XRD analysis result does not fall within the range of the present application, and if the amount exceeds 2,000 parts by weight, it does not satisfy the target peeling strength.

[0072] In one embodiment, using hydrogen polysiloxane as a curing agent of the release coating solution, any one of an addition reaction type hydrogen polysiloxane, a condensation reaction type hydrogen polysiloxane, and an ultraviolet curing type hydrogen polysiloxane can be used, and the type used is not particularly limited. Also, the hydrogen polysiloxane has a linear type, a branched type, or a cyclic type molecular structure, or a combination thereof. Its viscosity or molecular weight is not limited to a particular value, but it must be well compatible with the organopolysiloxane A and the organosilicon polysiloxane B. The hydrogen polysiloxane can not have a fluorine group, but it is preferable to have the same fluorine group as that of the organopolysiloxane A.

[0073] In one embodiment, based on 100 parts by weight of the organosilicon polysiloxane B not containing a fluorine group, the hydrogen polysiloxane is preferably included in an amount of 3 to 5 parts by weight. If the amount of the hydrogen polysiloxane is less than 3 parts by weight, the residual adhesion is reduced and defects can occur in appearance, and if the amount thereof exceeds 5 parts by weight, there is a problem that the peeling strength is greatly increased.

[0074] Also, based on one alkenyl group of the organopolysiloxane A containing a fluorine group and the organosilicon polysiloxane B not containing a fluorine group, the hydrogen polysiloxane preferably has 1.0 to 3.0 hydrogen groups bonded to a silicon atom. If the number of hydrogen groups bonded to the silicon atom of the hydrogen polysiloxane is less than 1.0 based on one alkenyl group of the organopolysiloxane, there can be a problem with curing. If the number thereof exceeds 3.0, many hydrogen atoms can remain in the coating after curing, resulting in a problem such as a change in peeling strength over time.

[0075] Also, the release coating solution can include a platinum chelate catalyst. In this case, it is preferable to include 410 to 890 ppm of the platinum chelate catalyst in the release coating solution. If the amount of the platinum chelate catalyst is less than 410 ppm, the residual adhesion is reduced and defects can occur in appearance, and if the amount thereof exceeds 890 ppm, the peeling strength will be increased too much.

[0076] Also, the release layer 20 is preferably formed by diluting the release coating solution in a solvent to include a total amount of 2 to 6% by weight of solid contents, and then coating the release coating solution on at least one surface of the base film 10. In this case, as a solvent for the release coating solution, any type of solvent can be used without limitation, as long as the solid contents of the present application can be dispersed and applied on the base film 10. If the total amount of the solid contents of the release coating solution is less than 2% by weight, a uniform release coating layer cannot be formed, which can result in a problem such as poor peeling between the silicone-based adhesive layer and the fluorine group-containing release film. If the total amount thereof exceeds 6% by weight, the viscosity of the coating solution is high, which can result in uneven leveling, thereby causing the thickness uniformity of the release layer to deteriorate.

[0077] Further, the release layer 20 formed by coating the base film 10 can be obtained by applying a release coating solution using a conventionally well-known coating method such as bar coating, gravure coating, die coating, and the like.

[0078] In one embodiment, the thickness of the release layer 20 after drying is preferably 100 nm to 300 nm. If the thickness of the release layer 20 after drying is less than 100 nm, the appearance of the coating is deteriorated and the peel strength is increased. If the thickness of the release layer 20 after drying exceeds 300 nm, the appearance of the coating is deteriorated and the residual adhesion is reduced.

[0079] Further, the release layer 20 is divided into a first region containing Si and a second region containing F, and more specifically, it is characterized in that the release layer 20 is divided into a first region adjacent to the base film 10 and containing Si in the release layer 20, and a second region adjacent to the surface of the release layer 20 not in contact with the base film 10 and containing F. The first region and the second region have a difference in brightness, the first region being a black silicon region and the second region being a white fluorine-containing group silicon region. In particular, the wider the second region, the better the peel strength.

[0080] In one embodiment, the thickness of the second region is preferably 0.001% to 40% of the total thickness of the release layer. When the thickness of the second region is less than 0.001% of the total thickness of the release layer, there are problems of matching the peel strength and the 2θ value being outside the range, and when it exceeds 40%, the residual adhesion is reduced.

[0081] The residual adhesion of the fluorine-containing group release film 100 according to one embodiment of the present application is preferably 90% or more. If the residual adhesion is less than 90%, the release layer 20 is not sufficiently cured, which can result in problems such as the release agent being transferred to the laminated adhesive layer and deteriorating the adhesive properties of the adhesive.

[0082] The peel strength of the fluorine-containing group release film 100 according to one embodiment of the present application is preferably 5 gf / inch to 25 gf / inch, the peel strength being measured by placing the release film 100 at 25°C and 65% RH for 24 hours, then adhering an organic silicon-based adhesive tape (MY2G, Taiwan) to the surface of the release layer not in contact with the base film, applying 20 g / cm2of weight to the tape at 50°C for 5 minutes, and then peeling the tape at a speed of 10 cm / minute. 2peeling at a peeling angle of 180° and at a peeling speed of 0.3 mpm. If the peeling strength is less than 5 gf / inch, the adhesion property between the release layer and the silicone-based adhesive deteriorates, and thus a problem such as a tunneling phenomenon that lifts the adhesive interface can occur, and if the peeling strength exceeds 25 gf / inch, peeling from the silicone-based adhesive cannot be properly performed, which can cause a process problem.

[0083] In the fluorine group-containing release film 100 according to one embodiment of the present application, it is preferable that the 2θ value according to the XRD analysis result be greater than 12.0 degrees and less than 13.5 degrees throughout the release layer 20. If the 2θ value according to the XRD analysis result is 12.0 degrees or less, the peeling strength excessively increases, and if the 2θ value is 13.5 degrees or more, the residual adhesion rate decreases.

[0084] The fluorine group-containing release film 100 according to one embodiment of the present application preferably has a change in haze of 5.0% or less after the following: placing a foreign matter-free wear-resistant nonwoven fabric on the surface of the release layer that does not contact the base film, and then performing 5 round trips by using a rubbing tester (CT-RB series) while maintaining a load of 300 g. If the change in haze after the rubbing test exceeds 5.0%, a push-back phenomenon can occur during the rub test.

[0085] Hereinafter, the configuration of the present application and its effects will be described in more detail through examples and comparative examples. The following examples are provided to further illustrate the present application and are not intended to limit the scope of the present application.

[0086] [Example]

[0087] [Example 1]

[0088] A release coating solution was manufactured, which included 100 parts by weight of an organic polysiloxane B (manufactured by Dow Chemical Inc., LTC-750A) not containing a fluorine group, 4.5 parts by weight of a hydrogen polysiloxane (manufactured by Dow Chemical Inc., Q2-7560), and 600 ppm of a platinum chelate catalyst (manufactured by Dow Chemical Inc., SYL-OFF 4000) based on 60 parts by weight of an organic polysiloxane A (manufactured by sooyangchemtec, SY-FSRA-B603) containing a fluorine group, after which the release coating solution was diluted in a hexane solution to obtain a total amount of 5% by weight of solid content. The release coating solution was then applied on a polyester film (Toray Advanced Materials Korean Inc., XD500P, 50 µm). After applying the release coating solution, the polyester film was dried with a hot air dryer at 150°C for 50 seconds to manufacture a fluorine group-containing release film by forming a release layer having a thickness of 0.2 µm.

[0089] [Example 2]

[0090] A fluorine group-containing release film was manufactured in the same manner as in Example 1, except that 5 parts by weight of the organic polysiloxane A (manufactured by sooyangchemtec, SY-FSRA-B603) containing a fluorine group was used.

[0091] [Example 3]

[0092] A fluorine group-containing release film was manufactured in the same manner as in Example 1, except that 200 parts by weight of the organic polysiloxane A (manufactured by sooyangchemtec, SY-FSRA-B603) containing a fluorine group was used.

[0093] [Example 4]

[0094] A fluorine group-containing release film was manufactured in the same manner as in Example 1, except that a release coating solution having a total solid content of 6% by weight was prepared and applied to form a release layer having a thickness of 0.3 µm.

[0095] [Example 5]

[0096] A fluorine group-containing release film was manufactured in the same manner as in Example 1, except that a release coating solution having a total solid content of 2% by weight was prepared and applied to form a release layer having a thickness of 0.1 µm.

[0097] [Comparative Example]

[0098] [Comparative Example 1]

[0099] A release film containing a fluorine group was manufactured in the same manner as in Example 1, except that the organic polysiloxane A containing a fluorine group (manufactured by sooyangchemtec, SY-FSRA-B603) was not used.

[0100] [Comparative Example 2]

[0101] A release film containing a fluorine group was manufactured in the same manner as in Example 1, except that the organic polysiloxane B not containing a fluorine group (manufactured by Dow Chemical Inc., LTC-750A) was not used.

[0102] [Comparative Example 3]

[0103] A release film containing a fluorine group was manufactured in the same manner as in Example 1, except that a release coating solution having a total solid content of 1.5 wt% was prepared and applied to form a release layer having a thickness of 0.08 µm.

[0104] [Comparative Example 4]

[0105] A release film containing a fluorine group was manufactured in the same manner as in Example 1, except that a release coating solution having a total solid content of 7 wt% was prepared and applied to form a release layer having a thickness of 0.35 µm.

[0106] The physical properties were measured by the following experimental examples using the release films according to Examples 1 to 5 and Comparative Examples 1 to 4, and the results are shown in Table 1 below.

[0107] [Experimental Examples]

[0108] 1. Evaluation of the surface of the release layer by XPS analysis

[0109] The surface of the release film containing a fluorine group prepared in the above examples and comparative examples was measured for 2θ value using an XRD analyzer (X-ray diffractometer: Model name Ultima-4), and the 2θ value is listed in Table 1.

[0110] 2. Measurement of the release strength of the release film

[0111] [Sample Preparation]

[0112] ① The release-coated sample was left at 25°C and 65% RH for 24 hours.

[0113] ② An adhesive tape based on silicone (MY2G, Taiwan) was adhered to the release-coated surface of the sample, and then the tape was pressed at a temperature of 50°C for 24 hours with a load of 20 g / cm 2 , and then the physical properties were measured.

[0114] [Measurement Instrument]

[0115] Chemical instrument AR-2000

[0116] [How to measure]

[0117] ① The peeling angle was 180° and the peeling speed was 0.3 mpm

[0118] ② The sample size was 500 mm x 1500 mm and the size for measuring the peeling strength was 250 mm x 1500 mm.

[0119] [Measurement data]

[0120] The peeling strength was expressed in gf / inch and the measured values were averaged after measuring the peeling strength of the sample five times, respectively.

[0121] 3. Analysis of residual adhesion rate of release film

[0122] [Sample preparation]

[0123] ① The release-coated sample was left at 25°C and 65% RH for 24 hours.

[0124] ② A standard adhesive tape (Nitto 31B) was adhered to the release-coated surface of the sample, and then the tape was pressed at room temperature for 24 hours with a load of 20 g / cm 2 .

[0125] ③ Then, the adhesive tape laminated on the silicone-coated surface was peeled off without contamination, and then adhered to the surface of a smooth and clean PET film, and pressed by reciprocating a 2 kg tape roller (ASTM D-1000-55T) once.

[0126] [Measurement instrument]

[0127] Chemical instrument AR-2000

[0128] [How to measure]

[0129] ① The peeling angle was 180° and the peeling speed was 0.3 mpm

[0130] ② The sample size was 500 mm x 1500 mm and the size for measuring the peeling strength was 250 mm x 1500 mm.

[0131] [Measurement data]

[0132]

[0133] 4. Thickness evaluation of release film

[0134] The fluorine group-containing release films prepared in the Examples and Comparative Examples were prepared, and the thickness of the fluorine group-containing release films was measured using a TEM (Transmission Electron Microscope, Model Name: JEM-ARM200F), and the results are shown in Table 1.

[0135] 5. Appearance evaluation of release film

[0136] The appearance of the release layer surfaces of the Examples and Comparative Examples in which the rubbing test was completed in Experimental Example 3 was evaluated, and Table 1 shows the results.

[0137] O: Good appearance (no cratering, or good film coating properties, or no scratches)

[0138] Δ: Partially defective appearance (1 to 3 craters, or partially poor film coating properties, or 1 to 3 scratches)

[0139] X: Poor appearance (more than 3 craters, or film coating defects, or more than 3 scratches)

[0140] [Table 1]

[0141]

[0142]

[0143] As can be seen from Table 1, the fluorine group-containing release films of Examples 1 to 5 according to the present application have excellent peelability against the organic silicon-based adhesive-based, and it can be seen that the 2θ value according to the XRD analysis result is greater than 12.0 degrees and less than 13.5 degrees. In addition, it can be seen that the fluorine group-containing release films according to Examples 1 to 5 have excellent release strength and residual adhesion rate properties. In addition, as described in Figure 2 and Figure 3 Example 1 can be determined to satisfy the 2θ value according to the XRD analysis result of greater than 12.0 degrees and less than 13.5 degrees and the release layer thickness of 0.2 μm. In addition, in the TEM photograph shown in Figure 3 , the second region having a high F density appears a relatively bright white color.

[0144] On the other hand, Comparative Examples 1 and 2 in which the 2θ value in the XRD analysis did not fall within the range of greater than 12.0 degrees and less than 13.5 degrees and Comparative Examples 3 and 4 in which the coating thickness of the release layer was not optimized resulted in poor coating appearance properties and deteriorated the release strength and / or residual adhesion rate.

[0145] As described above, the present application provides a fluorine group-containing release film including a release layer formed by applying a release coating solution containing a fluorine group-containing organopolysiloxane and a non-fluorine group-containing organopolysiloxane on at least one surface of a base film and having a 2θ value according to XRD analysis results of greater than 12.0 degrees and less than 13.5 degrees. Accordingly, dilution and coating of the coating solution can be performed without using a fluorine-based solvent, which improves processability and makes the coating uniform, thereby improving peelability and peel strength variation. In addition, the amount of the expensive fluorine group-containing organopolysiloxane used can be minimized, and thus a product having excellent physical properties and high cost effectiveness can be manufactured. When the fluorine group-containing release film according to the present application is applied to an organic silicon-based adhesive treatment process, a cost reduction effect as well as excellent physical properties can be obtained.

[0146] In the present specification, only some examples of a plurality of embodiments performed by the inventors are illustrated by way of example, but it should be noted that the technical scope of the present application is not limited thereto, and of course can be modified and changed by those skilled in the art.

[0147] Reference Signs

[0148] 100: fluorine group-containing release film

[0149] 10: base film

[0150] 20: release layer

Claims

1. A fluorine group-containing release film, comprising: a base film; and a release layer formed on at least one surface of the base film by applying a release coating solution containing a fluorine group-containing organopolysiloxane (A) and a non-fluorine group-containing organopolysiloxane (B) on the at least one surface of the base film, wherein the 2Θ value according to the results of XRD analysis is greater than 12.0 degrees and less than 13.5 degrees throughout the release layer, wherein the release layer is divided into a first region adjacent to the base film and containing Si in the release layer, and a second region adjacent to the surface of the release layer not contacting the base film and containing F, wherein the first region and the second region have a contrast difference, wherein the content of the non-fluorine group-containing organopolysiloxane (B) is in an amount of 50 parts by weight to 2,000 parts by weight based on 100 parts by weight of the fluorine group-containing organopolysiloxane (A), wherein the thickness of the release layer after drying is 100 nm to 300 nm, wherein the thickness of the second region is 0.001% to 40% of the total thickness of the release layer.

2. The fluorine group-containing release film according to claim 1, having a peel strength of 5 gf / inch to 25 gf / inch, the peel strength being measured by adhering an organic silicon-based adhesive tape to a surface of the release layer after the release film is left at 25°C and 65% RH for 24 hours, pressing the tape at 50°C with a load of 20 g / cm 2 for 24 hours, and then peeling the tape at a peel angle of 180° and at a peel speed of 0.3 mpm.

3. The fluorine group-containing release film according to claim 1, wherein the residual adhesion rate of the fluorine group-containing release film is 90% or more.

4. The fluorine group-containing release film according to claim 1, wherein the first region is black, and the second region is white.

5. The fluorine group-containing release film according to claim 1, wherein the fluorine group-containing organopolysiloxane (A) contains at least one fluorine-containing substituent selected from an alkenyl group having 2 to 10 carbon atoms, and a fluoroalkyl group or a fluoroether group in one molecule.

6. The fluorine group-containing release film according to claim 1, wherein the non-fluorine group-containing organopolysiloxane (B) contains an alkenyl group or an alkyl group having 2 to 10 carbon atoms in one molecule.

7. The fluorine group-containing release film according to claim 1, wherein the release coating solution contains a total amount of 2% by weight to 6% by weight of solid content.

8. A method of manufacturing the fluorine group-containing release film according to any one of claims 1 to 7, comprising: preparing a base film; and forming a release layer by applying a release coating solution containing a fluorine group-containing organopolysiloxane (A), a non-fluorine group-containing organopolysiloxane (B), a hydrosilicone, and a platinum chelate catalyst on at least one surface of the base film and drying the release coating solution, wherein the 2Θ value according to the results of XRD analysis is greater than 12.0 degrees and less than 13.5 degrees throughout the release layer, wherein the release layer is divided into a first region adjacent to the base film and containing Si in the release layer, and a second region adjacent to the surface of the release layer not contacting the base film and containing F, wherein the first region and the second region have a contrast difference.

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