WO2020209450A1 - Fluorine group-containing release film - Google Patents

Abstract

The present invention relates to a fluorine group-containing release film. The present invention can provide a fluorine group-containing release film which has superior peelability, is excellent in appearance characteristics of the release layer thereof due to improved coating properties, can reduce the number of defects, such as pinholes, occurring during coating, and can improve the cost effectiveness of a product.

Description

Fluorine group-containing release film

The present invention relates to a release film containing a fluorine group, and more particularly, on at least one surface of a polyester base film, fluorine in which a release coating solution containing an organo polysiloxane containing a fluorine group and an organo polysiloxane containing no fluorine group is applied. It relates to a group-containing release film.

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

When using such a silicone adhesive, a release film having excellent peelability is required. In the case of a generally known silicone release film, there is a problem that when the silicone of the release coating layer has good compatibility with the silicone adhesive layer, it does not peel. For this reason, as a release film for use with a silicone pressure-sensitive adhesive, a film coated with a release agent containing a fluorine-based resin is commonly used.

However, since the release agent containing fluorine-based resin used as a release agent has low surface energy and is not compatible with general organic oils, it may cause coating defects such as pinhole defects.Therefore, a fluorine-based solvent must be used when diluting or coating the coating solution. In addition, in the case of such a fluorine-based solvent, since it is very volatile, it is difficult to keep the coating thickness constant when coating the film, and thus, staining of the coating layer due to poor leveling during coating, and variations in peel force due to variations in coating thickness may occur. . In order to solve the problem that the fluorine-based polymer cannot be dissolved as such an organic solvent that does not contain fluorine, it has been proposed that peeling is possible with a combination of a silicone pressure-sensitive adhesive containing a phenyl group and an addition-reactive silicone release agent (for example, Japanese patent Publication No. 10-147758), there was a problem such as an increase in peeling force as time passed.

In addition, since fluorine-based solvents and releasing agents containing fluorine-based resins are tens of times more expensive than general organic solvents and silicone-based releasing agents, they have various disadvantages in terms of productivity. Despite the excellent properties of silicone-based adhesives, these disadvantages of the release film The amount of usage is not increasing exponentially.

[Prior technical literature]

[Patent Literature]

(Patent Document 1) Japanese Patent Laid-Open Publication No. Hei 10-147758

The present invention was conceived to solve the above problems and to meet the conventional requirements, and the object of the present invention is to improve the coating property at the same time excellent peelability, so that the appearance characteristics of the release layer are excellent, and pinholes generated during coating. It is intended to provide a release film containing a fluorine group that can reduce the number of defects in the product and improve the cost-effectiveness ratio of the product.

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

The object includes a base film and a release layer positioned on at least one side of the base film, wherein the release layer comprises organo polysiloxane (A) containing a fluoro group and organo polysiloxane (B) containing no fluoro group. It is a cured layer of the included release coating liquid, and the release layer is achieved by a fluorine group-containing release film in which the fluorine atom/silicon atom content ratio decreases from the surface to the core.

Here, the release coating liquid is characterized in that it further comprises a hydroelectric polysiloxane.

Preferably, the organopolysiloxane (A) containing a fluoro group is characterized in that it contains at least one fluorine-containing substituent of at least one of an alkenyl group having 2 to 10 carbon atoms and a fluoroalkyl group or a fluoroether group per molecule. do.

Preferably, the organo polysiloxane (A) containing a fluoro group has the structure of the following formula (1),

(Chemical Formula 1)

And Ra is a monovalent hydrocarbon group excluding an aliphatic unsaturated group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and Rb is a monovalent hydrocarbon group excluding an aliphatic unsaturated group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms Or a hydrogen group, Rc is a fluoroalkyl group or a fluoroether group containing at least one of at least one fluorinated substituent, a monovalent hydrocarbon group excluding an aliphatic unsaturated group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and At least one type of hydrogen group is included, and each of X, Y, and Z is an integer of 1 or more.

Preferably, the fluoroalkyl group has the structure of the following formula (2),

(Chemical Formula 2)

And n is an integer of 1 to 8, and m is an integer of 1 to 5.

Preferably, the fluoroether group has the structure of the following formula (3),

(Chemical Formula 3)

And 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.

Preferably, the organopolysiloxane (B) containing no fluoro group is characterized in that it contains an alkyl group or an alkenyl group having 2 to 10 carbon atoms in one molecule.

Preferably, the organo polysiloxane (B) that does not contain a fluoro group has the structure of the following formula (4),

(Formula 4)

And Ra is a monovalent hydrocarbon group excluding an aliphatic unsaturated group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and Rb is a monovalent hydrocarbon group excluding an aliphatic unsaturated group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms Or a hydrogen group, and X and Y are each an integer of 1 or more.

Preferably, the base film is a polyester base film, which is characterized in that it is polyethylene terephthalate (PET) or polyethylene-2,6-nathalenedicarboxylate (PEN).

Preferably, the organo polysiloxane (B) containing no fluoro group is characterized in that it contains 10 parts by weight to 900 parts by weight based on 100 parts by weight of the organo polysiloxane (A) containing a fluoro group.

Preferably, the hydroelectricity bonded to the silicon atom of the hydroelectric polysiloxane is characterized in that it contains 1.0 to 3.0 hydroelectricity with respect to one total alkenyl group of the organopolysiloxane (A, B).

Preferably, the organopolysiloxane (A) and the organopolysiloxane (B) of the release layer are characterized in that they contain at least one form of addition reaction type, condensation reaction type and ultraviolet curing type siloxane resin.

Preferably, the surface of the release layer is characterized in that it contains 80 Atomic% or more of fluorine atoms relative to 100 Atomic% of silicon atoms as a result of XPS analysis.

Preferably, the deep portion of the release layer is characterized in that it contains less than 80 Atomic% of fluorine atoms relative to 100 Atomic% of silicon atoms as a result of XPS analysis.

Preferably, the thickness after drying of the release layer is characterized in that 0.03 to 2.0 ㎛.

Preferably, the release film is characterized in that the peeling force between the release layer and the silicone adhesive is 0.5gf/25mm to 20 gf/25mm at a peeling angle of 180° and a peeling speed of 0.3mpm.

Preferably, the release film is characterized in that the residual adhesion rate is 85% or more.

Preferably, the release layer is characterized in that the number of pinholes is 2 / A4 size or less.

According to the present invention, it is possible to dilute and apply the coating solution without using a fluorine-based solvent in the release coating solution, so that the coating property is improved, the appearance characteristics of the release layer are improved, and the number of defects such as pinholes generated during coating is reduced. have.

Further, the present invention has an effect such as improvement in peelability and peel force deviation by a uniform coating layer.

In addition, the present invention has effects such as reducing the amount of use of organopolysiloxane containing an expensive fluorine group, and improving the cost-effectiveness ratio of a product since it is possible not to use an expensive fluorine-based solvent.

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 following description.

1 is a schematic cross-sectional view of a release film containing a fluorine group 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 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. Also, although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.

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

In describing and/or claiming the present 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 order copolymers.

First, a fluorine group-containing release film according to an aspect of the present invention will be described in detail with reference to FIG. 1, which is a schematic cross-sectional view of a release film containing a fluorine group according to a preferred embodiment of the present invention.

Referring to FIG. 1, a fluorine group-containing release film 100 according to an embodiment of the present invention includes a base film 10 and a release layer 20 positioned on at least one side of the base film, and a release layer ( 20) is a cured layer of a release coating solution containing an organo polysiloxane (A) containing a fluoro group and an organo polysiloxane (B) containing no fluoro group.

As a result of trying to provide a release film capable of satisfying excellent release characteristics and appearance characteristics for a silicone-based adhesive, organo polysiloxane containing fluorine group on at least one side of polyester base film and organo polysiloxane containing no fluorine group By applying a release coating solution including a bar to provide a release film having excellent release characteristics and coating appearance characteristics and improved cost-effectiveness, each component will be described in detail below.

1. Base film (10)

The base film is a polyester base film, and the polyester resin used therein may use 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 applicant of the present invention. The polyester base film disclosed in Korean Patent Registration No. 10-1268584, Korean Patent Application Publication Nos. 2012-45213 and 2012-99546, which are prior inventions, will be applied. However, in the embodiments of the present invention, in order to describe only the features of the present invention, the polyester base film is described without particular limitation, but it should be understood that the polyester base film includes the technical features of the known polyester base film.

Specifically, the base film is described centering on polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, but the base material of the silicone release coating solution of the present invention is not limited to a polyester sheet or film. The polyester resin forming the base film is a polyester obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic glycol, and the aromatic dicarboxylic acid is 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 as aliphatic glycols, ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanol, Neopentyl glycol or the like can be used. These polyester resins may be used in combination of two or more of a dicarboxylic acid component and a glycol component, and a copolymer containing a third component is also possible.

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

In addition, the polyester base film according to the present invention may contain particles to impart excellent rolling characteristics between rolls, and there is no particular limitation on the kind as long as the added particles can exhibit excellent sliding characteristics.

Specifically, particles such as silica, silicon oxide, calcium carbonate, calcium sulfate, calcium phosphate, magnesium carbonate, magnesium phosphate, barium carbonate, kaolin, aluminum oxide, titanium oxide, etc. may be included. Although not limited, preferably, any of spherical, bulk, rod, and plate particles may be used.

In addition, the hardness, specific gravity and color of the particles are not particularly limited, but two or more types may be used in parallel if necessary, and the average particle diameter of the particles used is preferably 0.1 to 5 μm, more preferably 0.1 It is used in the range of 2 μm. At this time, if the average particle diameter of the particles is less than 0.1 μm, aggregation between particles may occur, resulting in poor dispersion. On the other hand, if the average particle diameter of the particles exceeds 5 μm, the surface roughness characteristics of the film deteriorate during post-processing. Coating failure may occur.

In addition, when the polyester base film contains particles, the preferred particle content is 0.01 to 5% by weight, more preferably 0.01 to 3% by weight. If the particle content is less than 0.01% by weight, the slip property of the polyester film may be deteriorated, resulting in poor running characteristics between rolls, and if the content exceeds 5% by weight, the surface smoothness of the film may be deteriorated.

2. Release layer (20)

The release layer is located on at least one side of the base film, and is a cured layer of a release coating solution containing organo polysiloxane (A) containing a fluorine group and organo polysiloxane (B) containing no fluorine group.

In the release coating solution of the present invention, organopolysiloxane (A, B) is a main component of the release coating solution, and organopolysiloxane (A) and organopolysiloxane (B) may be present as respective molecules, and are connected by one copolymer. It may be. In addition, these can be used in any type of addition reaction type, condensation reaction type, and ultraviolet curing type siloxane resin, and are not specifically limited to any one.

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

Specifically, it is preferable to have the structure of the following formula (1).

(Chemical Formula 1)

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

Rb is a monovalent hydrocarbon group excluding an aliphatic unsaturated group 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 a hydroxy group, a cyano group, etc., and an alke having 2 to 10 carbon atoms It may be a nil group or a hydrogen group.

Rc is a monovalent hydrocarbon group excluding an aliphatic unsaturated group having 1 to 10 carbon atoms and containing at least one fluorinated substituent in at least one fluoroalkyl group or fluoroether group, specifically an alkyl group, an aryl group, and a hydrogen atom of these groups At least one of a hydroxy group, a hydrocarbon group having a cyano group, an alkenyl group having 2 to 10 carbon atoms, and a hydrogen group may be included.

In addition, X, Y, and Z are integers of X≥1, Y≥1, and Z≥1, respectively.

In one embodiment, it is preferable that the fluoroalkyl group of Formula 1 is the following Formula 2, and the fluoroether group has the structure of Formula 3 below.

(Chemical Formula 2)

Here, n is an integer of 1 to 8 and m is an integer of 1 to 5.

(Chemical Formula 3)

Here, 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) without a fluorine group may have an alkenyl group bonded to a silicon atom in any part of the molecule, preferably contains at least two or more, and, The molecular structure is any one selected from linear or branched, and a structure in which linear and branched coexist is also preferable.

Specifically, it is preferable to have the structure of the following formula (4).

(Formula 4)

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

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

In addition, X and Y are integers of X≥1 and Y≥1, respectively.

In one embodiment, the organo polysiloxane (B) is preferably 10 parts by weight to 900 parts by weight based on 100 parts by weight of the organo polysiloxane (A). If the amount is less than 10 parts by weight, the peeling characteristics are not improved and compatibility with non-fluorine-based solvents deteriorates, causing problems in appearance characteristics such as pinholes during coating.If the amount exceeds 900 parts by weight, the fluorine atom on the surface is small, so when bonding with a silicone adhesive. A problem that does not peel off occurs.

In one embodiment, when the surface of the release layer is analyzed with an XPS analyzer, it is preferable that the surface of the release layer contains 80 Atomic% or more of fluorine atoms relative to 100 Atomic% of silicon atoms. If the fluorine atom is less than 80 Atomic%, there is a problem that peeling does not occur when laminated with a silicone adhesive.

In addition, when the surface of the release layer is etched by plasma treatment and the inside of the release layer is analyzed by an XPS analyzer, it is preferable that the deep portion of the release layer contain less than 80 Atomic% of fluorine atoms relative to 100 Atomic% of silicon atoms. In the present specification, "deep" refers to the inside of the release layer in which the surface of the release layer is etched with plasma, and more specifically, the release layer in which the Atomic% of C (carbon) is 60% from the surface of the release layer when analyzed with an XPS analyzer Refers to the point inside the floor. Since the fluorine atoms in the release layer are more advantageous in releasability as they are located on the surface of the coating layer, when the fluorine atom is 80 Atomic% or more inside the release layer, the specific gravity of fluorine atoms on the surface of the release layer decreases, resulting in a relatively increased content of silicon atoms, resulting in a combination with a silicone adhesive. There is a problem that the peeling does not occur.

In addition, as the content of the fluorine atom relative to the silicon atom is higher, the release layer has a better peeling property when laminating with a silicon-based adhesive, and when the content of the silicon atom relative to the fluorine atom is high, the peeling property is deteriorated. For this reason, it is preferable in terms of peelability that the content ratio of fluorine atoms to silicon atoms in the release layer tends to decrease from the surface layer to the deep part of the release layer.

In addition, the release coating solution may further contain a hydroelectric polysiloxane as a curing agent, and any type such as an addition type, a condensation type, and an ultraviolet curing type may be used, and it is not specifically limited to any one. In addition, the hydroelectric polysiloxane may be linear, branched, or cyclic, and a mixture thereof may be used. In addition, the viscosity or molecular weight is not limited, but the compatibility with the organopolysiloxane (A,B) should be good, and the hydropre-polysiloxane does not have to contain a fluorine group, but preferably the same fluorine as the organopolysiloxane (A). It is more preferable that a group is included.

In addition, the amount of hydroelectric polysiloxane is preferably in the range of 1.0 to 3.0 hydroelectricity bonded to silicon atoms with respect to one total alkenyl group of the organopolysiloxane (A, B). If the number of hydrogen atoms bonded to silicon atoms for one alkenyl group of organopolysiloxane is less than 1.0, good curability cannot be obtained, and if it exceeds 3.0, there are many hydrogen atoms remaining in the coating layer after curing, causing problems such as changes in peel force over time. There is a possibility of occurrence.

In addition, the release coating liquid may include a platinum chelate catalyst as a catalyst.

In addition, the release coating solution is diluted with a solvent so that the total solid content is 0.5 to 10% by weight, and then coated on at least one side of the base film. At this time, the solvent used for the release coating solution may be used without limitation of the kind as long as it can be applied on the base film by dispersing the solid content of the present invention. If the total solid content of the release coating liquid is less than 0.5% by weight, a uniform release coating layer is not formed, which may cause problems such as not being properly peeled between the silicone-based adhesive layer and the release film. If it exceeds 10% by weight, the coating liquid The high viscosity of the coating layer may cause unevenness in the leveling of the coating layer, and thus the thickness uniformity of the release layer may deteriorate.

The release layer according to the present invention may use a conventionally known coating method such as bar coating, gravure coating, and die coating.

In one embodiment, the thickness of the release layer after drying is preferably 0.03 to 2.0 μm. If the thickness of the release layer is less than 0.03㎛, the coverage of the release layer is not good, so there may be a problem of not being peeled when laminating with a silicone adhesive. If the thickness of the release layer exceeds 2㎛, problems such as drying may occur. There is a problem that the peeling property is not improved, and the cost-effectiveness ratio is deteriorated.

In one embodiment, the release film has a peeling force between the release layer and the silicone adhesive is 0.5 gf/25mm to 20 gf/25mm at a 180° peeling angle and a 0.3mpm peeling rate, and preferably 1gf/25mm to 10 gf/25mm to be. At this time, if the peel force is less than 0.5 gf/25mm, the adhesion between the release layer and the silicone adhesive may deteriorate, resulting in a problem of lifting the laminated interface such as tunneling, and if the peeling force exceeds 20 gf/25mm, the silicone adhesive It may not be properly peeled off, which may cause problems in the process.

In one embodiment, it is preferable that the release film has a residual adhesion ratio of 85% or more. If the residual adhesive rate is less than 85%, the release agent may be transferred to the adhesive layer due to insufficient curing of the release layer, and the adhesive properties of the adhesive may deteriorate.

In one embodiment, it is preferable that the number of pinholes in the release layer is 2/A4 size or less. When the number of pinholes exceeds 2/A4 size, a pinhole defect may occur, and for example, transfer marks and peeling defects of the same type may occur on the adhesive layer.

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

[Example]

[Example 1]

For 100 parts by weight of organo polysiloxane (A, Dow Chemical, Q2-7785) containing a fluoro group in a polyester film (Toray Advanced Materials, XD500P-30㎛), organopolysiloxane (B , Shin-Etsu Silicone Co., KS-847H) 100 parts by weight, Hydrogen polysiloxane (manufactured by Dow Chemical, Q2-7560) 3 parts by weight, platinum chelate catalyst (manufactured by Dow Chemical, SYL-OFF 4000) 500 ppm in a heptane solution It was diluted to prepare and apply a release coating solution having a total solid content of 6% by weight. After coating, heat treatment was performed in a hot air dryer at 150° C. for 60 seconds to form a release layer having a thickness of 0.5 μm to prepare a release film.

[Example 2]

In Example 1, a release film was prepared in the same manner as in Example 1, except that 10 parts by weight of organopolysiloxane (B, manufactured by Shin-Etsu Silicone, KS-847H) was used.

[Example 3]

In Example 1, a release film was prepared in the same manner as in Example 1, except that 500 parts by weight of organopolysiloxane (B, manufactured by Shin-Etsu Silicone, KS-847H) was used.

[Example 4]

In Example 1, a release film was prepared in the same manner as in Example 1, except that 900 parts by weight of organo polysiloxane (B, manufactured by Dow Chemical, LTC-750A) was used.

[Example 5]

A release film was prepared in the same manner as in Example 1, except that a release coating solution having a total solid content of 8% by weight was prepared in Example 1 to form a release layer having a thickness of 1.0 μm.

[Example 6]

A release film was prepared in the same manner as in Example 1, except that a release coating solution having a total solid content of 10% by weight was prepared in Example 1 to form a release layer having a thickness of 1.8 μm.

[Comparative Example]

[Comparative Example 1]

A release film was prepared in the same manner as in Example 1, except that the organo polysiloxane (B) was not used in Example 1.

[Comparative Example 2]

In Example 1, a release film was prepared in the same manner as in Example 1, except that 1,250 parts by weight of organo polysiloxane (B, manufactured by Shin-Etsu Silicone, KS-847H) was used.

[Comparative Example 3]

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

[Comparative Example 4]

A release film was prepared in the same manner as in Example 1, except that a release coating solution having a total solid content of 15% by weight was prepared in Example 1 to form a release layer having a thickness of 2.5 μm.

Physical properties were measured through the following experimental examples using the release films according to Examples 1 to 6 and Comparative Examples 1 to 4, 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. Coating layer surface analysis

The surface of the release film prepared in Examples and Comparative Examples was analyzed by using an XPS analyzer (ThermoFisher company: model name K-ALPHA) to an analysis area (Spot size) of 400 µm to determine the composition of Si, F, C, and O atoms. The analysis was expressed as Atomic %, and the results are shown in Table 1 as follows.

1-2. In-depth analysis of coating layer

The surface of the coating layer of the release film prepared in Examples and Comparative Examples was subjected to Ar plasma treatment for 30 seconds under the condition of Ion Energy 3000eV to etch the surface of the coating layer, and then the above 1-1. XPS analysis was performed under the same conditions as the surface analysis of the coating layer, 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 at which the Atomic% of C (carbon) is 60% from the surface of the release layer is expressed as a deep part, and the XPS analysis results in the deep part are shown in Table 1 below.

2. Measurement of peel force of release film

The release films prepared in Examples and Comparative Examples were measured as follows, and the results are shown in Table 1 below.

[Sample preparation]

① Release-coated measurement sample is stored at 25℃ and 65%RH for 24 hours

② After attaching silicone adhesive tape (Nitto 903UL) to the release coated surface, measure the physical properties after compressing this sample with a load of 20g/cm ² at 50℃ for 24 hours

[Measurement equipment]

cheminstrument AR-1000

[How to measure]

① 180° peeling angle, peeling speed 0.3mpm

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

[Measurement data]

Peel force unit is gf/25mm and the measured value is measured 5 times to calculate the average value

3. Analysis of residual adhesion rate of release film

[Sample preparation]

① Release-coated measurement sample is stored at 25 ℃, 65%RH for 24 hours

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

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

[Measurement equipment]

cheminstrument AR-1000

[How to measure]

① 180° peeling angle, peeling speed 0.3mpm

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

[Measurement data]

4. Evaluation of coating layer appearance of release film

The surface appearance of the coating layer of the release films prepared in Examples and Comparative Examples was evaluated, and the results are shown in Table 1 below.

[Assessment Methods]

The release films prepared in Examples and Comparative Examples were prepared in A4 size, placed on an evaluation plate with a black bottom, and the number of pinholes of 300 μm or more was recorded under a fluorescent lamp.

○: Less than 2 pinholes/A4 size

△: 3 to 5 pinholes/A4 size

	Surface XPS(Atomic%)			Deep XPS (Atomic %)			Peel force (gf/25mm)	Residual adhesion rate (%)	Appearance evaluation
	Si	F	F/Si ratio	Si	F	F/Si ratio
Example 1	16	32	2.00	30	3	0.10	8.2	94	○
Example 2	14	36	2.57	15	5	0.33	7.9	92	○
Example 3	15	32	2.13	21	2	0.10	9.8	95	○
Example 4	18	28	1.55	20	3	0.15	11.5	94	○
Example 5	16	32	2.00	22	3	0.14	6.8	92	○
Example 6	15	33	2.20	18	5	0.28	5.3	91	○
Comparative Example 1	12	36	3.00	17	13	0.76	8.1	91	X
Comparative Example 2	26	18	0.69	18	3	0.17	82.0	97	○
Comparative Example 3	16	20	1.25	3	4	1.33	112.1	95	△
Comparative Example 4	21	32	1.52	17	16	0.94	53.4	83	X

As can be seen from Table 1, it can be seen that the release films prepared in Examples 1 to 6 according to the present invention have excellent releasability to silicone-based adhesives and excellent coating appearance characteristics. On the other hand, when the composition of the organopolysiloxane of the release layer is not suitable (Comparative Examples 1 and 2), or the coating thickness of the release layer is not optimized (Comparative Examples 3 and 4), the coating appearance characteristics deteriorate and the peeling characteristics are poor. It can be seen that it is settling.

As described above, the present invention provides a release film comprising a release layer positioned by applying a release coating solution including an organo polysiloxane containing a fluorine group and an organo polysiloxane containing no fluorine group on at least one surface of a base film, It is possible to dilute and coat the coating solution without using a fluorine-based solvent, so that workability is improved, and uniform coating is possible, so that the peelability and deviation of the peel force can be improved.

Furthermore, since the use of organopolysiloxane containing expensive fluorine can be minimized, a product having a high cost-effectiveness ratio to excellent physical properties can be manufactured, and excellent physical properties when the release film according to the present invention is applied in the silicone-based adhesive processing process. In addition, cost savings can be expected.

In the present 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 it is obvious that it may be modified and variously implemented by those skilled in the art.

[Explanation of code]

100: fluorine group-containing release film

10: base film

20: release layer

Claims (18)

1. Base film,

   Including a release layer located on at least one side of the base film,

   The release layer is a cured layer of a release coating solution comprising an organo polysiloxane (A) containing a fluoro group and an organo polysiloxane (B) not containing a fluoro group,

   The release layer is a fluorine group-containing release film in which the fluorine atom/silicon atom content ratio decreases from the surface to the deep part.
2. The method of claim 1,

   The release coating solution further comprises a hydroelectric polysiloxane, a fluorine group-containing release film.
3. The method of claim 1,

   The organopolysiloxane (A) containing a fluoro group contains at least one fluorine-containing substituent of at least one of an alkenyl group having 2 to 10 carbon atoms and a fluoroalkyl group or a fluoroether group in one molecule. .
4. The method of claim 1,

   The organo polysiloxane (A) containing the fluoro group has the structure of the following formula (1),

   (Chemical Formula 1)

   

   And Ra is a monovalent hydrocarbon group excluding an aliphatic unsaturated group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and Rb is a monovalent hydrocarbon group excluding an aliphatic unsaturated group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms Or a hydrogen group, Rc is a fluoroalkyl group or a fluoroether group, wherein at least one fluorinated substituent is included, and a monovalent hydrocarbon group excluding an aliphatic unsaturated group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and At least one type of hydrogen group is contained, and X, Y, and Z are each an integer of 1 or more.
5. The method of claim 4,

   The fluoroalkyl group has the structure of the following formula (2),

   (Chemical Formula 2)

   

   And, n is an integer of 1 to 8, m is an integer of 1 to 5, a fluorine group-containing release film.
6. The method of claim 4,

   The fluoroether group has the structure of the following formula (3),

   (Chemical Formula 3)

   

   And 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.
7. The method of claim 1,

   The organopolysiloxane (B) not containing a fluoro group contains an alkyl group or an alkenyl group having 2 to 10 carbon atoms in one molecule.
8. The method of claim 1,

   The organo polysiloxane (B) that does not contain a fluoro group has the structure of the following formula (4),

   (Formula 4)

   

   And Ra is a monovalent hydrocarbon group excluding an aliphatic unsaturated group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and Rb is a monovalent hydrocarbon group excluding an aliphatic unsaturated group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms Or a hydrogen group, X and Y are each an integer of 1 or more, a fluorine group-containing release film.
9. The method of claim 1,

   The base film is a polyester base film, which is polyethylene terephthalate (PET) or polyethylene-2,6-nathalenedicarboxylate (PEN), a fluorine group-containing release film.
10. The method of claim 1,

    The organo polysiloxane (B) containing no fluoro group includes 10 parts by weight to 900 parts by weight based on 100 parts by weight of the organo polysiloxane (A) containing the fluoro group.
11. The method of claim 1,

    Hydroelectricity bonded to the silicon atom of the hydroelectric polysiloxane contains 1.0 to 3.0 hydroelectricity with respect to one total alkenyl group of the organopolysiloxane (A, B), a fluorine group-containing release film.
12. The method of claim 1,

    The organo polysiloxane (A) and the organo polysiloxane (B) contain one or more forms of addition reaction type, condensation reaction type and ultraviolet curing type siloxane resin, a fluorine group-containing release film.
13. The method of claim 12,

    A release film containing a fluorine group containing 80 Atomic% or more of fluorine atoms relative to 100 Atomic% of silicon atoms as a result of XPS analysis on the surface of the release layer.
14. The method of claim 12,

    A release film containing a fluorine group containing less than 80 Atomic% of fluorine atoms relative to 100 Atomic% of silicon atoms as a result of XPS analysis of the deep portion of the release layer.
15. The method of claim 1,

    The thickness after drying of the release layer is 0.03 to 2.0 ㎛, a fluorine group-containing release film.
16. The method of claim 1,

    The release film is a release film containing a fluorine group having a peeling force of the release layer and the silicone adhesive is 0.5 gf/25mm to 20 gf/25mm at a peeling angle of 180° and a peeling rate of 0.3mpm.
17. The method of claim 1,

    A release film containing a fluorine group having a residual adhesion rate of 85% or more of the release film.
18. The method of claim 1,

    The release layer is the number of pinholes 2 / A4 size or less, a fluorine group-containing release film.

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