KR20230132223A - Release film comprising fluorine group and manufacturing method thereof - Google Patents

Abstract

A heterogeneous film containing a fluorine group according to the present invention comprises a base film and a heterogeneous layer formed by applying a heterogeneouscoating solution containing an organopolysiloxane (A) containing a fluorine group and an organopolysiloxane (B) not containing a fluorine group located on at least one side of the base film, and has effects of improving processability by allowing dilution and coating of the coating solution without using a fluorine-based solvent, reducing the haze change in the existing rub-off by improving the degree of crosslinking, and improving the peelability and peeling force deviation since uniform coating is possible. In addition, since the amount of expensive organopolysiloxane containing a fluorine group may be minimized, it is possible to manufacture a product with excellent physical properties and high cost-effectiveness, and when applying the fluorine-containing heterogeneous film according to the present invention in a silicone-based adhesive processing process, it is possible to expect a cost-saving effect along with excellent physical properties.

Description

Fluorine-containing release film and manufacturing method thereof {RELEASE FILM COMPRISING FLUORINE GROUP AND MANUFACTURING METHOD THEREOF}

The present invention relates to a release film, and more specifically, to a release coating containing a fluorine group applied to at least one side of a polyester base film with a release coating solution containing an organopolysiloxane containing a fluorine group and an organopolysiloxane without a fluorine group. The present invention relates to a fluorine-containing release film with improved crosslinking and less haze change and a method for manufacturing the same.

In general, silicone-based adhesives have advantages such as heat resistance, friction resistance, and flexibility, and have recently been widely applied to flexible displays. In addition, it is used in a wide range of applications because it has excellent electrical insulation, low toxicity, and cold resistance.

When using such a silicone-based adhesive, a release film with excellent peelability is required. However, in the case of the widely known silicone-based release film, the silicone of the release coating layer has good compatibility with the silicone-based adhesive layer, so there is a problem of not peeling when laminated. For this reason, release films for silicone-based adhesives are often films coated with a release agent containing fluorine-based resin.

However, the release agent containing fluorine-based resin used as a release agent has low surface energy and is not compatible with general organic solvents, so it can cause coating defects such as pinhole defects. Therefore, a fluorine-based solvent must be used when diluting or coating the coating solution. In addition, since these fluorine-based solvents are very volatile, it is difficult to maintain a constant coating thickness when coating on a film, which may cause stains on the coating layer due to poor leveling during coating and deviation in peeling force due to deviation in coating thickness. . In order to solve the problem that fluorine-based polymers cannot be dissolved in organic solvents that do not contain fluorine, it has been proposed that peeling is possible through a combination of a phenyl group-containing silicone adhesive and an addition reaction type silicone release agent (e.g., Japanese patent Publication No. 10-147758), there was a problem such as an increase in peeling force over time.

In addition, when the release agent containing fluorine resin was evaluated for the degree of cross-linking through a rub-off test, there was a problem in that some of the release agent was pushed away or the physical properties of the haze changed.

In addition, release agents containing fluorine-based solvents and fluorine-based resins are dozens of times more expensive than general organic solvents and silicone-based release agents, so they have several disadvantages in terms of productivity. Despite the excellent characteristics of silicone-based adhesives, these disadvantages of the release film cause The reality is that usage is not increasing exponentially.

Japanese Patent Laid-open Publication No. 10-147758

The present invention was created to solve the above problems and meet the conventional requirements. The problem that the present invention aims to solve is excellent peelability and improved coating properties, thereby providing excellent appearance characteristics of the release layer and improving the degree of cross-linking. The aim is to provide a fluorine-containing release film with small haze change during existing rub-off and a method for manufacturing the same.

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

The above purpose is to form a release layer formed by applying a release coating solution located on a base film and at least one side of the base film and containing an organopolysiloxane (A) containing a fluorine group and an organopolysiloxane (B) containing no fluorine group. This is achieved by a release film containing a fluorine group.

Preferably, the release film is maintained with a weight of 300 g using a rubbing test (CT-RB Series), and a wear-resistant nonwoven fabric free of foreign substances is placed on the surface of the release layer and performed back and forth 5 times. The haze change may be less than 5.0%.

Preferably, the surface of the release layer has an F (fluorine atom)/Si (silicon atom) value of 1.5 to 3.0 according to the XPS analysis results, and the deep portion adjacent to the base film of the release layer has an F (fluorine atom) value according to the XPS analysis results. )/Si (silicon atom) value may be 0.2 to 0.8.

Preferably, the release layer may have a fluorine atom/silicon atom content ratio that decreases from the surface to the depth.

Preferably, the fluorine-containing release film may have a residual adhesion rate of 85% or more.

Preferably, the fluorine-containing release film is stored at 25°C and 65%RH for 24 hours, then a silicone-based adhesive tape (MY2G, Taiwan) is attached to the surface of the release layer, and then applied for 24 hours at 50°C with a load of 20g/cm ² After time compression, the peeling force measured by peeling at a peeling angle of 180° and a peeling speed of 0.3mpm may be 10 gf/inch or less.

Preferably, the organopolysiloxane (A) containing a fluorine group may contain at least one fluorinated substituent of at least one of an alkenyl group having 2 to 10 carbon atoms, a fluoroalkyl group, or a fluoroether group in one molecule.

Preferably, the organopolysiloxane (B) that does not contain a fluorine group may contain an alkyl group or an alkenyl group having 2 to 10 carbon atoms in one molecule.

Preferably, the organopolysiloxane (B) that does not contain a fluorine group may contain 60 to 300 parts by weight compared to 100 parts by weight of the organopolysiloxane (A) that contains a fluorine group.

Preferably, the release coating solution may further include hydroelectric polysiloxane and a platinum chelate catalyst.

Preferably, the hydroelectric polysiloxane may contain 3 to 4 parts by weight based on 100 parts by weight of the organopolysiloxane (A) containing a fluorine group.

Preferably, the platinum chelate catalyst may be included in the release coating solution at 410 to 890 ppm.

Preferably, the hydroelectric bond bonded to the silicon atom of the hydropolysiloxane is 1.0 to 3.0 hydroelectric groups for each alkenyl group of the organopolysiloxane containing a fluorine group (A) and the organopolysiloxane (B) not containing a fluorine group. It may contain electricity.

Preferably, the thickness of the release layer after drying may be 0.03 to 2.0 ㎛.

In addition, the above purpose includes preparing a base film and preparing an organopolysiloxane (A) containing a fluorine group on at least one side of the base film, an organopolysiloxane (B) containing no fluorine group, a hydroelectric polysiloxane, and a platinum chelate catalyst. It includes the step of forming a release layer by applying and drying the release coating solution contained therein. Using a rubbing test (CT-RB Series), the weight is maintained at 300 g and a wear-resistant nonwoven fabric free of foreign substances is used as the release layer. This is achieved by a method of manufacturing a release film containing a fluorine group in which the haze change is 5.0% or less after placing it on the surface and performing five round trips.

The fluorine-containing release film according to an embodiment of the present invention has an improved degree of cross-linking, which has the effect of improving the existing problem of the film not peeling off and hazing during rub-off.

In addition, the fluorine-containing release film according to an embodiment of the present invention can reduce the amount of organopolysiloxane containing expensive fluorine groups and improve the cost-effectiveness of the product because expensive fluorine-based solvents can be eliminated. It has effects such as:

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

1 is a configuration diagram of a fluorine-containing release film according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to embodiments of the present invention and drawings. These examples are merely presented as examples to explain the present invention in more detail, and it will be apparent to those skilled 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 in this specification have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. In case of conflict, the present specification, including definitions, will control. Although methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, suitable methods and materials are described herein.

As used herein, “comprise,” “comprising,” “include,” “including,” “containing,” “~ The terms "characterized by", "has", "having" or any other variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of elements is not necessarily limited to only those elements and may include other elements not explicitly listed or inherent to such process, method, article, or apparatus. It may be possible. Additionally, unless explicitly stated to the contrary, “or” refers to an inclusive “or” and does not refer to an exclusive “or.”

In describing and/or claiming the invention, the term “copolymer” is used to refer to a polymer formed by copolymerization of two or more monomers. Such copolymers include binary copolymers, terpolymers or higher copolymers.

First, the fluorine group-containing release film according to an embodiment of the present invention will be described in detail with reference to Figure 1, which is a structural diagram of the fluorine group-containing release film according to an embodiment of the present invention.

Referring to FIG. 1, the fluorine group-containing release film 100 according to an embodiment of the present invention includes a base film 10 and a release layer 20 located on at least one side of the base film 10. The release layer 20 includes organopolysiloxane (A) containing a fluorine group and organopolysiloxane (B) not containing a fluorine group, and the release coating solution further containing hydrogenopolysiloxane and a platinum chelate catalyst is applied to the base film (10). ) can be applied and placed on.

As a result of the present invention's efforts to provide a release film that can satisfy excellent release properties and appearance properties for silicone-based adhesives, the present invention has been developed to provide an organopolysiloxane containing a fluorine group on at least one side of the polyester base film 10 and an organopolysiloxane containing no fluorine group. By forming the release layer 20 by applying a release coating solution containing organopolysiloxane, a release film with excellent release characteristics and coating appearance characteristics and improved cost-effectiveness is provided. Each component will be described in detail below. do.

1. Base film (10)

The base film 10 is a polyester base film, and the polyester resin used herein may be a known base film commonly used in the field of silicone release coating. In particular, the polyester base film described in the present invention is The polyester base film disclosed in Republic of Korea Patent No. 10-1268584, a prior invention by the applicant of the invention, can be applied. However, in the embodiments of the present invention, the polyester base film is described without particular limitation in order to explain only the technical features of the present invention, but it should be understood that the technical features related to known polyester base films are included.

Specifically, the base film 10 is explained focusing on polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, but the base film of the silicone release coating solution of the present invention is limited to polyester sheets or films. It doesn't work. The polyester resin that forms the base film is a polyester obtained by polycondensing aromatic dicarboxylic acid and aliphatic glycol, and aromatic dicarboxylic acids include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, Adipic acid, sebacic acid, oxycarboxylic acid (e.g., p-oxybenzoic acid, etc.) are used, and aliphatic glycols include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanol, Neopentyl glycol, etc. can be used. This polyester resin may be a combination of two or more of a dicarboxylic acid component and a glycol component, and may also be a copolymer containing a third component.

In addition, the polyester base film according to an embodiment of the present invention uses a uniaxially or biaxially oriented film that has high transparency and excellent productivity and processability. Representative polyester resins include polyethylene terephthalate (PET) and polyethylene-2,6-nathalenedicarboxylate (PEN).

In addition, the polyester base film 10 according to the present invention may contain particles to provide excellent running characteristics between rolls, and there is no particular limitation on the type of added particles as long as they can exhibit excellent sliding characteristics.

Specifically, it may include particles such as silica, silicon oxide, calcium carbonate, calcium sulfate, calcium phosphate, magnesium carbonate, magnesium phosphate, barium carbonate, kaolin, aluminum oxide, titanium oxide, etc., and the shape of the particles used may be special. Although not limited, any of spherical, lumpy, rod-shaped, or plate-shaped particles may be preferably used.

In addition, there are no particular restrictions on the hardness, specific gravity, and color of the particles, but two or more types may be used in parallel as needed, and the average particle diameter of the particles used is preferably 0.1 to 5㎛, more preferably 0.1. Use one in the range of 2㎛ to 2㎛. At this time, if the average particle diameter of the particles is less than 0.1㎛, agglomeration between particles may occur, resulting in poor dispersion. On the other hand, if the average particle diameter of the particles exceeds 5㎛, the surface roughness characteristics of the film deteriorate, making it difficult to use during post-processing. Coating defects may occur.

Additionally, when the base film 10, which is a polyester film, contains particles, the preferred particle content is 0.01 to 5% by weight, and more preferably 0.01 to 3% by weight. If the particle content is less than 0.01% by weight, the sliding characteristics of the polyester film may deteriorate and the running characteristics between rolls may deteriorate, and if the particle content exceeds 5% by weight, the surface smoothness of the film may deteriorate.

The thickness of the base film 10 is not limited, but is preferably 30 to 125 ㎛. If the thickness of the base film 10 is too thin (less than 30㎛), deformation occurs due to heat treatment, and if it is too thick (more than 125㎛), heat is not sufficiently transmitted and curing problems occur.

2. Release layer (20)

The release layer 20 is located on at least one side of the base film 10, includes organopolysiloxane (A) containing a fluorine group and organopolysiloxane (B) without a fluorine group, and includes hydrogenated polysiloxane and a platinum chelate catalyst. It may be formed by applying a release coating solution further comprising the coating.

In the release coating solution of the present invention, organopolysiloxane (A, B) is the main component of the release coating solution, and organopolysiloxane (A) and organopolysiloxane (B) may exist as individual molecules or be connected as a copolymer. It may be. Additionally, any type of addition reaction type, condensation reaction type, or ultraviolet curing type siloxane resin can be used, and use is not particularly limited to any one type.

In one embodiment, the organopolysiloxane (A) containing a fluorine group has at least one fluorine-containing substituent among an alkenyl group having 2 to 10 carbon atoms bonded to a silicon atom and a fluoroalkyl group or fluoroether group bonded to a silicon atom in one molecule. It is desirable to include at least one.

Specifically, the organopolysiloxane (A) containing a fluorine group preferably has the structure of Formula 1 below.

(Formula 1)

In Formula 1, Ra is a monovalent hydrocarbon group excluding aliphatic unsaturated groups having 1 to 10 carbon atoms. Specifically, alkyl groups, aryl groups, and some or all of the hydrogen atoms of these groups may be hydroxy groups, cyano groups, etc., and may have 2 carbon atoms. It may be an alkenyl group of ~10.

Rb is a monovalent hydrocarbon group excluding aliphatic unsaturated groups having 1 to 10 carbon atoms. Specifically, an alkyl group, an aryl group, and some or all of the hydrogen atoms of these groups may be hydroxy groups, cyano groups, etc., and an alkyl group having 2 to 10 carbon atoms. It may be a nyl group or a hydrogen group.

Rc is a monovalent hydrocarbon group containing at least one fluorine-containing substituent in a fluoroalkyl group or a fluoroether group, excluding an aliphatic unsaturated group having 1 to 10 carbon atoms, and is specifically an alkyl group, an aryl group, and a hydrogen atom of these groups. Some or all of may include at least one type of a hydroxy group, a hydrocarbon group including a cyano group, an alkenyl group having 2 to 10 carbon atoms, and a hydrogen group.

Additionally, X, Y, and Z are each integers greater than or equal to 1.

Additionally, in Formula 1, the fluoroalkyl group preferably has the structure of Formula 2 below.

(Formula 2)

In Formula 2, n is an integer from 1 to 8 and m is an integer from 1 to 5.

Additionally, in Formula 1, the fluoroether group preferably has the structure of Formula 3 below.

(Formula 3)

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

In one embodiment, the organopolysiloxane (B) that does not contain a fluorine group may have at least two alkenyl groups bonded to a silicon atom in one molecule, and preferably contains at least two alkenyl groups bonded to a silicon atom. The structure is either linear or branched, and a structure in which both linear and branched forms coexist is also preferred.

Specifically, the organopolysiloxane (B) that does not contain a fluorine group preferably has the structure of the following formula (4).

(Formula 4)

In Formula 4, Ra is a monovalent hydrocarbon group excluding aliphatic unsaturated groups having 1 to 10 carbon atoms. Specifically, alkyl groups, aryl groups, and some or all of the hydrogen atoms of these groups may be hydroxy groups, cyano groups, etc., and may have 2 carbon atoms. It may be an alkenyl group of ~10. And Rb is a monovalent hydrocarbon group excluding aliphatic unsaturated groups having 1 to 10 carbon atoms. Specifically, alkyl groups, aryl groups, and some or all of the hydrogen atoms of these groups may be hydroxy groups, cyano groups, etc., and may be hydrocarbon groups having 2 to 10 carbon atoms. It may be an alkenyl group or a hydrogen group. Additionally, X and Y are each integers greater than 1.

In one embodiment, the organopolysiloxane (B) containing no fluorine group is preferably contained in an amount of 60 to 300 parts by weight relative to 100 parts by weight of the organopolysiloxane (A) containing a fluorine group. At this time, if the amount is less than 60 parts by weight, the peeling properties are not improved and the compatibility with non-fluorine-based solvents deteriorates, causing problems with the appearance characteristics during coating. If it exceeds 300 parts by weight, the fluorine atoms on the surface are insufficient, causing peeling when laminated with a silicone adhesive. It doesn't work.

In one embodiment, hydroelectric polysiloxane is used as a curing agent for a release coating solution, and any type such as addition type, condensation type, or ultraviolet curing type can be used, and its use is not particularly limited to any one type. Additionally, the hydroelectric polysiloxane may be linear, branched, or cyclic, and a mixture thereof may also be used. In addition, the viscosity or molecular weight is not limited, but it must have good compatibility with the organopolysiloxane (A, B), and the hydrogenopolysiloxane does not need to contain a fluorine group, but preferably contains the same fluorine group as the organopolysiloxane (A). It is more preferable that a group is included.

In one embodiment, the hydrogen polysiloxane preferably contains 3 to 4 parts by weight based on 100 parts by weight of the organopolysiloxane (A) containing a fluorine group. At this time, if the hydropolysiloxane content is less than 3 parts by weight, the residual adhesion rate decreases and defects in appearance occur, and if it exceeds 4 parts by weight, the peeling force significantly increases, so it is preferable to set it within the above range.

In addition, the hydroelectric group bonded to the silicon atom of the hydroelectric polysiloxane represents 1.0 to 3.0 hydroelectric groups per total alkenyl group of the organopolysiloxane (A) containing a fluorine group and the organopolysiloxane (B) without a fluorine group. It is desirable to include it. At this time, if there are less than 1.0 hydroelectric groups bonded to the silicon atoms of the hydroelectric polysiloxane relative to one alkenyl group of the organopolysiloxane, there is a problem in curing, and if it exceeds 3.0, there are many hydrogen atoms remaining in the coating layer after curing, which reduces the peeling ability. Problems such as changes over time arise.

Additionally, the release coating liquid may include a platinum chelate catalyst as a catalyst. At this time, the platinum chelate catalyst preferably contains 410 to 890 ppm relative to the release coating solution. At this time, if the platinum chelate catalyst content is less than 410 ppm, the residual adhesion rate decreases and appearance defects occur, and if it exceeds 890 ppm, the peeling force increases excessively, so it is preferable to set it within the above range.

In addition, the release coating solution is preferably diluted in a solvent to have a total solid content of 0.5 to 10% by weight and then coated on at least one side of the base film 10 to form the release layer 20. At this time, the solvent used in the release coating solution can be used without limitation as long as it can disperse the solid content of the present invention and apply it on the base film 10. If the total solids content of the release coating solution is less than 0.5% by weight, a uniform release coating layer may not be formed, which may cause problems such as poor peeling between the silicone-based adhesive layer and the release film. If it exceeds 10% by weight, the coating solution may Due to the high viscosity, uneven leveling of the coating layer may occur, which may deteriorate the thickness uniformity of the release layer.

In addition, the release layer 20 formed by coating on the base film 10 may be a release coating solution applied using a conventionally known coating method such as bar coating, gravure coating, or die coating.

In one embodiment, the thickness of the release layer 20 after drying is preferably 0.03 to 2.0 ㎛. At this time, if the thickness of the release layer 20 after drying is less than 0.03㎛, the coverage of the release layer 20 may be poor, which may cause problems of peeling when laminated with a silicone-based adhesive, and the drying of the release layer 20 may occur. If the post thickness exceeds 2.0㎛, problems such as drying may occur, and the peeling properties are not improved, so there is a problem of poor cost-effectiveness.

The fluorine-containing release film 100 according to an embodiment of the present invention is maintained at a weight of 300 g using a rubbing test (CT-RB Series), and a wear-resistant nonwoven fabric free from foreign substances is used as the base film of the release layer. It is desirable that the haze change is 5.0% or less after placing it on a surface that is not in contact with it and performing 5 round trips. If the haze change exceeds 5.0% after such a rubbing test, a problem occurs due to slipping during the rub-off test.

When the surface of the release layer 20 of the fluorine group-containing release film 100 according to an embodiment of the present invention is analyzed with an XPS analysis device, it is preferable that the fluorine atom/silicon atom content ratio decreases from the surface to the deep part. Meanwhile, in the present invention, “deep part” refers to the point where the atomic % of C (carbon) is 60% from the surface of the release layer.

More specifically, the surface of the release layer 20 preferably has an F (fluorine atom)/Si (silicon atom) value of 1.5 to 3.0 according to the results of XPS analysis. At this time, if the F/Si value of the surface of the release layer 20 is less than 1.5, a problem of not peeling occurs when bonded with a silicone-based adhesive, and if it is more than 3.0, the residual adhesion rate decreases and the haze change after the rubbing test exceeds 5%. I do it.

In addition, the deep portion of the release layer 20 adjacent to the base film 10 preferably has an F (fluorine atom)/Si (silicon atom) value of 0.2 to 0.8 according to the XPS analysis results. At this time, if the F/Si value of the core part of the release layer 20 is less than 0.2, the fluorine group content is insufficient and peeling is not easy when laminated with a silicone-based adhesive, and if it is more than 0.8, the residual adhesion rate decreases and the amount of haze change after the rubbing test exceeds 5%.

The fluorine-containing release film 100 according to an embodiment of the present invention preferably has a residual adhesion rate of 85% or more. At this time, if the residual adhesion rate is less than 85%, curing of the release layer 20 is insufficient, which may cause the release agent to transfer to the laminated adhesive layer and deteriorate the adhesive properties of the adhesive.

The fluorine-containing release film 100 according to an embodiment of the present invention is stored at 25°C and 65%RH for 24 hours, and then a silicone-based adhesive tape (MY2G, Taiwan) is applied to the surface not in contact with the base film of the release layer. After attaching, pressing at 50°C with a load of 20g/cm ² for 24 hours, peeling at a peeling angle of 180° and a peeling speed of 0.3mpm, the measured peeling force is preferably 10 gf/inch or less. At this time, if the peeling force is more than 10 gf/inch, the peeling from the silicone-based adhesive may not be done properly, which may cause problems in the process.

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

[Example]

[Example 1]

For 100 parts by weight of organopolysiloxane (A, Dow Chemical Co., Ltd., Q2-7785) containing a fluorine group on a polyester film (Toray Advanced Materials, , 100 parts by weight of hydroelectric polysiloxane (Q2-7560, manufactured by Dow Chemical), 700 ppm of platinum chelate catalyst (SYL-OFF 4000, manufactured by Dow Chemical) in heptane solution. It was diluted to prepare a release coating solution with a total solid content of 6% by weight and applied. After application, it was heat treated in a hot air dryer at 150°C for 50 seconds to form a release layer with a thickness of 0.5 μm, thereby preparing a release film.

[Example 2]

A release film was manufactured in the same manner as in Example 1, except that a release layer with a thickness of 2.0 μm was formed in Example 1.

[Example 3]

A release film was manufactured in the same manner as in Example 1, except that 60 parts by weight of organopolysiloxane (B, manufactured by Dow Chemical, LTC-750A), which does not contain a fluorine group, was used.

[Example 4]

A release film was manufactured in the same manner as in Example 1, except that 300 parts by weight of organopolysiloxane (B, manufactured by Dow Chemical, LTC-750A), which does not contain a fluorine group, was used.

[Comparative example]

[Comparative Example 1]

A release film was manufactured in the same manner as in Example 1, except that 300 parts by weight of organopolysiloxane (A, manufactured by Dow Chemical, Q2-7785) containing a fluorine group was used.

[Comparative Example 2]

A release film was manufactured in the same manner as in Example 1, except that 30 parts by weight of organopolysiloxane (A, manufactured by Dow Chemical, Q2-7785) containing a fluorine group was used.

[Comparative Example 3]

A release film was manufactured in the same manner as in Example 1, except that 5 parts by weight of hydroelectric polysiloxane (Q2-7560, manufactured by Dow Chemical) was used.

[Comparative Example 4]

A release film was manufactured in the same manner as in Example 1, except that 2 parts by weight of hydroelectric polysiloxane (Q2-7560, manufactured by Dow Chemical) was used.

[Comparative Example 5]

A release film was prepared in the same manner as in Example 1, except that 900 ppm of the platinum chelate catalyst (SYL-OFF 4000, manufactured by Dow Chemical) was used.

[Comparative Example 6]

A release film was prepared in the same manner as in Example 1, except that 400 ppm of the platinum chelate catalyst (SYL-OFF 4000 manufactured by Dow Chemical) was used.

[Comparative Example 7]

A release film was manufactured in the same manner as in Example 1, except that 310 parts by weight of organopolysiloxane (B, Shin-Etsu Silicone Co., Ltd., KS-847H), which does not contain a fluorine group, was used.

[Comparative Example 8]

A release film was manufactured in the same manner as in Example 1, except that 55 parts by weight of organopolysiloxane (B, manufactured by Shin-Etsu Silicone, KS-847H) was used.

[Comparative Example 9]

A release film was manufactured in the same manner as in Example 1, except that a release layer with a thickness of 2.1 ㎛ was formed in Example 1.

[Comparative Example 10]

A release film was manufactured in the same manner as in Example 1, except that a release layer with a thickness of 0.02 ㎛ was formed.

Using the release films according to Examples 1 to 4 and Comparative Examples 1 to 10, physical properties were measured through the following experimental examples, and the results are shown in Table 1 below.

[Experimental example]

(1) XPS (X-ray photoelectron spectroscopy) analysis evaluation of the release layer

1-1. Release layer surface analysis

The surface of the release layer of the release film prepared in Examples and Comparative Examples was analyzed with an analysis area (Spot size) of 400 ㎛ using an It is indicated as , and the results are listed in Table 1 below.

1-2. Heterogeneous layer deep analysis

The surface of the release layer of the release film prepared in Examples and Comparative Examples was treated with Ar plasma for 30 seconds under the condition of Ion Energy 3000 eV to etch the surface of the release layer, and then etched as described in 1-1 above. XPS analysis was performed under the same conditions as the release layer surface analysis, and plasma treatment and XPS analysis were repeated until a layer with an atomic % of C (carbon) of 80% or more was analyzed. The point where the atomic % of C (carbon) is 60% from the surface of the release layer is referred to as the deep part, and the XPS analysis results at the deep part are shown in Table 1 below.

2. Release film Peel force measurement

[Sample preparation]

① Store the release-coated measurement sample at 25℃, 65%RH for 24 hours.

② After attaching a silicone-based adhesive tape (MY2G, Taiwan) to the release coating surface, the sample was compressed for 24 hours at 50℃ with a load of 20g/cm ² and the physical properties were measured.

[Measurement equipment]

Chemistry AR-2000

[measurement method]

① 180° peeling angle, peeling speed 0.3mpm

② Sample size: 500mm x 1500mm, peel force measurement size: 250mm x 1500mm

[Measurement data]

The peel force unit is gf/inch, and the measured value is measured 5 times and the average value is calculated.

3. Analysis of residual adhesion rate of release film

[Sample preparation]

① Store the release-coated measurement sample at 25°C and 65%RH for 24 hours.

② After attaching a standard adhesive tape (Nitto 31B) to the release coating surface, the sample was compressed for 24 hours at room temperature with a load of 20g/cm ² .

③ After collecting the adhesive tape that was attached to the silicone surface above without contamination, attach it to the PET FILM surface with a flat and clean surface, and then press it back and forth once with a 2kg tape roller (ASTMD-1000-55T).

[Measurement equipment]

Chemistry AR-2000

[measurement method]

① 180° peeling angle, peeling speed 0.3mpm

② Sample size: 500mm x 1500mm, peel force measurement size: 250mm x 1500mm

[Measurement data]

4. Measurement of haze change in release film

The release film manufactured in the Examples and Comparative Examples was prepared in A4 size, maintained with a weight of 300g using a rubbing test (CT-RB Series), and a wear-resistant nonwoven fabric free of foreign substances was placed on the wear surface. Afterwards, five round trips were performed. Then, the haze before and after treatment was measured using a haze meter (NDH-5000), and the amount of haze change was calculated.

5. Appearance evaluation of release film

The surface appearance of the release layer was evaluated for the Examples and Comparative Examples for which the wear resistance test was completed in Experimental Example 3, and the results are listed in Table 1 below.

○: Good appearance (no scratches, good film applicability, or no scratches)

△: Partial appearance defects (1 to 3 defects or 1 to 3 defects in film applicability or 1 to 3 scratches)

X: Appearance defect (exceeding more than 3EA, or exceeding more than 3EA scratches or scratches)

SurfaceXPS
(Atomic%) DeepXPS
(Atomic%) △Haze(%) Peel force
(gf/inch) residual
Adhesion rate (%) Exterior
evaluation Si F F/Si F/Si jeon after △ Example 1 13.7 35.9 2.62 0.75 22.4 18.2 4.2 8.1 92 ○ Example 2 13.0 37.2 2.86 0.80 22.4 18.2 4.2 5.5 89 ○ Example 3 13.0 37.7 2.9 0.70 22.6 18.4 4.2 6.0 90 ○ Example 4 19.1 31 1.6 0.76 22.1 18.1 4.0 7.9 92 ○ Comparative Example 1 13.3 36 2.7 0.95 28.3 18.5 9.8 5.0 86 ○ Comparative example 2 22 30 1.36 0.40 20 18.1 1.9 40.0 95 ○ Comparative example 3 13.5 36.1 2.67 0.76 21.7 18.1 3.6 49.3 84 △ Comparative example 4 13 37 2.84 0.78 22.4 18.0 4.4 6.0 84 × Comparative Example 5 13.4 37.1 2.76 0.78 22.2 18.2 4.0 82.0 84 ○ Comparative Example 6 13.3 37 2.78 0.79 22.5 18.4 4.1 10.0 80 × Comparative example 7 20 28 1.4 0.90 20 18.4 1.6 38.0 93 ○ Comparative example 8 10 27 2.7 0.68 28.5 18.1 10.4 7.4 87 × Comparative Example 9 13 36.5 2.80 0.82 24.5 18.5 6.0 29.0 90 × Comparative Example 10 13.3 36 2.7 0.80 22.0 18.1 3.9 92.0 90 △

As can be seen in Table 1, the fluorine-containing release films according to Examples 1 to 4 of the present invention have excellent peelability against silicone-based adhesives, and the haze change is almost 5.0% or less, showing almost no difference in the rub-off test. It can be confirmed that the peeling phenomenon does not occur and the physical properties and coating appearance characteristics of the film are excellent.

On the other hand, if the composition of the organopolysiloxane of the release layer is not appropriate or the coating thickness of the release layer is not optimized, it can be seen that the coating appearance characteristics deteriorate and peeling characteristics become poor.

More specifically, it can be confirmed that Comparative Example 1 is not suitable as a release film due to its increased fluorine content and large haze difference.

In addition, Comparative Example 2 has a low fluorine content compared to Si, so the haze difference is good, but the F/Si value on the XPS surface deviates, and the peeling force increases, making it unsuitable as a release film.

In addition, in Comparative Example 3, it can be seen that the residual adhesion rate was lowered due to the excessive content of the curing agent, and the peeling force was excessively increased due to the unreacted curing agent.

In addition, it can be seen that Comparative Example 4 contained a small amount of curing agent, resulting in poor curing and poor appearance.

In addition, it can be seen that Comparative Example 5 had an excessive catalyst content and thus had an excessively high peeling force.

In addition, it can be seen that in Comparative Example 6, the catalyst content was small, and curing was not possible, resulting in a lower residual adhesion rate and poor appearance.

In addition, it can be confirmed that Comparative Example 7 is not suitable as a release film due to the excessive amount of organopolysiloxane (B) containing no fluorine group, which reduces the XPS surface F/Si value and increases the peeling force.

In addition, it can be confirmed that Comparative Example 8 is not suitable as a release film because it contains less organopolysiloxane (B) that does not contain a fluorine group, which increases the XPS surface F/Si value, increases the haze change, and worsens the appearance.

In addition, it can be confirmed that Comparative Example 9 is not suitable as a release film because the thickness of the release layer was excessive after drying, so the appearance deteriorated, the haze difference increased, and the peeling force increased.

In addition, it can be confirmed that Comparative Example 10 is not suitable as a release film because the release layer thickness is too thin, the appearance is poor, and the peeling force is excessively large.

As described above, the present invention includes a release layer formed by applying a release coating solution containing an organopolysiloxane containing a fluorine group and an organopolysiloxane without a fluorine group on at least one side of the base film, and the amount of haze change under predetermined conditions. By providing a release film containing a fluorine group of 5.0% or less, the coating solution can be diluted and coated without using a fluorine-based solvent, improving processability, and uniform coating is possible, improving peelability and peel force variation. You can. Furthermore, since the amount of organopolysiloxane containing expensive fluorine groups can be minimized, products with excellent physical properties and high cost-effectiveness can be manufactured. When the release film according to the present invention is applied in the silicone-based adhesive processing process, excellent physical properties and In addition, cost reduction effects can be expected.

In this specification, only a few examples of various embodiments performed by the present inventors are described, but the technical idea of the present invention is not limited or limited thereto, and of course, it can be modified and implemented in various ways by those skilled in the art.

100: Release film containing fluorine group
10: Base film
20: release layer

Claims (15)

Base film; and
A release layer located on at least one side of the base film and formed by applying a release coating solution containing organopolysiloxane (A) containing a fluorine group and organopolysiloxane (B) not containing a fluorine group;
A release film containing a fluorine group. According to paragraph 1,
The fluorine-containing release film is maintained with a weight of 300 g using a rubbing test (CT-RB Series), and a wear-resistant nonwoven fabric free of foreign substances is placed on the surface of the release layer and performed back and forth 5 times. A release film containing a fluorine group with a haze change of 5.0% or less. According to paragraph 1,
The surface of the release layer has an F (fluorine atom)/Si (silicon atom) value of 1.5 to 3.0 according to the XPS analysis results,
A release film containing a fluorine group in which the deep portion adjacent to the base film of the release layer has an F (fluorine atom)/Si (silicon atom) value of 0.2 to 0.8 according to the results of XPS analysis. According to paragraph 1,
The release layer is a fluorine-containing release film in which the fluorine atom/silicon atom content ratio decreases from the surface to the depth. According to paragraph 1,
The release film containing a fluorine group has a residual adhesion rate of 85% or more. According to paragraph 1,
The fluorine-containing release film was stored at 25°C and 65%RH for 24 hours, and then a silicone-based adhesive tape (MY2G, Taiwan) was attached to the surface of the release layer and compressed at 50°C with a load of 20g/cm ² for 24 hours. After peeling, the release film containing a fluorine group has a peeling force of 10 gf/inch or less, as measured by peeling at a peeling angle of 180° and a peeling speed of 0.3mpm. According to paragraph 1,
The organopolysiloxane (A) containing a fluorine group includes at least one fluorine-containing substituent of at least one alkenyl group having 2 to 10 carbon atoms, a fluoroalkyl group, or a fluoroether group in one molecule, a release film containing a fluorine group. According to paragraph 1,
The organopolysiloxane (B), which does not contain a fluorine group, is a release film containing a fluorine group containing an alkyl group or an alkenyl group having 2 to 10 carbon atoms in one molecule. According to paragraph 1,
A release film containing a fluorine group, wherein the organopolysiloxane (B) not containing a fluorine group contains 60 to 300 parts by weight compared to 100 parts by weight of the organopolysiloxane (A) containing a fluorine group. According to paragraph 1,
The release coating liquid is a fluorine-containing release film further comprising hydroelectric polysiloxane and a platinum chelate catalyst. According to clause 10,
The hydroelectricity bonded to the silicon atom of the hydroelectric polysiloxane is 1.0 to 3.0 hydroelectricity per total alkenyl group of the organopolysiloxane (A) containing the fluorine group and the organopolysiloxane (B) without the fluorine group. A release film containing a fluorine group. According to clause 10,
A release film containing a fluorine group, wherein the hydroelectric polysiloxane contains 3 to 4 parts by weight based on 100 parts by weight of the organopolysiloxane (A) containing a fluorine group. According to clause 10,
The platinum chelate catalyst is a fluorine-containing release film containing 410 to 890 ppm in the release coating solution. According to paragraph 1,
A release film containing a fluorine group, wherein the release layer has a thickness of 0.03 to 2.0 ㎛ after drying. Preparing a base film; and
A release coating solution containing organopolysiloxane (A) containing a fluorine group, organopolysiloxane (B) without a fluorine group, hydrogenated polysiloxane, and a platinum chelate catalyst is applied and dried on at least one side of the base film to form a release layer. Including, forming a
Using a rubbing test (CT-RB Series), a wear-resistant nonwoven fabric free of foreign substances is maintained at a weight of 300 g and placed on the surface of the release layer, and after 5 round trips, the haze change is less than 5.0%, Method for manufacturing a release film containing a fluorine group.