Release film and method of manufacturing the same

Abstract

A release film and a method of manufacturing the same are disclosed. The release film includes a release layer having both ultra-light release properties of low release force to both acrylic adhesives and silicone adhesives and excellent adhesion with little change in haze before and after abrasion. The release film includes a substrate and a release layer on at least one side of the substrate, wherein the release layer is a cured layer of a composition including a blend of a first fluorine-containing organopolysiloxane, a second fluorine-containing organopolysiloxane, and a non-fluorine-containing organopolysiloxane. The release film is used in industries such as displays, tapes, and labels.

Description

Technical Field

[0001] This invention relates to a release film and its manufacturing method. Background Technology

[0002] In recent years, industries such as displays, tapes, and labels have been increasing their use of ultralight release films with low peel strength in order to improve processes and increase production efficiency. Manufacturing such ultralight release films requires either increasing the release layer thickness or reducing surface energy.

[0003] Release agents containing fluorinated resins in the release layer have low surface energy, making them difficult to mix with common organic solvents and potentially causing coating defects. Therefore, fluorinated solvents are required. The longer the fluorine chain in the release agent containing the fluorinated resin, the lower its solubility due to surface tension, making it difficult to coat and inhibiting curing. This not only reduces adhesion but also makes it difficult to synthesize, thus increasing its price by tens of times compared to common silicone release agents. Conversely, the shorter the fluorine chain, the better the solubility or adhesion of the release agent containing the fluorinated resin, but its surface energy or peel strength is not significantly different from that of silicone release agents.

[0004] Therefore, there is still a need for a release film that includes a release layer that can be made of both acrylic and silicone adhesives, and has low peel strength, excellent adhesion, and minimal haze change before and after wear for these adhesives (hereinafter, this refers to pressure-sensitive adhesives). Summary of the Invention

[0005] Technical issues

[0006] One aspect provides a release film comprising a release layer that exhibits ultra-light peel strength and excellent adhesion to both acrylic and silicone adhesives, and shows minimal haze change before and after abrasion.

[0007] On the other hand, a method for manufacturing the release film is provided.

[0008] Technical solution

[0009] According to one aspect, a release film is provided, comprising:

[0010] A substrate; and a release layer located on at least one side of the substrate.

[0011] The release layer is the cured layer of the composition, which includes a blend of a first fluorinated organopolysiloxane, a second fluorinated organopolysiloxane, and a non-fluorinated organopolysiloxane.

[0012] The release layer is divided into a first region and a second region.

[0013] The first region is the surface of the release layer and the region adjacent to the surface, and is the region where the content of F atoms decreases and the content of Si atoms increases during XPS analysis while plasma etching is performed from the surface along the thickness direction.

[0014] The second region is the area on one side of the release layer in contact with the substrate and the area adjacent to that side, and it is the region where the content of F atoms and Si atoms remains constant during the XPS analysis.

[0015] The first region satisfies equations 1 and 2 below.

[0016] The second region satisfies the following equation 3:

[0017] [Formula 1]

[0018]

[0019] in,

[0020] F can represent the fluorine content (at%) present on the surface of the first region as determined by XPS analysis.

[0021] Si+O+C can represent the total content (at%) of silicon, oxygen, and carbon present on the surface of the first region as determined by XPS analysis.

[0022] [Equation 2]

[0023] BA<10

[0024] in,

[0025] A can be the haze (%) of the surface of the first area before it is rubbed five times using a rubbing tester with a 300g weight.

[0026] B can be the haze (%) of the surface of the first area after rubbing it five times using a rubbing tester with a 300g weight.

[0027] [Formula 3]

[0028] F1-F2=△F≤5at%

[0029] in,

[0030] F1 can be the content (at%) of F atoms at the time point (T1) when the C atom content reaches 50 at% during XPS analysis of the second region.

[0031] F2 can be the F atom content (at%) at twice the time point (T1) when the C atom content reaches 50 at% during XPS analysis of the second region (2×T1).

[0032] The first region includes a first fluorinated organopolysiloxane and a second fluorinated organopolysiloxane.

[0033] The first fluorinated organopolysiloxane and the second fluorinated organopolysiloxane may include substituents containing fluorinated alkyl groups.

[0034] The second fluorinated organopolysiloxane may have a fluorinated alkyl group that is longer than that of the first fluorinated organopolysiloxane.

[0035] The first fluorinated organopolysiloxane may include an organopolysiloxane represented by the following chemical formula 1:

[0036] [Chemical Formula 1]

[0037]

[0038] [Chemical Formula 2]

[0039]

[0040] in,

[0041] R1 can be a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group or a substituted or unsubstituted C2 to C10 alkenyl group;

[0042] R2 can be a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group or a substituted or unsubstituted C2 to C10 alkenyl group or hydrogen;

[0043] R3 and R4 can be independently derived from fluorinated alkyl groups, substituted or unsubstituted C1 to C10 monovalent hydrocarbon groups, substituted or unsubstituted C2 to C10 alkenyl groups, or hydrogen groups represented by the chemical formula 2.

[0044] Furthermore, at least one of R3 and R4 can be a fluorinated alkyl group represented by the chemical formula 2;

[0045] n can be an integer from 1 to 3, and m can be an integer from 1 to 5;

[0046] x, y, and z can be integers greater than or equal to 1;

[0047] * can be a binding site with an adjacent atom;

[0048] However, at least one of R1 and R2 can be a substituted or unsubstituted C2 to C10 alkenyl group.

[0049] The second fluorinated organopolysiloxane may include an organopolysiloxane represented by the following chemical formula 1:

[0050] [Chemical Formula 1]

[0051]

[0052] [Chemical Formula 2]

[0053]

[0054] in,

[0055] R1 can be a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group or a substituted or unsubstituted C2 to C10 alkenyl group;

[0056] R2 can be a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group or a substituted or unsubstituted C2 to C10 alkenyl group or hydrogen;

[0057] R3 and R4 can be independently derived from fluorinated alkyl groups, substituted or unsubstituted C1 to C10 monovalent hydrocarbon groups, substituted or unsubstituted C2 to C10 alkenyl groups, or hydrogen groups represented by the chemical formula 2.

[0058] Furthermore, at least one of R3 and R4 can be a fluorinated alkyl group represented by the chemical formula 2;

[0059] n can be an integer from 4 to 9, and m can be an integer from 1 to 5;

[0060] x, y, and z can be integers greater than or equal to 1;

[0061] * can be a binding site with an adjacent atom;

[0062] However, at least one of R1 and R2 can be a substituted or unsubstituted C2 to C10 alkenyl group.

[0063] Based on 100 parts by weight of the non-fluorinated organopolysiloxane, the contents of the first fluorinated organopolysiloxane and the second fluorinated organopolysiloxane can be from 5 parts by weight to 100 parts by weight, respectively.

[0064] The non-fluorinated organopolysiloxane may include organopolysiloxanes containing vinyl and methyl groups.

[0065] The release layer may further include at least one of hydrogen polysiloxane and a catalyst.

[0066] The release layer may further comprise organic or inorganic particles with an average particle size (D50) of 1 μm to 5 μm.

[0067] The thickness of the release layer can be from 0.03 μm to 2.0 μm.

[0068] The surface energy of the release layer can be from 14 dyne / cm to 17 dyne / cm.

[0069] The reduced modulus of the release layer, measured by nanoindentation technology, can be from 3.5 GPa to less than 4.2 GPa.

[0070] The surface hardness of the release layer, measured by nanoindentation technology, can be from 0.3 GPa to 0.45 GPa.

[0071] According to another aspect, a method for manufacturing a release film is provided, which includes the following steps:

[0072] Prepare the substrate; and

[0073] A composition comprising a first fluorinated organopolysiloxane, a second fluorinated organopolysiloxane, a non-fluorinated organopolysiloxane, and a hydrogen-containing polysiloxane is coated onto at least one side of the substrate and a release layer is formed by heat treatment.

[0074] The release layer is divided into a first region and a second region.

[0075] The first region is the surface of the release layer and the region adjacent to the surface, and it is the region where the content of F atoms decreases and the content of Si atoms increases sharply during XPS analysis while plasma etching is performed from the surface along the thickness direction.

[0076] The second region is the area on one side of the release layer in contact with the substrate and the area adjacent to that side, and it is the region where the content of F atoms and Si atoms remains constant during the XPS analysis.

[0077] The first region satisfies equations 1 and 2 below.

[0078] The second region satisfies the following equation 3:

[0079] [Formula 1]

[0080]

[0081] in,

[0082] F can represent the fluorine content (at%) present on the surface of the first region as determined by XPS analysis.

[0083] Si+O+C can represent the total content (at%) of silicon, oxygen, and carbon present on the surface of the first region as determined by XPS analysis.

[0084] [Equation 2]

[0085] BA<10

[0086] in,

[0087] A can be the haze (%) of the surface of the first area before it is rubbed five times using a rubbing tester with a 300g weight.

[0088] B can be the haze (%) of the surface of the first area after rubbing it five times using a rubbing tester with a 300g weight.

[0089] [Formula 3]

[0090] F1-F2=△F≤5at%

[0091] in,

[0092] F1 can be the content (at%) of F atoms at the time point (T1) when the C atom content reaches 50 at% during XPS analysis of the second region.

[0093] F2 can be the F atom content (at%) at twice the time point (T1) when the C atom content reaches 50 at% during XPS analysis of the second region (2×T1).

[0094] Based on a total of 100% by weight of the composition, the content of the hydrogen-containing polysiloxane may be from 1% by weight to 10% by weight.

[0095] The solid content of the composition can be from 0.5% by weight to 10% by weight. Attached Figure Description

[0096] Figure 1 This is a cross-sectional schematic diagram of a release film according to one embodiment.

[0097] Figure 2 The results are obtained by transmission electron microscopy (TEM) analysis of the release layer of the release film manufactured in Example 1.

[0098] Figure 3 The results are obtained by XPS analysis of the release layer of the release film manufactured in Example 1, while plasma etching is performed from the surface along the thickness direction. Detailed Implementation

[0099] The release film and its manufacturing method are described in detail below with reference to embodiments and accompanying drawings. It will be apparent to those skilled in the art that these embodiments are merely for the purpose of describing the invention in more detail, and the scope of the invention is not limited thereto.

[0100] All technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains, unless otherwise defined. In case of conflict, the definitions included in this specification shall prevail.

[0101] Similar or equivalent methods and materials to those described in this specification may be used in the implementation or experimentation of this invention, but suitable methods and materials are described in this specification.

[0102] The term "comprising" in this specification means that other constituent elements may be included, but not excluded, unless otherwise defined.

[0103] The term "combination of them" in this specification means a mixture or combination with at least one of the plurality of constituent elements described.

[0104] The term "and / or" in this specification means any and all combinations of one or more of the listed items. The term "or" in this specification means "and / or". In this specification, "at least one" or "one or more" preceding a constituent element does not imply a complete list of constituent elements or supplements the individual constituent elements described above.

[0105] In this specification, when referring to a component being disposed "above" or "on top of" another component, a component is directly disposed on top of another component, or there are components sandwiched between the components. Conversely, when referring to a component being disposed "directly" above or on top of another component, there may be no sandwiched component.

[0106] In this specification, “~ type of resin”, “~ type of polymer” and / or “~ type of copolymer” are broad concepts that include “~ type of resin”, “~ type of polymer”, “~ type of copolymer” and / or “derivatives of ~ type of resin, polymer or copolymer”.

[0107] The term "polymer or copolymer crosslinked by its resin" in this specification means "polymer or copolymer crosslinked by the aforementioned resin".

[0108] In this specification, "long-length fluorinated alkyl group" means "a fluorinated alkyl group that has a relatively long length due to the large number of carbon atoms in the chain that makes up the fluorinated alkyl group".

[0109] In this description, each component is expressed in both singular and plural forms.

[0110] In this specification, all percentages, parts, proportions, etc., are based on weight unless otherwise stated. Furthermore, when a quantity, concentration, or other value or parameter is shown as any of a range, preferred range, or a list of preferred upper and lower limits, it should be understood as specifically disclosing the entire range formed by any pair of any upper or preferred range value and any lower or preferred range value, regardless of whether a range is provided separately.

[0111] In this specification, when a range of numerical values ​​is referred to, the range is intended to include its endpoints and all integers and fractions within its range, unless otherwise stated. The scope of this invention is not intended to be limited to the specific values ​​mentioned when defining the range.

[0112] According to one embodiment, a release film includes a substrate and a release layer, the release layer being located on at least one side of the substrate.

[0113] Figure 1 This is a cross-sectional schematic diagram of the release film 120 according to one embodiment.

[0114] See Figure 1 According to one embodiment, the release film 120 has a structure in which a substrate 100 and a release layer 110 are arranged in sequence.

[0115] Release layer 110 is a cured layer of the composition, which may include a first fluorinated organopolysiloxane, a second fluorinated organopolysiloxane, and a blend of non-fluorinated organopolysiloxanes. Release layer 110 is divided into a first region and a second region. The first region is the surface of the release layer and the region adjacent to the surface, and is the region where the content of F atoms decreases and the content of Si atoms increases during XPS analysis while plasma etching is performed along the thickness direction from the surface. The second region is the side of the release layer in contact with the substrate and the region adjacent to the side, and is the region where the content of F atoms and Si atoms remains constant during the XPS analysis. The first region satisfies Equations 1 and 2, and the second region satisfies Equation 3.

[0116] [Formula 1]

[0117]

[0118] in,

[0119] F represents the fluorine content (at%) present on the surface of the first region as determined by XPS analysis.

[0120] Si+O+C represents the total content (at%) of silicon, oxygen, and carbon present on the surface of the first region as determined by XPS analysis.

[0121] [Equation 2]

[0122] BA<10

[0123] in,

[0124] A is the surface haze (%) of the first area before it is rubbed five times using a rubbing tester with a 300g weight.

[0125] B is the haze (%) of the surface of the first area after rubbing it five times using a rubbing tester with a 300g weight.

[0126] [Formula 3]

[0127] F1-F2=△F≤5at%

[0128] in,

[0129] F1 is the F atom content (at%) at the time point (T1) when the C atom content reaches 50 at% during XPS analysis of the second region.

[0130] F2 is the F atom content (at%) at twice the time point (T1) when the C atom content reaches 50 at% during XPS analysis of the second region (2×T1).

[0131] According to one embodiment, the release film 120 has ultra-light peel strength and excellent adhesion to both acrylic and silicone adhesives, and exhibits minimal haze change before and after abrasion.

[0132] The following describes in detail the substrate 100 constituting the release film 120, the release layer 110, and the manufacturing method of the release film 120.

[0133] <Substrate 100>

[0134] The substrate used in this specification can be any known substrate film or sheet used as a release film substrate. For example, a polyester resin film can be used as the substrate. The polyester resin can be any known substrate film conventionally used in the field of release films. For example, the polyester substrate film can be any polyester substrate film disclosed in Korean Registered Patent No. 10-1268584, Korean Patent Publication No. 2012-45213, and Korean Patent Publication No. 2012-99546. In one embodiment of the invention, the described polyester substrate film is not limited in order to be described solely by the features of the invention, but it should be understood to include known technical features related to polyester substrate films.

[0135] The polyester substrate film may include polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate, etc.

[0136] The polyester resin forming the substrate film can be a polyester obtained by condensing an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid and an aliphatic ethylene glycol.

[0137] Examples of the aromatic or aliphatic dicarboxylic acids may include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, and hydroxycarboxylic acids (e.g., p-hydroxybenzoic acid). Examples of the aliphatic ethylene glycols may include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanediol, and neopentyl glycol. The polyester resin may be a polyester obtained by combining two or more of the dicarboxylic acid and glycol components, or a copolymer containing a third component may be used.

[0138] In addition, polyester resin substrate films can be uniaxial or biaxially oriented films with high transparency, excellent manufacturability, and processability. The polyester substrate film can be made of polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), etc.

[0139] In addition, polyester-based films can contain particles to improve the running performance between rollers, and the added particles can exhibit excellent sliding properties, so they can be used without restrictions.

[0140] Examples of the particles may include particles of silica, silicon oxide, calcium carbonate, calcium sulfate, calcium phosphate, magnesium carbonate, magnesium phosphate, barium carbonate, kaolin, alumina, titanium oxide, etc., and there are no restrictions on the shape of the particles used; for example, any of spherical, blocky, rod-shaped, and plate-shaped particles may be used.

[0141] Furthermore, there are no particular restrictions on the hardness, specific gravity, and color of the particles, but two or more types can be used in combination as needed, and the average particle size can be from 0.1 μm to 5 μm, for example, from 0.1 μm to 2 μm. However, when the average particle size is less than 0.1 μm, dispersion defects may occur due to particle aggregation; when the average particle size is greater than 5 μm, the surface roughness characteristics of the film deteriorate, potentially leading to coating defects during post-processing.

[0142] Additionally, when the polyester substrate film includes particles, the particle content can be from 0.01% to 5% by weight of the total weight of the polyester substrate film, for example, from 0.01% to 3% by weight. When the particle content is less than 0.01% by weight, the running performance between rollers may deteriorate due to the deterioration of the sliding characteristics of the polyester film. When the particle content is greater than 5% by weight, the surface smoothness of the film may deteriorate.

[0143] The thickness of polyester substrate films is not limited, but can range from 20μm to 125μm.

[0144] When the thickness of the polyester substrate film is too thin (less than or equal to 20 μm), it may deform during heat treatment in the processing. When its thickness is too thick (greater than or equal to 125 μm), it may harden due to insufficient heat transfer.

[0145] <Release Layer 110>

[0146] According to one embodiment, the release layer of the release film can be a cured layer of a composition comprising a first fluorinated organopolysiloxane, a second fluorinated organopolysiloxane, and a blend of a non-fluorinated organopolysiloxane.

[0147] The release layer can be divided into a first region and a second region. The first region is the surface of the release layer and the region adjacent to the surface, and is the region where the content of F atoms decreases and the content of Si atoms increases during XPS analysis while plasma etching is performed along the thickness direction from the surface. The second region is the side of the release layer in contact with the substrate and the region adjacent to that side, and is the region where the content of F atoms and Si atoms remains constant during XPS analysis. That is, the first region refers to the region near the outer surface of the release layer, and the second region refers to the region near the substrate. This can be further explained later. Figure 2 TEM analysis and Figure 3 XPS analysis was used to confirm this separation of the release layer.

[0148] In the first region, the ratio of fluorine atoms relative to the total content of silicon, oxygen, and carbon atoms can decrease from the surface along the thickness direction. The higher the ratio of fluorine atoms relative to the total content of silicon, oxygen, and carbon atoms on the release layer surface, the better the peel force when laminating the release layer with silicone adhesives. Therefore, the release layer has low peel force and low peel force variation rate to silicone adhesives, in addition to acrylic adhesives.

[0149] The first region can satisfy the following equations 1 and 2:

[0150] [Formula 1]

[0151]

[0152] in,

[0153] F can represent the fluorine content (at%) present on the surface of the first region as determined by XPS analysis.

[0154] Si+O+C can represent the total content (at%) of silicon, oxygen, and carbon present on the surface of the first region as determined by XPS analysis.

[0155] [Equation 2]

[0156] BA<10

[0157] in,

[0158] A can be the haze (%) of the surface of the first area before it is rubbed five times using a rubbing tester with a 300g weight.

[0159] B can be the haze (%) of the surface of the first area after rubbing it five times using a rubbing tester with a 300g weight.

[0160] In Formula 1, when the ratio of fluorine atoms present on the surface of the first region to the total content of silicon, oxygen, and carbon atoms is less than 0.4, peeling may fail during the lamination of the release layer and silicone adhesive. In Formula 1, when the ratio of fluorine atoms present on the surface of the first region to the total content of silicon, oxygen, and carbon atoms is greater than 0.7, the curing of the first and second fluorinated organopolysiloxanes requires a large amount of heat, potentially causing thermal deformation of the substrate. Furthermore, the increased folded modulus and surface hardness of the release layer may increase the peel force against acrylic adhesives.

[0161] In Equation 2, when the haze change (BA) is greater than or equal to 10, the release agent may transfer to the adhesive layer to be bonded due to insufficient curing of the release layer, and the adhesiveness of the adhesive deteriorates.

[0162] The second region can satisfy the following equation 3:

[0163] [Formula 3]

[0164] F1-F2=△F≤5at%

[0165] in,

[0166] F1 is the F atom content (at%) at the time point (T1) when the C atom content reaches 50 at% during XPS analysis of the second region.

[0167] F2 is the F atom content (at%) at twice the time point (T1) when the C atom content reaches 50 at% during XPS analysis of the second region (2×T1).

[0168] In the second region, the content of F atoms remains constant.

[0169] The first region may include a first fluorinated organopolysiloxane and a second fluorinated organopolysiloxane, wherein the first

[0170]

[0171] The fluorinated organopolysiloxane and the second fluorinated organopolysiloxane may include substituents containing fluorinated alkyl groups, and the second fluorinated organopolysiloxane may have a fluorinated alkyl group that is longer than that of the first fluorinated organopolysiloxane.

[0172] The first fluorinated organopolysiloxane may include an organopolysiloxane represented by the following chemical formula 1:

[0173]

[0174] [Chemical Formula 1]

[0175]

[0176] [Chemical Formula 2]

[0177] in,

[0178] R1 can be a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group or a substituted or unsubstituted C2 to C10 alkenyl group;

[0179] R2 can be a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group or a substituted or unsubstituted C2 to C10 alkenyl group or hydrogen;

[0180] R3 and R4 can be independently derived from fluorinated alkyl groups, substituted or unsubstituted C1 to C10 monovalent hydrocarbon groups, substituted or unsubstituted C2 to C10 alkenyl groups, or hydrogen groups represented by the chemical formula 2.

[0181] Furthermore, at least one of R3 and R4 can be a fluorinated alkyl group represented by the chemical formula 2;

[0182] n can be an integer from 1 to 3, and m can be an integer from 1 to 5;

[0183] x, y, and z can be integers greater than or equal to 1;

[0184] * can be a binding site with an adjacent atom;

[0185] However, at least one of R1 and R2 can be a substituted or unsubstituted C2 to C10 alkenyl group.

[0186] The second fluorinated organopolysiloxane may include an organopolysiloxane represented by the following chemical formula 1:

[0187] [Chemical Formula 1]

[0188]

[0189] [Chemical Formula 2]

[0190]

[0191] in,

[0192] R1 can be a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group or a substituted or unsubstituted C2 to C10 alkenyl group;

[0193] R2 can be a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group or a substituted or unsubstituted C2 to C10 alkenyl group or hydrogen;

[0194] R3 and R4 can be independently derived from fluorinated alkyl groups, substituted or unsubstituted C1 to C10 monovalent hydrocarbon groups, substituted or unsubstituted C2 to C10 alkenyl groups, or hydrogen groups represented by the chemical formula 2.

[0195] Furthermore, at least one of R3 and R4 can be a fluorinated alkyl group represented by the chemical formula 2;

[0196] n can be an integer from 4 to 9, and m can be an integer from 1 to 5;

[0197] x, y, and z can be integers greater than or equal to 1;

[0198] * can be a binding site with an adjacent atom;

[0199] However, at least one of R1 and R2 can be a substituted or unsubstituted C2 to C10 alkenyl group.

[0200] Based on 100 parts by weight of the non-fluorinated organopolysiloxane, the contents of the first fluorinated organopolysiloxane and the second fluorinated organopolysiloxane can be from 5 parts by weight to 100 parts by weight, respectively. When, based on 100 parts by weight of the non-fluorinated organopolysiloxane, the contents of the first fluorinated organopolysiloxane and the second fluorinated organopolysiloxane are less than 5 parts by weight, the surface energy may increase and the hardness may decrease due to insufficient curing of the fluorine groups on the release layer surface, resulting in significant changes over time due to adhesion and adhesive penetration. Therefore, peeling is prevented when laminating the release layer and the silicone adhesive. When, based on 100 parts by weight of the non-fluorinated organopolysiloxane, the contents of the first fluorinated organopolysiloxane and the second fluorinated organopolysiloxane are greater than 100 parts by weight, the curing of the fluorinated organopolysiloxane requires a large amount of energy, thus the substrate may deform and its adhesion may be poor.

[0201] The non-fluorinated organopolysiloxane may include organopolysiloxanes containing vinyl and methyl groups.

[0202] The release layer may further include at least one of hydrogen-containing polysiloxane and a catalyst.

[0203] The hydrogen-containing polysiloxane may include at least one of addition-reactive siloxane resins, condensation-reactive siloxane resins, and UV-curable siloxane resins. The hydrogen-containing polysiloxane may have a linear, branched, or cyclic shape, and may be a mixture thereof. The viscosity or molecular weight of the hydrogen-containing polysiloxane is not limited, but it should have good compatibility with the aforementioned organopolysiloxanes, and the hydrogen-containing polysiloxane may not contain fluorine groups. However, the hydrogen-containing polysiloxane may also include the same fluorinated alkyl groups and / or fluorinated diethyl ethers as the aforementioned organopolysiloxanes.

[0204] The catalyst may use at least one metal or amphoteric atom selected from Groups 4 to 14, for example, at least one selected from Rh, Pt, Sn, Ti, Pd, Ir, W, and Co. For example, the catalyst may include a platinum chelate catalyst.

[0205] Depending on the specific circumstances, the release layer may further include additives for imparting various functions, such as reaction modifiers and antistatic agents.

[0206] The release layer may further comprise organic or inorganic particles with an average particle size (D50) of 1 μm to 5 μm.

[0207] For example, the average particle size (D50) of the organic particles and the continuously variable particles can be 3 μm to 5 μm or 1 μm to 2 μm. In this specification, "average particle size (D50)" refers to the value from the smallest particle size to the corresponding 50% particle size when the total number of particles is set to 100% according to the cumulative distribution curve from the smallest particle size to the largest particle size. The D50 value can be measured by methods known to those skilled in the art, for example, using a laser particle size analyzer or by TEM or scanning electron microscope (SEM) images. Alternatively, the D50 value can be easily obtained by calculation after measuring and analyzing the data using a dynamic light-scattering measurement device, thereby counting the number of particles in each particle size range.

[0208] When the average particle size (D50) of the organic or inorganic particles is less than 1 μm, sufficient surface roughness cannot be obtained, thus failing to prevent adhesion. When the average particle size (D50) of the organic or inorganic particles is greater than 5 μm, it may become a drawback of the membrane.

[0209] The organic or inorganic particles are natural minerals; oxides, hydroxides, sulfides, nitrides or halides of atoms from Groups 1 to 4, 11 to 12, 14, 16 to 18; carbonates, sulfates, acetates, phosphates, phosphites, carboxylates, silicates, titanates, borates or their hydrates; and inorganic particles selected from their complexes.

[0210] The organic or inorganic particles may be organic particles selected from fluorinated resins, melamine resins, styrene resins, acrylic resins, silicone resins, styrene-divinylbenzene copolymer resins, and polymers or copolymers crosslinked from these resins.

[0211] There are no particular restrictions on the shape of the organic or inorganic particles used; they can be spherical, blocky, rod-shaped, or flat. Furthermore, the hardness, specific gravity, color, etc., of the organic or inorganic particles are also unrestricted. The organic or inorganic particles can be used alone, or two or more types can be used as needed.

[0212] The thickness of the release layer can be from 0.03 μm to 2.0 μm. When the thickness of the release layer is less than 0.03 μm, it may be unable to peel off when laminated with acrylic and / or silicone adhesives due to poor coverage. When the thickness of the release layer is greater than 2.0 μm, a large amount of heat is required during the curing process, which may cause thermal deformation of the substrate, and increases costs due to the lack of improved peelability.

[0213] The surface energy of the release layer can be between 14 dyne / cm and 17 dyne / cm. When the surface energy of the release layer is less than 14 dyne / cm, the adhesive may not be able to be applied due to the low surface energy. When the surface energy of the release layer is greater than 17 dyne / cm, the fluorinated organopolysiloxane on the surface of the release layer may not be sufficiently cured, resulting in the release layer and the silicone adhesive being unable to peel off.

[0214] The reduced modulus of the release layer, measured using nanoindentation technology, can range from 3.5 GPa to less than 4.2 GPa. When the reduced modulus of the release layer is less than 3.5 GPa, adhesion may occur during winding due to the softening of the release layer. When the reduced modulus of the release layer is greater than 4.2 GPa, the peel force will be increased due to the harder release layer.

[0215] The surface hardness of the release layer, measured by nanoindentation technology, can range from 0.3 GPa to 0.45 GPa. When the surface hardness of the release layer, measured by nanoindentation technology, is less than 0.3 GPa, the reduced surface hardness may allow the adhesive to penetrate, leading to significant changes over time. When the surface hardness of the release layer, measured by nanoindentation technology, is greater than 0.45 GPa, the peel force may be increased due to the higher surface hardness.

[0216] The release film including the release layer can have a peel force of 0.3gf / 25mm to 10gf / 25mm on acrylic and silicone adhesives at a peel angle of 180° and a peel speed of 0.3mpm.

[0217] When the release film exhibits a peel force of less than 0.3 gf / 25 mm against acrylic and silicone adhesives at a peel angle of 180° and a peel speed of 0.3 mpm, the adhesion between the release layer and the silicone adhesive decreases, potentially causing the lamination interface to detach, such as through tunneling. When the release film exhibits a peel force of less than 10 gf / 25 mm against acrylic and silicone adhesives at a peel angle of 180° and a peel speed of 0.3 mpm, incomplete peeling from the acrylic and silicone adhesives leads to process engineering problems.

[0218] According to another method for manufacturing a release film, the method includes the following steps: preparing a substrate; and coating a composition comprising a first fluorinated organopolysiloxane, a second fluorinated organopolysiloxane, a non-fluorinated organopolysiloxane, and a hydrogen-containing polysiloxane onto at least one side of the substrate and forming a release layer by heat treatment, wherein the release layer is divided into a first region and a second region, the first region being the surface of the release layer and the region adjacent to the surface, and being a region where the content of F atoms decreases and the content of Si atoms increases during XPS analysis while plasma etching is performed along the thickness direction from the surface, the second region being the side of the release layer in contact with the substrate and the region adjacent to the side, and being a region where the content of F atoms and Si atoms remains constant during the XPS analysis, the first region satisfying Equations 1 and 2, and the second region satisfying Equation 3:

[0219] [Formula 1]

[0220]

[0221] in,

[0222] F can represent the fluorine content (at%) present on the surface of the first region as determined by XPS analysis.

[0223] Si+O+C can represent the total content (at%) of silicon, oxygen, and carbon present on the surface of the first region as determined by XPS analysis.

[0224] [Equation 2]

[0225] BA<10

[0226] in,

[0227] A can be the haze (%) of the surface of the first area before it is rubbed five times using a rubbing tester with a 300g weight.

[0228] B can be the haze (%) of the surface of the first area after rubbing it five times using a rubbing tester with a 300g weight.

[0229] [Formula 3]

[0230] F1-F2=△F≤5at%

[0231] in,

[0232] F1 can be the content (at%) of F atoms at the time point (T1) when the C atom content reaches 50 at% during XPS analysis of the second region.

[0233] F2 can be the F atom content (at%) at twice the time point (T1) when the C atom content reaches 50 at% during XPS analysis of the second region (2×T1).

[0234] First, prepare the substrate. The descriptions related to the substrate have been described above, and therefore will not be repeated below.

[0235] Then, a composition comprising a first fluorinated organopolysiloxane, a second fluorinated organopolysiloxane, a non-fluorinated organopolysiloxane, and a hydrogen-containing polysiloxane is coated on at least one side of the substrate and a release layer is formed by heat treatment.

[0236] Based on the total weight of the composition, the content of the hydrogen-containing polysiloxane can be from 1% by weight to 10.0% by weight.

[0237] The solid content of the composition can be from 0.5% by weight to 10% by weight. The solvent used for the composition can be unlimited as long as the solid can be dispersed and coated onto a substrate. For example, aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane, and isoparaffins; hydrocarbon solvents such as industrial gasoline (rubber gasoline, etc.), petroleum benzene, and solvent naphtha; ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, acetone-based acetone, and cyclohexanone; and ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, etc. Ester solvents such as isobutyl ester; ether solvents such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1,2-dimethoxyethane, and 1,4-dioxane; solvents having both ester and ether moieties such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, and 2-butoxyethyl acetate; siloxane solvents such as hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tris(trimethylsiloxy)methylsilane, and tetra(trimethylsiloxy)silane; fluorinated solvents such as trifluorotoluene, hexafluoroxylene, methyl nonafluorobutyl ether, and ethyl nonafluorobutyl ether; or mixtures thereof. For example, heptane can be used as a solvent for the composition used to form the release layer.

[0238] When the solids content of the composition is less than 0.5% by weight, sufficient coating thickness cannot be formed, and therefore release properties may not be exhibited. When the solids content of the composition is greater than 10% by weight, uneven leveling occurs due to the high viscosity of the composition, thereby deteriorating the uniformity of the release layer thickness and preventing curing due to the increased coating thickness.

[0239] The composition can be applied to one side of the substrate using offline coating methods known to those skilled in the art, such as bar coating, gravure coating, and die coating. There are no particular limitations on the curing energy used to form the release layer composition; for example, heat treatment, ultraviolet irradiation, or electron beam irradiation can be used, and these can be used alone or in combination, such as heat treatment alone or in combination with ultraviolet irradiation.

[0240] The release film manufactured by the aforementioned method exhibits ultra-light peel strength and excellent adhesion to both acrylic and silicone adhesives, and shows minimal haze change before and after wear.

[0241] In this specification, "substitution" is induced by exchanging at least one hydrogen atom in an unsubstituted parent group for another atom or functional group. When a functional group is considered to be "substituted," it means that the functional group is substituted by at least one substituent selected from alkyl groups having 1 to 40 carbon atoms, alkenyl groups having 2 to 40 carbon atoms, alkynyl groups having 2 to 40 carbon atoms, cycloalkyl groups having 3 to 40 carbon atoms, cycloalkenyl groups having 3 to 40 carbon atoms, and aryl groups having 7 to 40 carbon atoms. When a functional group is described as being "selectively substituted," it means that the functional group may be substituted by the aforementioned substituents.

[0242] In this specification, C1 to C10 monovalent hydrocarbon groups refer to, for example, straight-chain alkyl groups such as methyl, ethyl, hexyl, octyl, and decyl; branched alkyl groups such as isopropyl, tert-butyl, neopentyl, and isohexyl; cyclic alkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl and tolyl; and aralkyl groups such as benzyl and phenethyl. Among these, alkyl groups may be used to facilitate the supply of raw materials, while methyl or ethyl groups may be used to consider the usefulness of the product.

[0243] In this specification, C2 to C10 alkenyl groups refer to branched or unbranched hydrocarbons having at least one carbon-carbon double bond. Non-limiting examples of alkenyl groups may include vinyl, allyl, butenyl, isopropenyl, or isobutenyl.

[0244] The technical features and effects of the present invention will be described in more detail below with reference to embodiments and comparative examples. However, these embodiments are intended to illustrate the present invention in more detail, and it is obvious that the scope of the present invention is not limited to the various embodiments.

[0245] [Example]

[0246] Example 1: Release film

[0247] As a substrate, a polyester film with a thickness of 50 μm (Toray Advanced Materials Co., Ltd., XD500P) was prepared.

[0248] Individually, 100 parts by weight of an organopolysiloxane containing fluorinated alkyl groups (n=1) represented by the following chemical formula (manufactured by Sooyang Chemtec, 2382) as the first fluorinated organopolysiloxane, 100 parts by weight of an organopolysiloxane containing fluorinated alkyl groups (n=4) represented by the following chemical formula (manufactured by Dow Chemical, Q2-7785) as the second fluorinated organopolysiloxane, 100 parts by weight of a non-fluorinated organopolysiloxane including vinyl and methyl groups (manufactured by Shinetsu, KS847H), 3 parts by weight of a hydrogen-containing polysiloxane (manufactured by Dow Chemical, Q2-7560), and 0.1 parts by weight of a platinum chelating catalyst (manufactured by Dow Chemical, SYL-OFF 4000) are diluted in heptane solvent to prepare a composition with a solid content of 5% by weight.

[0249] After coating the composition onto one side of the polyester film, heat-treating it in a hot air dryer at 150°C for 60 seconds forms a release layer with a thickness of 0.3 μm, thereby manufacturing a release film.

[0250] [Chemical Formula 1]

[0251]

[0252] [Chemical Formula 2]

[0253]

[0254] In the chemical formula 1,

[0255] R1 is vinyl, R2 and R3 are methyl groups respectively, and R4 is a fluoroalkyl group represented by Formula 2.

[0256] n is 1 or 4, m is 2, and * represents the binding site with adjacent atoms.

[0257] Example 2: Release film

[0258] Release films were manufactured using the same method as in Example 1, except that 50 parts by weight of the first fluorinated organopolysiloxane and the second fluorinated organopolysiloxane were used respectively.

[0259] Example 3: Release film

[0260] Release films were manufactured using the same method as in Example 1, except that 30 parts by weight of the first fluorinated organopolysiloxane and the second fluorinated organopolysiloxane were used respectively.

[0261] Example 4: Release film

[0262] Release films were manufactured using the same method as in Example 1, except that 5 parts by weight of the first fluorinated organopolysiloxane and the second fluorinated organopolysiloxane were used respectively.

[0263] Example 5: Release film

[0264] The release film was manufactured using the same method as in Example 1, except that a release layer with a thickness of 1 μm was formed instead of 0.3 μm.

[0265] Example 6: Release film

[0266] Release films were manufactured by the same method as in Example 1, except that silica with a particle size of 2 μm was further mixed into the composition at 1% by weight based on the total solids content of the composition.

[0267] Comparative Example 1: Release Film

[0268] Release films were manufactured using the same method as in Example 1, except that 2.5 parts by weight of the first fluorinated organopolysiloxane and the second fluorinated organopolysiloxane were used respectively.

[0269] Comparative Example 2: Release Film

[0270] Release films were manufactured using the same method as in Example 1, except that 200 parts by weight of the first fluorinated organopolysiloxane and the second fluorinated organopolysiloxane were used respectively.

[0271] Comparative Example 3: Release Film

[0272] The release film was manufactured using the same method as in Example 1, except that a release layer with a thickness of 2.5 μm was formed instead of 0.3 μm.

[0273] Comparative Example 4: Release Film

[0274] The release film was manufactured using the same method as in Example 1, except that a release layer with a thickness of 0.01 μm was formed instead of 0.3 μm.

[0275] Comparative Example 5: Release Film

[0276] The release film was manufactured using the same method as in Example 1, except that no non-fluorinated organopolysiloxane was used.

[0277] Comparative Example 6: Release Film

[0278] Release films were manufactured using the same method as in Example 1, except that no non-fluorinated organopolysiloxanes and no second fluorinated organopolysiloxanes were used.

[0279] Comparative Example 7: Release Film

[0280] Release films were manufactured using the same method as in Example 1, except that non-fluorinated organopolysiloxanes and the first fluorinated organopolysiloxane were not used.

[0281] Comparative Example 8: Release Film

[0282] The release film was manufactured using the same method as in Example 1, except that a second fluorinated organopolysiloxane was not used.

[0283] Comparative Example 9: Release Film

[0284] The release film was manufactured using the same method as in Example 1, except that the first fluorinated organopolysiloxane was not used.

[0285] Analysis of Example 1: Analysis of Transmission Electron Microscopy Images

[0286] The release layer of the release film manufactured in Example 1 was analyzed by TEM. The instrument used for analysis was a FE-TEM (Jeo Corporation - JEM-ARM200F). The results are shown below. Figure 2 .

[0287] refer to Figure 2 It can be confirmed that the release layer of the release film manufactured by Example 1 is separated into a region (first region) extending from the surface along the thickness direction of about 90 nm and a region (second region) extending from the surface along the thickness direction of about 90 nm to the substrate surface (about 200 nm).

[0288] Evaluation Example 1: Assessing Physical Properties

[0289] The physical properties of the release films manufactured in Examples 1 to 6 and Comparative Examples 1 to 9 were evaluated using the following methods, and the results are shown in Tables 1 and 3.

[0290] (1) XPS analysis of the first and second regions of the release layer

[0291] The atomic composition of silicon (Si), fluorine (F), carbon (C), and oxygen (O) in the first region of the release layer of each release film was analyzed using XPS analysis equipment and expressed as atomic% (%). The XPS analysis equipment used was Thermo Fisher's K-ALPHA, with the analysis spot size. The first and second regions were analyzed simultaneously with plasma etching along the thickness direction from the release layer surface. The results of XPS analysis of the release film manufactured according to Example 1 are shown below. Figure 3 .

[0292] In addition, the atomic content analyzed in the first region is substituted into Equation 1-1 below and the content ratio between them is calculated. The fluorine (F) atomic content analyzed at the time point (T1) when the C element content reaches 50 (at%) in the second region, and the F atomic content (at%) at twice the time point (2×T1) when the C element content reaches 50 (at%), are substituted into Equation 3-1 below and the content difference (ΔF) is calculated.

[0293] [Equation 1-1]

[0294]

[0295] in,

[0296] F represents the fluorine content (at%) present on the surface of the first region as determined by XPS analysis.

[0297] Si+O+C represents the total content (at%) of silicon, oxygen, and carbon present on the surface of the first region as determined by XPS analysis.

[0298] [Equation 3-1]

[0299] F1-F2=△F(at%)

[0300] in,

[0301] F1 represents the F atom content (at%) at the time point (T1) when the C element content reaches 50 at% during XPS analysis of the second region.

[0302] F2 is the F atom content (at%) at twice the time point (2×T1) when the C element content reaches 50 at% during XPS analysis of the second region.

[0303] (2) Peel force of release film (gf / 25mm)

[0304] Samples were manufactured by cutting each release film to a size of 500mm × 1500mm. The samples were then placed at 25°C and 65% RH for 24 hours. Silicone tapes (SYMBIO, MY2G) and acrylic tapes (TESA, TESA7475) were then applied at 50°C and 20g / cm², respectively. 2 After the sample was subjected to a load for 24 hours, the peel force of a 250 mm × 1500 mm sample was measured using an AR-1000 peel force tester (manufactured by Cheminstrument) at a speed of 0.3 mpm at 180°.

[0305] (3) Folded modulus (GPa) and surface hardness (GPa) of the release layer

[0306] The folded modulus and surface hardness of the release layer of each release film were measured using nanomechanical testing equipment (Hysitron, TI950 Triboindenter).

[0307] (4) Haze variation in the first region of the release layer (ΔHaze)

[0308] Samples were manufactured by cutting each release film to a size of 500mm × 1500mm. The samples were placed at 25°C and 65% RH for 24 hours. Then, the change in haze before and after five rubbings on the surface of the first region of the release layer of the sample using a rubbing tester (manufactured by HAIAM ENG) with a 300g weight was calculated by substituting the following formula 2-1.

[0309] [Equation 2-1]

[0310] BA

[0311] in,

[0312] A is the surface haze (%) of the first area before it is rubbed five times using a rubbing tester with a 300g weight.

[0313] B is the haze (%) of the surface of the first area after rubbing it five times using a rubbing tester with a 300g weight.

[0314] (5) Surface energy (dyne / cm)

[0315] Diiodomethane and water were dropped onto the release layer surface of each release film. The contact angle was measured using a contact angle meter (Kyowa Dropmaster 300) and then calculated using the Owens-Wendt Method.

[0316] Table 1

[0317]

[0318]

[0319] Referring to Table 1, it can be seen that the release films manufactured through Examples 1 to 6 exhibit peel strengths of less than or equal to 9.2 gf / 25 mm for silicone adhesives and less than or equal to 9.5 gf / 25 mm for acrylic adhesives, demonstrating low peel strength and excellent adhesion. Furthermore, the haze variation (ΔHaze) in the first region is relatively low at 7.5. Additionally, the release films manufactured through Examples 1 to 6 exhibit good adhesion to the first region of the release layer. The content variation (ΔF) ranged from 0.43 to 0.65, the folded modulus (GPa) and surface hardness (GPa) of the release layer ranged from 3.54 GPa to 4.12 GPa and 0.3 GPa to 0.42 GPa, respectively, and the surface energy ranged from 14.2 dyne / cm to 16.8 dyne / cm.

[0320] In contrast, the release film manufactured by Comparative Example 1 (when the contents of the first fluorinated organopolysiloxane and the second fluorinated organopolysiloxane are relatively low) has a low fluorine content and therefore has excellent adhesion, but its peel strength is relatively high.

[0321] The release films manufactured by Comparative Example 2 (when the contents of the first fluorinated organopolysiloxane and the second fluorinated organopolysiloxane are relatively high) and Comparative Example 3 (when the release layer thickness is relatively thick) are not sufficiently hardened, and therefore have low peel strength, but the haze change (ΔHaze) is relatively high due to their low adhesion.

[0322] The release film manufactured by Comparative Example 4 (when the release layer thickness is thinner) has poor release layer coverage, thus improving the peel force when laminated with silicone tape and acrylic tape.

[0323] The release film manufactured by Comparative Example 5 (using only the first fluorinated organopolysiloxane and the second fluorinated organopolysiloxane) exhibited a peel force of less than or equal to 10 gf / 25 mm against silicone tapes, thus showing light peel characteristics. However, due to its higher folding modulus and surface hardness, the measured peel force against acrylic tapes was greater than or equal to 10 gf / 25 mm.

[0324] The release layer surfaces (first regions) of Comparative Examples 6 and 8 (when only a first fluorinated organopolysiloxane with a short-chain fluorinated alkyl group is used) have less fluorine content, and therefore exhibit higher peel strength and surface energy when laminated with silicone tapes.

[0325] Comparative Examples 7 and 9 (using only a second fluorinated organopolysiloxane with a long-chain fluorinated alkyl group) showed a decrease in peel strength and surface energy for silicone tapes, but the haze change (ΔHaze) increased to 10 or higher due to the decrease in adhesion caused by the long chain of the fluorinated alkyl group. Furthermore, the peel strength of acrylic tapes was higher than that of silicone tapes due to the higher folded modulus and surface hardness.

[0326] Comparative Examples 5 to 7 do not include non-fluorinated organopolysiloxanes, first fluorinated organopolysiloxanes, and / or second fluorinated organopolysiloxanes. Therefore, as the coating in the second region of the release layer becomes thinner, the difference in content (ΔF) reaches 5 or higher, and when XPS measurements are performed, the fluorine content in the second region of the release layer gradually decreases rather than remains constant.

[0327] The peel strength of a release film is exhibited through a combination of surface properties such as surface energy, folded modulus, and surface hardness of the release layer. The release layer of the release film of this invention has moderate folded modulus and surface hardness, thus demonstrating ultra-light peel strength against both acrylic and silicone tapes.

[0328] According to one aspect, the release film can be a cured layer of a composition comprising a blend of fluorinated organopolysiloxanes and non-fluorinated organopolysiloxanes. The release layer is divided into a first region and a second region. The first region is the surface of the release layer and the region adjacent to the surface, and is a region where the content of F atoms decreases and the content of Si atoms increases during XPS analysis while plasma etching is performed along the thickness direction from the surface. The second region is one side of the release layer in contact with the substrate and the region adjacent to that side, and is a region where the content of F atoms and Si atoms remains constant during the XPS analysis. The first region satisfies Equations 1 and 2 above, and the second region satisfies Equation 3 below. The release film exhibits ultra-light peel strength and excellent adhesion to both acrylic and silicone adhesives, with minimal haze change before and after abrasion.

[0329] Explanation of reference numerals in the attached figures

[0330] 100: Substrate, 110: Release layer, 120: Release film

Claims

1. A release film comprising: Substrate; and a release layer, which is located on at least one side of the substrate, The release layer is the cured layer of the composition, which includes a blend of a first fluorinated organopolysiloxane, a second fluorinated organopolysiloxane, and a non-fluorinated organopolysiloxane. The release layer is divided into a first region and a second region. The first region is the surface of the release layer and the region adjacent to the surface, and is the region where the content of F atoms decreases and the content of Si atoms increases during X-ray photoelectron spectroscopy (XPS) analysis while plasma etching is performed from the surface along the thickness direction. The second region is the area on one side of the release layer in contact with the substrate and the area adjacent to that side, and it is the region where the content of F atoms and Si atoms remains constant during the X-ray photoelectron spectroscopy (XPS) analysis. The first region satisfies equations 1 and 2 below. The second region satisfies the following equation 3: [Formula 1] 0.4 ≤ ≤ 0.7 in, F represents the fluorine content (at%) present on the surface of the first region, as determined by X-ray photoelectron spectroscopy (XPS). Si+O+C represents the total content (at%) of silicon, oxygen, and carbon present on the surface of the first region, as determined by X-ray photoelectron spectroscopy (XPS). [Equation 2] BA < 10 in, A is the value of haze A% on the surface of the first area before it is rubbed five times using a friction tester with a 300 g weight. B is the value of haze B% on the surface of the first area after 5 rubs using a friction tester with a 300 g weight. [Formula 3] F1-F2 = △F ≤ 5 at% in, F1 is the at% content of F atoms at the time point (T1) when the C atom content reaches 50 at% during X-ray photoelectron spectroscopy analysis of the second region. F2 is the F atom content at 2 × T1 at twice the time point (T1) when the C atom content reaches 50 at% during X-ray photoelectron spectroscopy analysis of the second region. The first region includes the first fluorinated organopolysiloxane and the second fluorinated organopolysiloxane. The first fluorinated organopolysiloxane and the second fluorinated organopolysiloxane include fluorinated alkyl substituents. The second fluorinated organopolysiloxane has a fluorinated alkyl group that is longer than that of the first fluorinated organopolysiloxane. The first fluorinated organopolysiloxane comprises an organopolysiloxane represented by the following chemical formula 1: [Chemical Formula 1] [Chemical Formula 2] in, R1 is a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group or a substituted or unsubstituted C2 to C10 alkenyl group; R2 is a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group or a substituted or unsubstituted C2 to C10 alkenyl group or hydrogen; R3 and R4 are independently derived from fluorinated alkyl groups, substituted or unsubstituted C1 to C10 monovalent hydrocarbon groups, substituted or unsubstituted C2 to C10 alkenyl groups, or hydrogen groups represented by the chemical formula 2. Furthermore, at least one of R3 and R4 is a fluorinated alkyl group represented by chemical formula 2; n is an integer from 1 to 3, and m is an integer from 1 to 5; x, y, and z are integers greater than or equal to 1; These are the binding sites with adjacent atoms; However, at least one of R1 and R2 is a substituted or unsubstituted C2 to C10 alkenyl group. Based on 100 parts by weight of the non-fluorinated organopolysiloxane, the contents of the first fluorinated organopolysiloxane and the second fluorinated organopolysiloxane are 5 to 100 parts by weight, respectively.

2. The release film according to claim 1, wherein, The second fluorinated organopolysiloxane comprises an organopolysiloxane represented by the following chemical formula 1: [Chemical Formula 1] [Chemical Formula 2] in, R1 is a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group or a substituted or unsubstituted C2 to C10 alkenyl group; R2 is a substituted or unsubstituted C1 to C10 monovalent hydrocarbon group or a substituted or unsubstituted C2 to C10 alkenyl group or hydrogen; R3 and R4 are independently derived from fluorinated alkyl groups, substituted or unsubstituted C1 to C10 monovalent hydrocarbon groups, substituted or unsubstituted C2 to C10 alkenyl groups, or hydrogen groups represented by the chemical formula 2. Furthermore, at least one of R3 and R4 is a fluorinated alkyl group represented by chemical formula 2; n is an integer from 4 to 9, and m is an integer from 1 to 5; x, y, and z are integers greater than or equal to 1; These are the binding sites with adjacent atoms; However, at least one of R1 and R2 is a substituted or unsubstituted C2 to C10 alkenyl group.

3. The release film according to claim 1, wherein, The non-fluorinated organopolysiloxanes include organopolysiloxanes containing vinyl and methyl groups.

4. The release film according to claim 1, wherein, The surface energy of the release layer is 14 dyne / cm to 17 dyne / cm.

5. The release film according to claim 1, wherein, The folded modulus of the release layer, measured by nanoindentation technology, is 3.5 GPa to less than 4.2 GPa.

6. The release film according to claim 1, wherein, The surface hardness of the release layer, measured by nanoindentation technology, ranges from 0.3 GPa to 0.45 GPa.

7. A method for manufacturing a release film according to any one of claims 1-6, comprising: Prepare the substrate; as well as A composition comprising a first fluorinated organopolysiloxane, a second fluorinated organopolysiloxane, a non-fluorinated organopolysiloxane, and a hydrogen-containing polysiloxane is coated onto at least one side of the substrate and a release layer is formed by heat treatment. The release layer is divided into a first region and a second region. The first region is the surface of the release layer and the region adjacent to the surface, and is the region where the content of F atoms decreases and the content of Si atoms increases during X-ray photoelectron spectroscopy analysis while plasma etching is performed along the thickness direction from the surface. The second region is the area on one side of the release layer in contact with the substrate and the area adjacent to that side, and it is the region where the content of F atoms and Si atoms remains constant during the X-ray photoelectron spectroscopy analysis. The first region satisfies equations 1 and 2 below. The second region satisfies the following equation 3: [Formula 1] 0.4 ≤ ≤ 0.7 in, F represents the fluorine content (at%) present on the surface of the first region, as determined by X-ray photoelectron spectroscopy analysis. Si+O+C represents the total content (at%) of silicon, oxygen, and carbon present on the surface of the first region as determined by X-ray photoelectron spectroscopy analysis. [Equation 2] BA < 10 in, A is the haze A% of the surface of the first area before it is rubbed five times using a friction tester with a 300g weight. B is the haze percentage of the surface of the first area after rubbing it five times using a friction tester with a 300g weight. [Formula 3] F1-F2 = △F ≤ 5 (at%) in, F1 is the F atom content (at%) at the time point (T1) when the C atom content reaches 50 (at%) during X-ray photoelectron spectroscopy analysis of the second region. F2 is the F atom content at 2 × T1 at twice the time point (T1) when the C atom content reaches 50 (at%) during X-ray photoelectron spectroscopy analysis of the second region. The first region includes the first fluorinated organopolysiloxane and the second fluorinated organopolysiloxane. The first fluorinated organopolysiloxane and the second fluorinated organopolysiloxane include fluorinated alkyl substituents. The second fluorinated organopolysiloxane has a fluorinated alkyl group that is longer than that of the first fluorinated organopolysiloxane.

Images