KR102220142B1 - Release film and method of manufacturing the same - Google Patents

Abstract

A release film and a method of manufacturing the release film are disclosed. The release film is a cured layer of a silicone release composition including a silicone resin and a silane coupling agent into which a phenyl group is introduced, and the release layer is X-ray photoelectron spectroscopy (XPS) in the thickness direction from the surface to the substrate. ) It may include a release layer in which the area ratio in which Si-Ph (phenyl group) bonds are distributed by analysis is reduced.

Description

Release film and method of manufacturing the release film {Release film and method of manufacturing the same}

It relates to a release film and a method of manufacturing the release film.

In general, a release film has a structure including a substrate and a release layer formed on the substrate, and is used as a film for protecting an adhesive. The release film is required for a release layer having various levels of physical properties for use in applications such as light peeling, heavy peeling, and super heavy peeling according to the characteristics of the adhesive used.

The release layer of the release film may be formed of a silicone release composition composed of, for example, organopolysiloxane, organohydrogenpolysiloxane, and a platinum catalyst. Such a silicone release composition is suitable for a release film for applications requiring light peeling properties, but it may be difficult to apply it to a release film for applications requiring a heavy peeling force over heavy peeling.

In addition, in the case of a pressure-sensitive adhesive whose surface becomes hard after drying, a heavy peeling force is required due to low tackiness with a release film, but there is a problem in that light peeling or ship breakage occurs with a general release film.

Therefore, there is a need for a new release film having various functions and a method of manufacturing the release film, which can be used for applications requiring a heavy peeling force over heavy peeling.

One aspect is provided with a release film having an improved adhesion between a substrate and a release layer, an improved degree of curing of the release layer, an improved heavy peeling force, and a reduced Si transfer rate.

Another aspect is provided with a method of manufacturing the release film.

According to one aspect,

materials; And

It may include; a release layer disposed on at least one side of the substrate,

The release layer may be a cured layer of a silicone release composition including a silicone resin into which a phenyl group represented by Formula 1 is introduced and a silane coupling agent represented by Formula 2 below,

The release layer is provided with a release film in which the area ratio in which Si-Ph (phenyl group) bonds are distributed by X-ray photoelectron spectroscopy (XPS) analysis in the thickness direction from the surface to the substrate is reduced:

<Formula 1>

In Formula 1,

x, y, z may be an integer of 1 or more;

R ₁ , R ₆ , R ₈ , R ₁₀ are each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C2-C20 alkenyl group, It may be a substituted or unsubstituted C2-C20 alkenylene group, or a combination thereof;

R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₉ , R ₁₁ may be each independently a substituted or unsubstituted C1-C20 alkyl group;

R ₈ may be each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

<Formula 2>

In Chemical Formula 2,

R _a , R _b , R _c may be each independently a substituted or unsubstituted C1-C20 alkyl group.

In Formula 1, R ₁ , R ₆ , R ₈ , R ₁₀ are each independently selected from -CH=CH ₂ , -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH=CH _2, and -CH ₃ There may be more than one type.

In Formula 1, R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₉ , R ₁₁ are each independently a methyl group, and R ₈ may be at least one selected from a methyl group and a phenyl group.

In Formula 2, R _a , R _b , and R _c may be each independently a methyl group.

In the silicone release composition, the molar ratio of the Si-Ph (phenyl group) bond to the Si-Me (methyl group) bond may be 100: 30 to 100: 50.

The silicone release composition may include a phenyl group in an amount of more than 20 mol% to 30 mol%.

The thickness of the release layer may be 30 nm to 2 μm.

The release layer may simultaneously satisfy the following Equations 1 to 3:

<Equation 1>

5 ≤ A ≤ 50

In Equation 1 above,

A may represent the peel force (gf/in) for the release layer using the epoxy resin adhesive.

<Equation 2>

10 ≤ B ≤ 800

In Equation 2 above,

B may represent the peel force (gf/in) for the release layer using the TESA7475 tape.

<Equation 3>

0 ≤ C ≤ 1

In Equation 3 above,

C may represent the Si transfer rate (%).

The substrate may be a polyester film or sheet.

The substrate may further include inorganic particles.

The thickness of the substrate may be 30 to 130㎛.

According to the other side,

Applying a silicone release composition including a silicone resin into which a phenyl group represented by the following formula (1) is introduced and a silane coupling agent represented by the following formula (2) on at least one side of the substrate; And

By curing the applied silicone release composition by heat treatment, the area ratio in which Si-Ph (phenyl group) bonds are distributed by X-ray photoelectron spectroscopy (XPS) analysis in the thickness direction from the surface to the substrate is reduced. Forming a release layer; there is provided a method for producing a release film comprising:

<Formula 1>

In Formula 1,

x, y, z may be an integer of 1 or more;

R ₁ , R ₆ , R ₈ , R ₁₀ are each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C2-C20 alkenyl group, It may be a substituted or unsubstituted C2-C20 alkenylene group, or a combination thereof;

R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₉ , R ₁₁ may be each independently a substituted or unsubstituted C1-C20 alkyl group;

R ₈ may be each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

<Formula 2>

In Chemical Formula 2,

R _a , R _b , R _c may be each independently a substituted or unsubstituted C1-C20 alkyl group.

The content after curing of the silicone release composition applied in the release layer may be ^{2 g/m 2 or more.}

The silicone release composition may further include a catalyst.

The release film according to one aspect is a cured layer of a silicone release composition including a silicone resin into which a phenyl group represented by Formula 1 is introduced and a silane coupling agent represented by Formula 2, and in the thickness direction from the surface to the substrate Including the release layer in which the area ratio in which Si-Ph (phenyl group) bonds are distributed by X-ray photoelectron spectroscopy (XPS) analysis is reduced, improved adhesion between the substrate and the release layer, improved hardening of the release layer, It can have an improved heavy peeling force, and a reduced Si transfer rate.

1 is a schematic cross-sectional view of a release film according to an embodiment.
2(a) to 2(i) are photographs of observing the surface after the release layers of each of the release films prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were painted with an oil-based ink pen.

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

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

Although methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present invention, suitable methods and materials are described herein.

In the present specification, the term "on (or on)" includes not only a case in which another part is located "directly on (or directly on)" but also a case in which another part is interposed therebetween. Conversely, the term "directly on (or directly on)" means that no other part is intervened.

In the present specification, "-based base material" is a concept in a broad sense including both "- polymer base material" or/and "- polymer base material derivative".

Unless otherwise specified in the specification, the unit "parts by weight" means a weight ratio between each component.

A release film according to one embodiment is a substrate; And a release layer disposed on at least one side of the substrate, wherein the release layer includes a silicone resin into which a phenyl group represented by Formula 1 is introduced and a silane coupling agent represented by Formula 2 below. The release layer may be a cured layer of, and the release layer may reduce the area ratio in which Si-Ph (phenyl group) bonds are distributed by X-ray photoelectron spectroscopy (XPS) analysis in the thickness direction from the surface to the substrate. Can be:

<Formula 1>

In Formula 1,

x, y, z may be an integer of 1 or more;

R ₁ , R ₆ , R ₈ , R ₁₀ are each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C2-C20 alkenyl group, It may be a substituted or unsubstituted C2-C20 alkenylene group, or a combination thereof;

R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₉ , R ₁₁ may be each independently a substituted or unsubstituted C1-C20 alkyl group;

R ₈ may be each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

<Formula 2>

In Chemical Formula 2,

R _a , R _b , R _c may be each independently a substituted or unsubstituted C1-C20 alkyl group.

1 is a schematic cross-sectional view of a release film according to an embodiment.

Referring to FIG. 1, in a release film 100 according to an embodiment, a release layer 120 may be disposed on a substrate 110 and at least one surface of the substrate 110.

Hereinafter, each of the substrates and release layers constituting the release film will be described in detail.

<material>

The substrate used for the release film according to one embodiment may be a polyester-based substrate. The polyester-based substrate may be a polyester-based film or sheet. However, the shape of the polyester-based substrate is not limited thereto, and any shape of the polyester-based substrate usable in the art may be used.

The polyester-based substrate may be polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate.

The polyester-based substrate may be a polyester resin obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic glycol. Examples of the aromatic dicarboxylic acid may be isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, or oxycarboxylic acid. Examples of the aliphatic glycol may include ethylene glycol, diethylene glycol, propylene glycol, butadiol, 1,4-cyclohexanedimethanol, or neopentyl glycol. The polyester resin may be used in combination of two or more of the examples of the aromatic dicarboxylic acid and the aliphatic glycol, and a copolymer containing a third component may also be used.

The polyester-based substrate may be a uniaxial or biaxially oriented film having high transparency and excellent productivity and processability.

The polyester resin may be, for example, polyethylene terephthalate (PET) or polyethylene-2,6-naphthalenedicarboxylate (PEN).

The substrate may further include inorganic particles. The inorganic particles may impart excellent rolling characteristics between rolls. Examples of such inorganic particles may include particles such as silica, silicon oxide, calcium carbonate, calcium sulfate, calcium phosphate, magnesium carbonate, barium carbonate, kaolin, aluminum oxide, or titanium oxide. However, it is not limited thereto, and all kinds of particles may be used as long as they exhibit excellent sliding properties.

The shape of the inorganic particles may be any shape such as a spherical shape, a block shape, a rod shape, or a plate shape, but is not limited thereto. In addition, the hardness, specific gravity and color of the inorganic particles are not limited. If necessary, the inorganic particles can be used in combination of two or more.

The average particle diameter of the inorganic particles may be, for example, 0.1 to 5.0 μm, and may be, for example, 0.1 to 2.0 μm. If the average particle diameter of the inorganic particles is less than 0.1 μm, aggregation between particles may occur, resulting in poor dispersion. If the average particle diameter of the inorganic particles exceeds 5 μm, the surface roughness characteristics of the base film or base sheet may deteriorate, and coating defects may occur during post-processing.

The content of the inorganic particles may be 0.01 to 5% by weight based on the total 100% by weight of the substrate, for example, may be 0.01 to 3% by weight. If the content of the inorganic particles is less than 0.01% by weight based on the total 100% by weight of the substrate, the running characteristics of the polyester-based film or sheet may deteriorate, and if it exceeds 5% by weight, the surface of the polyester-based film or sheet Smoothness may be poor.

The thickness of the substrate may be 30 to 130 μm, for example, 30 to 125 μm. If the thickness of the substrate is less than 30 μm, it may be deformed by heat during the drying process, and if the thickness of the substrate exceeds 130 μm, there is a concern that heat is not sufficiently transferred and thus uncured.

< Release layer >

The release layer used in the release film according to an embodiment may be a cured layer of a silicone release composition including a silicone resin into which a phenyl group represented by the following Formula 1 is introduced and a silane coupling agent represented by the following Formula 2, wherein the release layer is The area ratio in which Si-Ph (phenyl group) bonds are distributed by X-ray photoelectron spectroscopy (XPS) analysis in the thickness direction from the surface to the substrate can be reduced:

<Formula 1>

In Formula 1,

x, y, z may be an integer of 1 or more;

R ₁ , R ₆ , R ₈ , R ₁₀ are each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C2-C20 alkenyl group, It may be a substituted or unsubstituted C2-C20 alkenylene group, or a combination thereof;

R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₉ , R ₁₁ may be each independently a substituted or unsubstituted C1-C20 alkyl group;

R ₈ may be each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

<Formula 2>

In Chemical Formula 2,

R _a , R _b , R _c may be each independently a substituted or unsubstituted C1-C20 alkyl group.

The release film including the release layer may have an improved adhesion between the substrate and the release layer, an improved degree of curing of the release layer, an improved heavy peeling force, and a reduced Si transfer rate. For this reason, it can be used for a release film for applications that require heavy peeling force over heavy peeling.

For example, in Formula 1, R ₁ , R ₆ , R ₈ , R ₁₀ are independently of each other -CH=CH ₂ , -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH=CH _2, and -CH _It may be one or more selected from three.

For example, in Formula 1, R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₉ , and R ₁₁ are each independently a methyl group, and R ₈ may be at least one selected from a methyl group and a phenyl group.

For example, in Formula 2, R _a , R _b , and R _c may be each independently a methyl group.

In the silicone release composition, the molar ratio of the Si-Ph (phenyl group) bond to the Si-Me (methyl group) bond may be 100: 30 to 100: 50. When the molar ratio of Si-Ph (phenyl group) bonds to Si-Me (methyl group) bonds in the silicone release composition is less than 100:30, the area ratio in which Si-Ph (phenyl group) bonds are distributed by XPS analysis on the release layer surface is low. It may be difficult to implement the desired heavy peeling properties, and adhesion to the substrate may be lowered. If the molar ratio of Si-Ph (phenyl group) bonds to Si-Me (methyl group) bonds in the silicone release composition exceeds 100: 50, the area ratio in which Si-Ph (phenyl group) bonds are distributed by XPS analysis on the release layer surface increases. Thus, the peeling force for the release layer may be excessively increased.

The silicone release composition may include a phenyl group in an amount of more than 20 mol% to 30 mol%. The silicone release composition includes a phenyl group having an amount within the above range and controls the area ratio in which Si-Ph (phenyl group) bonds are distributed by XPS analysis on the surface of the release layer, thereby improving adhesion between the substrate and the release layer, and improving release. It is possible to implement a release film having a degree of curing of the layer, an improved heavy peeling force, and a reduced Si transfer rate.

The thickness of the release layer may be 30 nm to 2 μm. The thickness of the release layer may be, for example, 40 nm to 2 µm, for example, 50 nm to 2 µm, and for example, 60 nm to 1.8 µm, for example, 70 nm to 1.6 µm May be, for example, 80 nm to 1.5 µm, for example 90 nm to 1.5 µm, for example, 100 nm to 1.5 µm, for example, 200 nm to 1.5 µm And, for example, it may be 300 nm to 1.5 µm, for example, 400 nm to 1.5 µm, for example, 400 nm to 1.2 µm, and for example, it may be 500 nm to 1 µm. If the thickness of the release layer is less than 30 nm, the release property may be insignificant, and if the thickness of the release layer is more than 2 μm, it requires a lot of heat during curing, which may cause thermal deformation of the substrate.

The release layer may simultaneously satisfy the following Equations 1 to 3:

<Equation 1>

5 ≤ A ≤ 50

In Equation 1 above,

A may represent the peel force (gf/in) for the release layer using the epoxy resin adhesive.

<Equation 2>

10 ≤ B ≤ 800

In Equation 2 above,

B may represent the peel force (gf/in) for the release layer using the TESA7475 tape.

<Equation 3>

0 ≤ C ≤ 1

In Equation 3 above,

C may represent the Si transfer rate (%).

Since the release layer can have an improved adhesion between a substrate and a release layer, an improved degree of hardening of the release layer, an improved heavy peeling force, and a reduced Si transfer rate, it can be applied to a release film for applications requiring a heavy peeling force over heavy peeling. have.

<Manufacturing method of release film>

A method of manufacturing a release film according to another embodiment includes the steps of applying a silicone release composition including a silicone resin into which a phenyl group represented by Formula 1 is introduced and a silane coupling agent represented by Formula 2 to at least one surface of a substrate; And reducing the area ratio in which Si-Ph (phenyl group) bonds are distributed by X-ray photoelectron spectroscopy (XPS) analysis in the thickness direction from the surface to the substrate by curing the applied silicone release composition by heat treatment. Forming a release layer to be; may include:

<Formula 1>

In Formula 1,

x, y, z may be an integer of 1 or more;

R ₁ , R ₆ , R ₈ , R ₁₀ are each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C2-C20 alkenyl group, It may be a substituted or unsubstituted C2-C20 alkenylene group, or a combination thereof;

R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₉ , R ₁₁ may be each independently a substituted or unsubstituted C1-C20 alkyl group;

R ₈ may be each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.

<Formula 2>

In Formula 2,

R _a , R _b , and R _c may each independently be a substituted or unsubstituted C1-C20 alkyl group .

_{R 1} to R ₁₁ in Formula 1 _{and R a} , R _b , R _c in Formula 2, the molar ratio of Si-Ph (phenyl group) bond to Si-Me (methyl group) bond and phenyl group content in the silicone release composition, and Since the thickness of the release layer is the same as described above, it will be omitted.

The silicone release composition may include an organic solvent. An example of the organic solvent may be a mixed organic solvent obtained by mixing toluene and methyl ethyl ketone in a volume ratio of 1:1.

The silicone release composition may further include a catalyst. Examples of the catalyst may include a platinum catalyst. If necessary, the silicone release composition may further include a curing agent. In addition, the silicone release composition may include additives for imparting various functions such as antistatic agents and anti-blocking particles.

The content of the applied silicone release composition may be ^{2 g/m 2 or more.} Si-Ph (phenyl group) by X-ray photoelectron spectroscopy (XPS) analysis on the surface of the release layer because a sufficient coating thickness is not formed if the content of the applied silicone release composition is ^{less than 2 g/m 2} The area ratio in which bonds are distributed can be reduced. Accordingly, the release film including the same may exhibit light peeling properties.

As an example of the coating method, a method such as gravure coating, bar coating, or die coating may be used. As an example of curing, a method such as heat treatment or ultraviolet irradiation may be used.

Hereinafter, the definition of the substituent used in Formula 1 or/and Formula 2 is as follows.

The "substituted" of the alkyl group, alkylene group, alkenyl group and alkenylene group used in Formula 1 or/and Formula 2 is a halogen atom, a C1-C5 alkyl group substituted with a halogen atom (eg _{, CCF 3} , CHCF ₂ , CH ₂ F, CCl _3, etc.), hydroxy group, nitro group, cyano group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, or C1-C5 alkyl group, C2 It means substituted with an alkenyl group of -C5.

Specific examples of the "alkyl group" used in Formula 1 or/and Formula 2 may include methyl, ethyl, propyl, isobutyl, sec-butyl, ter-butyl, neo-butyl, iso-amyl, or hexyl. .

Specific examples of the "alkylene group" used in Formula 1 or/and Formula 2 include methylene, ethylene, propylene, isobutylene, sec-butylene, ter-butylene, neo-butylene, iso-amylene, or Hexylene, etc. are mentioned.

The "alkenyl group" used in Formula 1 or/and Formula 2 is methylene, ethylene, propylene, isobutylene, sec-butylene, ter-butylene, neo-butylene, iso-amylene, or hexylene. As a group in which one hydrogen atom has been removed from the same alkylene group, for example, a vinyl group or the like may be mentioned.

The "alkenylene group" used in Formula 1 or/and Formula 2 is -CH=CH-, -CH ₂ CH=CH-, -CH ₂ CH ₂ CH=CH-, -CH ₂ CH ₂ CH ₂ CH= CH-, CH ₂ CH ₂ CH ₂ CH ₂ CH=CH-, -CH=C(CH ₃ )-, or -CH ₂ CH=C(CH ₃ )-.

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

[Example]

Example 1: release film

Si-Ph (phenyl group) bond vs. Si-Me by using a silicone resin into which a phenyl group was introduced (X-62-9201A, manufactured by Shinetsu) and a silane coupling agent (manufactured by Shinetsu, KBM-503) represented by Formula 2-1 below. After weighing stoichiometrically so that the molar ratio of (methyl group) bonds was 100:30, it was added to an organic solvent (toluene: methyl ethyl ketone = 1:1 by volume) to prepare a mixture. A silicone release composition was prepared by adding 5 parts by weight of a platinum catalyst (PL-50T, manufactured by Shinetsu) to the mixture based on 100 parts by weight of the mixture.

The silicone release composition was applied to one side of a polyester base film (thickness: 75 μm, Toray Advanced Materials, Excell) at 2.0 g/m ² and cured by heat treatment in a hot air dryer at 150° C. for 1 minute to form a release layer (thickness: 1.0 μm) to prepare a release film:

<Formula 2-1>

Example 2: release film

Si-Ph (phenyl group) bond versus Si- Except that the molar ratio of Me (methyl group) bonds was stoichiometrically weighed to be 100:35 instead of 100:30, and then added to an organic solvent (toluene: methyl ethyl ketone = 1:1 volume ratio) to prepare a mixture. A release film was prepared in the same manner as in Example 1.

Example 3: release film

Si-Ph (phenyl group) bond vs. Si- by using the silicone resin into which the phenyl group was introduced (X-62-9201A) and the silane coupling agent represented by Chemical Formula 2-1 (KBM-503, manufactured by Shinetsu) Except that the molar ratio of Me (methyl group) bonds was stoichiometrically weighed to be 100:40 instead of 100:30, and then added to an organic solvent (toluene: methyl ethyl ketone = 1:1 by volume) to prepare a mixture A release film was prepared in the same manner as in Example 1.

Example 4: release film

Si-Ph (phenyl group) bond vs. Si- by using the silicone resin into which the phenyl group was introduced (X-62-9201A) and the silane coupling agent represented by Chemical Formula 2-1 (KBM-503, manufactured by Shinetsu) Except for preparing a mixture by stoichiometrically weighing so that the molar ratio of Me (methyl group) bonds is 100:45 instead of 100:30 and then added to an organic solvent (toluene: methyl ethyl ketone = 1:1 by volume) A release film was prepared in the same manner as in Example 1.

Example 5: release film

Si-Ph (phenyl group) bond vs. Si- by using the silicone resin into which the phenyl group was introduced (X-62-9201A) and the silane coupling agent represented by Chemical Formula 2-1 (KBM-503, manufactured by Shinetsu) Except that the molar ratio of Me (methyl group) bonds was stoichiometrically weighed to be 100:50 instead of 100:30, and then added to an organic solvent (toluene: methyl ethyl ketone = 1:1 by volume) to prepare a mixture A release film was prepared in the same manner as in Example 1.

Comparative example 1: release film

Si-Ph (phenyl group) bond vs. Si- by using the silicone resin into which the phenyl group was introduced (X-62-9201A) and the silane coupling agent represented by Chemical Formula 2-1 (KBM-503, manufactured by Shinetsu) Except that a mixture was prepared by stoichiometrically weighing so that the molar ratio of Me (methyl group) bonds was 100:20 instead of 100:30 and then added to an organic solvent (toluene: methyl ethyl ketone = 1:1 by volume). A release film was prepared in the same manner as in Example 1.

Comparative example 2: release film

Si-Ph (phenyl group) bond vs. Si- by using the silicone resin into which the phenyl group was introduced (X-62-9201A) and the silane coupling agent represented by Chemical Formula 2-1 (KBM-503, manufactured by Shinetsu) Except for preparing a mixture by stoichiometrically weighing so that the molar ratio of Me (methyl group) bonds is 100:60 instead of 100:30 and then added to an organic solvent (toluene: methyl ethyl ketone = 1:1 by volume) A release film was prepared in the same manner as in Example 1.

Comparative example 3: release film

Release in the same manner as in Example 1, except that ^{the silicone release composition was applied at 0.5 g/m 2} instead of 2.0 g/m 2 on one side of a polyester base film (thickness: 75 μm, Toray Advanced Materials, Excell). The film was prepared.

Comparative example 4: release film

Release in the same manner as in Example 1, except that the silicone release composition was applied to one side of a polyester base film (thickness: 75 μm, Toray Advanced Materials, Excell) ^{instead of 2.0 g/m 2} The film was prepared.

Analysis example 1: X-ray photoelectron spectroscopy (XPS) analysis

Si-Ph in the thickness direction from the surface of the release layer to the base film using X-ray photoelectron spectroscopy (XPS) for each release film prepared in Examples 1 to 5 and Comparative Examples 1 to 4 The area ratio in which (phenyl group) bonds and Si-Me (methyl group) bonds are distributed was analyzed. The results are shown in Tables 1 and 2 below.

Area ratio on the surface of the release layer From the surface of the release layer to the base film in the thickness direction of 0.3 ㎛
Area ratio Si-Ph (phenyl group) bond Si-Me (methyl group) bond Si-Ph (phenyl group) bond Si-Me (methyl group) bond Example 1 45 45 35 55 Example 2 48 42 38 52 Example 3 50 40 40 50 Example 4 52 38 42 48 Example 5 52 38 42 48 Comparative Example 1 20 70 23 67 Comparative Example 2 60 30 63 27 Comparative Example 3 30 60 32 58 Comparative Example 4 35 55 37 57

* Based on the total area ratio of 100%, the remaining area ratio of 10% represents "other" components

From the surface of the release layer to the base film in the thickness direction of 0.7 ㎛
Area ratio From the surface of the release layer to the base film in the thickness direction at 1.0 µm
Area ratio Si-Ph (phenyl group) bond Si-Me (methyl group) bond Si-Ph (phenyl group) bond Si-Me (methyl group) bond Example 1 25 65 15 75 Example 2 28 62 16 74 Example 3 30 60 15 75 Example 4 32 58 16 74 Example 5 32 58 17 73 Comparative Example 1 27 63 30 60 Comparative Example 2 67 23 70 20 Comparative Example 3 33 57 35 55 Comparative Example 4 38 52 40 45

* Based on the total area ratio of 100%, the remaining area ratio of 10% represents "other" components

Referring to Tables 1 and 2, it can be seen that in the release films prepared according to Examples 1 to 5, the area ratio in which Si-Ph (phenyl group) bonds are distributed in the thickness direction from the surface of the release layer to the base film is reduced. . In comparison, it can be seen that the release films prepared according to Comparative Examples 1 to 4 have a high area ratio in which Si-Ph (phenyl group) bonds are distributed in the thickness direction from the surface of the release layer to the base film.

Evaluation example 1: Evaluation of physical properties of release film

The physical properties of each of the release films prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were evaluated as follows. The results are shown in FIGS. 2(a) to 2(i) and Table 3 below.

(1) Peeling force on the release layer using an epoxy resin adhesive

A solution obtained by mixing 100 g of bisphenol epoxy resin (manufactured by Nippon Shool, RE-310) and 30 g of a silane coupling agent (Shinetsu, KBM-503) was diluted with methyl ethyl ketone solvent, and then 60 g of CaO (manufactured by Aldrich) was added as a moisture adsorbent. It was prepared by adding it to a methyl ethyl ketone solvent at a concentration of 30 wt%, and 30 g of an imidazole-epoxy adduct (manufactured by Ajinomoto, PN-40) as a curing agent was added and stirred for 2 hours to prepare a mixed solution. Then, the mixture was filtered through a filter having a diameter of 20 μm to prepare an epoxy resin adhesive.

The epoxy resin adhesive was applied to one side of a polyester base film (thickness: 50 μm, Toray Advanced Materials, Excell) to a thickness of 10 μm, dried at 100° C. for 50 seconds, and prepared in Examples 1 to 5 and Comparative Examples 1 to 4 It was laminated with each released release film. Each of the release films prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were stored at 50° C. for 12 hours, and then peeled off with a peel force meter (AR-1000) at a rate of 0.3 mpm. Peel force was measured. At this time, the peel force evaluation was obtained by measuring the peel force three times in the same manner as the above-described method, and then an average thereof.

(2) Peeling force for release layer using TESA7475 tape

The TESA7475 tape was placed on the surface of the release layer of each of the release films prepared in Examples 1 to 5 and Comparative Examples 1 to 4, rubbed twice using a 2 kg rubber roller, and then sampled in a size of 1 in × 20 cm. The samples were stored at 25° C. for 1 day and then peeled with a peel force measuring instrument (AR-1000) at a rate of 0.3 mpm to measure the peel force on the release layer. At this time, the peel force evaluation was obtained by measuring the peel force three times in the same manner as the above-described method, and then an average thereof.

(3) Si transfer rate

For each of the release films prepared in Examples 1 to 5 and Comparative Examples 1 to 4, the Si transfer rate of the release layer was calculated using X-ray fluorescence (XRF). At this time, the Si transfer rate was calculated using Equation 1 below.

<Equation 1>

[(P-Q)/P] X 100

In Equation 1,

P is an XRF analysis of the Si thickness of the release layer formed after applying and curing the silicone release composition of each release film prepared in Examples 1 to 5 and Comparative Examples 1 to 4 on one side of a polyester base film and heat treatment Represents one value,

Q is (1) laminated the base film coated with the epoxy resin adhesive layer used in the evaluation of the peel strength for the release layer using the epoxy resin adhesive and the release films prepared in Examples 1 to 5 and Comparative Examples 1 to 4 It shows the value obtained by analyzing the Si thickness of the release layer at the time of subsequent peeling by XRF.

(4) Adhesion between the base film and the release layer

After reciprocating the release layer of each release film prepared in Examples 1 to 5 and Comparative Examples 1 to 4 5 times with a thumb and rubbing it with force, the degree of peeling of the release layer was observed to determine the adhesion between the base film and the release layer. It was judged in the same grade as.

◎: Excellent (no smear phenomenon is observed)

○: good (smear phenomenon begins to be observed)

△: Insufficient (rub-off phenomenon begins to be observed)

Х: Poor (rub-off phenomenon is very observed)

(5) Hardening of the release layer

Each of the release films prepared in Examples 1 to 5 and Comparative Examples 1 to 4 was sampled in a size of 2 cm × 5 cm, stored in 100 ml of toluene for 10 hours, dried at 25° C. for 1 hour, and then the release layer was applied to an oil-based ink pen. After painting, the surface was observed with a photograph.

2(a) to 2(e), the degree of curing of the release layer of the release film prepared according to Examples 1 to 5 in Comparative Examples 1 to 4 of FIGS. 2(f) to 2(i) It can be seen that it is high compared to the manufactured release film.

Peel force for release layer using epoxy resin adhesive (gf/in) Peeling force for release layer using TESA7475 tape (gf/in) Si transfer rate (%) Adhesion rating Example 1 5 50 0.2 ◎ Example 2 15 100 0.2 ◎ Example 3 25 300 0.2 ◎ Example 4 40 500 0.1 ◎ Example 5 50 700 0.1 ◎ Comparative Example 1 3.0 50 2.0 △ Comparative Example 2 80 900 0.2 ○ Comparative Example 3 1.5 50 3.0 △ Comparative Example 4 2.0 75 2.0 Х

Referring to Table 3, the release films prepared in Examples 1 to 5 were excellent in the peel strength for the release layer using the epoxy resin adhesive, the peel strength for the release layer using the TESA7475 tape, the Si transfer rate, and the adhesion rating. .

From this, the area ratio in which Si-Ph (phenyl group) bonds are distributed by X-ray photoelectron spectroscopy (XPS) analysis on the surface of the release layer of the release films prepared in Examples 1 to 5 is high, and the adhesion grade is high. It can be seen that not only high, but also a release film having low heavy peeling properties and low Si transfer rate can be realized.

In comparison, the area ratio in which Si-Ph (phenyl group) bonds are distributed by X-ray photoelectron spectroscopy (XPS) analysis on the surface of the release layer of the release films prepared in Comparative Examples 1, 3 and 4 is low. It was shown that it is a release film with insufficient or poor adhesion grade, as well as light peeling properties and high Si transfer rate.

The release film prepared in Comparative Example 2 is composed of a release layer formed of a silicone release composition having a molar ratio of Si-Ph (phenyl group) bonds to Si-Me (methyl group) bonds of 100:60, so X-ray photoelectron spectroscopy (X- By ray photoelectron spectroscopy (XPS) analysis, the area ratio in which Si-Me (methyl group) bonds are distributed is high, so that the peel strength is decreased.

100: release film, 110: substrate,
120: release layer

Claims (20)

materials; And
Including; a release layer disposed on at least one side of the substrate,
The release layer is a cured layer of a silicone release composition including a silicone resin into which a phenyl group represented by Formula 1 is introduced and a silane coupling agent represented by Formula 2 below,
In the release layer, the area ratio in which Si-Ph (phenyl group) bonds are distributed by X-ray photoelectron spectroscopy (XPS) analysis in the thickness direction from the surface to the substrate is reduced,
A release film having a molar ratio of Si-Ph (phenyl group) bond to Si-Me (methyl group) bond in the silicone release composition is 100: 30 to 100: 50:
<Formula 1>

In Formula 1,
x, y, z are integers of 1 or more;
R ₁ , R ₆ , R ₈ , R ₁₀ are each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C2-C20 alkenyl group, A substituted or unsubstituted C2-C20 alkenylene group, or a combination thereof;
R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₉ , R ₁₁ are each independently a substituted or unsubstituted C1-C20 alkyl group;
R ₈ is each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.
<Formula 2>

In Chemical Formula 2,
R _a , R _b , and R _c are each independently a substituted or unsubstituted C1-C20 alkyl group. The method of claim 1,
In Formula 1, R ₁ , R ₆ , R ₈ , R ₁₀ are each independently selected from -CH=CH ₂ , -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH=CH _2, and -CH ₃ More than one type of release film. The method of claim 1,
In Chemical Formula 1, R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₉ , R ₁₁ are each independently a methyl group, and R ₈ is at least one selected from a methyl group and a phenyl group. The method of claim 1,
In Formula 2, R _a , R _b , and R _c are each independently a methyl group. delete The method of claim 1,
The silicone release composition is a release film comprising a phenyl group content of more than 20 mol% to 30 mol%. The method of claim 1,
A release film having a thickness of the release layer of 30 nm to 2 µm. The method of claim 1,
The release layer is a release film that simultaneously satisfies the following Equations 1 to 3:
<Equation 1>
5 ≤ A ≤ 50
In Equation 1 above,
A represents the peeling force (gf/in) for the release layer using the epoxy resin adhesive.
<Equation 2>
10 ≤ B ≤ 800
In Equation 2 above,
B represents the peel force (gf/in) for the release layer using the TESA7475 tape.
<Equation 3>
0 ≤ C ≤ 1
In Equation 3 above,
C represents the Si transfer rate (%). The method of claim 1,
The substrate is a release film of a polyester-based film or sheet. The method of claim 1,
The substrate is a release film further comprising inorganic particles. The method of claim 1,
A release film having a thickness of the substrate of 30 nm to 130 μm. A silicone resin into which a phenyl group represented by the following formula 1 is introduced and a silane coupling agent represented by the following formula 2 are included on at least one side of the substrate, and the molar ratio of the Si-Ph (phenyl group) bond to the Si-Me (methyl group) bond is Applying a silicone release composition of 100: 30 to 100: 50; And
By curing the applied silicone release composition by heat treatment, the area ratio in which Si-Ph (phenyl group) bonds are distributed by X-ray photoelectron spectroscopy (XPS) analysis in the thickness direction from the surface to the substrate is reduced. Forming a release layer; method for producing a release film comprising:
<Formula 1>

In Formula 1,
x, y, z are integers of 1 or more;
R ₁ , R ₆ , R ₈ , R ₁₀ are each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C2-C20 alkenyl group, A substituted or unsubstituted C2-C20 alkenylene group, or a combination thereof;
R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₉ , R ₁₁ are each independently a substituted or unsubstituted C1-C20 alkyl group;
R ₈ is each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 aryl group, or a combination thereof.
<Formula 2>

In Chemical Formula 2,
R _a , R _b , and R _c are each independently a substituted or unsubstituted C1-C20 alkyl group. The method of claim 12,
In Formula 1, R ₁ , R ₆ , R ₈ , R ₁₀ are each independently selected from -CH=CH ₂ , -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH=CH _2, and -CH ₃ A method of manufacturing one or more release films. The method of claim 12,
In Formula 1, R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₉ , R ₁₁ are each independently a methyl group, and R ₈ is at least one selected from a methyl group and a phenyl group. The method of claim 12,
In Formula 2, R _a , R _b , and R _c are each independently a methyl group. delete The method of claim 12,
The silicone release composition is a method for producing a release film comprising a phenyl group in an amount of more than 20 mol% to 30 mol%. The method of claim 12,
A method for producing a release film having a thickness of the release layer of 30 nm to 2 µm. The method of claim 12,
A method for producing a release film in which the content of the applied silicone release composition is 2 g/m ^{2 or more.} The method of claim 12,
The silicone release composition is a method for producing a release film further comprising a catalyst.

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