KR102054615B1 - Release film comprising fluorine group - Google Patents

Abstract

The present invention relates to a fluorine group-containing release film and, more specifically, to a fluorine group-containing release film, which has excellent appearance properties of a release layer due to excellent peelability and improved coating properties, reduces the number of defects such as a pinhole and the like generated during coating, and improves cost effectiveness of a product.

Description

Fluorine group containing release film {RELEASE FILM COMPRISING FLUORINE GROUP}

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

In general, silicone-based pressure-sensitive adhesives have advantages such as heat resistance, friction resistance, and flexibility, and have been recently 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 pressure-sensitive adhesive is required a release film excellent in peelability, in the case of a generally known silicone-based release film there is a problem that the silicone of the release coating layer is not peeled when the compatibility with the silicone pressure-sensitive adhesive layer is good. For this reason, the film to which the mold release agent containing a fluorine-type resin was apply | coated is often used for the release film for silicone type adhesive use.

However, the release agent containing fluorine-based resin used as a release agent has low surface energy and is not compatible with general organic emulsions, which may cause coating defects such as pinhole defects. Therefore, a fluorine-based solvent should be used when diluting or coating the coating solution. In addition, in the case of such a fluorine-based solvent is very volatile, it is difficult to maintain a constant coating thickness when coating on the film, the coating may cause a staining of the coating layer due to the leveling defects and the peel force variation due to the coating thickness variation may occur. . As described above, in order to solve the problem of not being able to dissolve the fluorine-based polymer as the organic solvent which does not contain fluorine, it is proposed that peeling is possible by a combination of a silicone pressure-sensitive adhesive containing a phenyl group and an addition reaction type silicone release agent (for example, Japanese Patent Publication No. Hei 10-147758), there was a problem that the peel force is increased over time.

In addition, the release agent containing a fluorine-based solvent and a fluorine-based resin has several disadvantages in terms of productivity since it is tens of times more expensive than a general organic solvent and a silicone-based release agent. Usage is not growing exponentially.

Japanese Patent Laid-Open No. 10-147758

The present invention has been made to solve the above problems and to meet the conventional requirements, the object of the present invention is excellent peelability and coating property is improved at the same time, the appearance characteristics of the release layer is excellent, such as pinholes generated during coating It is an object of the present invention to provide a fluorine group-containing release film which can reduce the number of defects and improve the cost-effectiveness of a product.

These 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 surface of the base film, wherein the release layer comprises an organo polysiloxane (A) containing a fluoro group and an organo polysiloxane (B) not containing a fluoro group. It is a cured layer of the release coating liquid containing, and a release layer is achieved by the fluorine-group containing release film in which the fluorine atom / silicon atom content ratio decreases from the surface to the deep part.

Here, the release coating solution is characterized in that it further comprises a hydropolysiloxane.

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

Preferably, the organopolysiloxane (A) containing a fluoro group has the structure of Formula 1,

(Formula 1)

Ra is a monovalent hydrocarbon group or an alkenyl group having 2 to 10 carbon atoms except for an aliphatic unsaturated group having 1 to 10 carbon atoms, and Rb is a monovalent hydrocarbon group or an alkenyl group having 2 to 10 carbon atoms except an aliphatic unsaturated group having 1 to 10 carbon atoms Or a hydrogen group, Rc includes at least one fluorine-containing substituent in at least one fluoroalkyl group or fluoroether group, a monovalent hydrocarbon group other than 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.

Preferably, the fluoroalkyl group has the structure of Formula 2,

(Formula 2)

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

Preferably, the fluoroether group has a structure of Formula 3,

(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, X is an oxygen atom or a single bond.

Preferably, the organopolysiloxane (B) not containing a fluoro group is characterized by including an alkyl group or an alkenyl group having 2 to 10 carbon atoms in one molecule.

Preferably, the organo polysiloxane (B) not containing a fluoro group has a structure of Formula 4,

(Formula 4)

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

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

Preferably, the organopolysiloxane (B) not containing a fluoro group is characterized in that it comprises 10 parts by weight to 900 parts by weight relative to 100 parts by weight of the organo polysiloxane (A) containing a fluoro group.

Preferably, the hydroelectrode bonded to the silicon atom of the hydropolypolysiloxane is characterized in that it comprises 1.0 to 3.0 hydroelectrodes 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 by including at least one type of addition reaction type, condensation reaction type and ultraviolet curing siloxane resin.

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

Preferably, the core portion of the release layer is characterized in that less than 80 Atomic% fluorine atoms compared to 100 Atomic% 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 of the release layer and the silicone pressure-sensitive adhesive is 0.5gf / 25mm to 20 gf / 25mm at 180 ° peel angle, 0.3mpm peeling speed.

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

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

According to the present invention, it is possible to dilute and coat the coating liquid without using a fluorine-based solvent in the release coating liquid, thereby improving coating properties, thereby improving appearance characteristics of the release layer, and reducing the number of defects such as pinholes generated during coating. have.

Furthermore, the present invention has the effect that the peelability and the peeling force deviation are improved by the uniform coating layer.

In addition, the present invention can reduce the amount of the organopolysiloxane containing an expensive fluorine group, and because it can not use an expensive fluorine-based solvent has the effect of improving the caustic ratio of the product.

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

1 is a schematic cross-sectional view of a fluorine group-containing release film according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to embodiments and drawings of the present invention. These examples are only presented by way of example only to more specifically describe the present invention, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples. .

Unless defined otherwise, 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 non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of elements is not necessarily limited to such elements and may not be explicitly listed or include other elements inherent to such process, method, article, or apparatus. It may be. Also, 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 the copolymerization of two or more monomers. Such copolymers include binary copolymers, terpolymers or higher copolymers.

First, the fluorine group-containing release film according to one aspect of the present invention will be described in detail with reference to FIG. 1, which is a cross-sectional schematic diagram of a fluorine group-containing release film according to a preferred 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 positioned on at least one surface of the base film, and includes a release layer ( 20) is a cured layer of a release coating liquid containing an organo polysiloxane (A) containing a fluoro group and an organo polysiloxane (B) not containing a fluoro group.

The present invention is an effort to provide a release film that can satisfy the excellent release properties and appearance properties with respect to the silicone pressure-sensitive adhesive, as a result, at least one surface of the polyester base film organo polysiloxane containing a fluorine group and organo polysiloxane containing no fluorine group It is to provide a release film having excellent release properties and coating appearance properties and improved cost-effectiveness by applying a release coating solution, including, will be described in detail for each component below.

1. Base Film (10)

The base film is a polyester base film, and the polyester resin used therein may be a known base film conventionally used in the field of silicone release coating, but in particular, the polyester base film described in the present invention is an applicant of the present invention. The polyester base film disclosed in the Republic of Korea Patent No. 10-1268584, Republic of Korea Patent Publication No. 2012-45213 and 2012-99546, etc., which are the prior invention by the present invention 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 to include technical features related to a known polyester base film.

Specifically, the base film will be described based on a polyester-based resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc., but the base material of the silicone release coating liquid of the present invention is not limited to a polyester sheet or a film. The polyester resin forming the base film is a polyester obtained by polycondensing aromatic dicarboxylic acid and aliphatic glycol, and examples of the aromatic dicarboxylic acid are isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, Adipic acid, sebacic acid, oxycarboxylic acid (for example, 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. Such polyester-based resin can also use together 2 or more types of a dicarboxylic acid component and a glycol component, and the copolymer containing a 3rd 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. Representative polyester resins include polyethylene terephthalate (PET), polyethylene-2,6-naphthalenedicarboxylate (PEN), and the like.

In addition, the polyester base film according to the present invention may contain particles to give excellent roll-to-roll running characteristics, there is no particular limitation of the kind if the added particles can exhibit excellent slip characteristics.

Specifically, particles of silica, silicon oxide, calcium carbonate, calcium sulfate, calcium phosphate, magnesium carbonate, magnesium phosphate, barium carbonate, kaolin, aluminum oxide, titanium oxide, and the like may be included. Although not limited, Preferably, any of spherical shape, block shape, rod shape, and plate shape particle | grains can be used.

The particle size, specific gravity, and color of the particles are not particularly limited, but two or more kinds 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. Use is in the range of 2 μm. At this time, if the average particle diameter of the particles is less than 0.1㎛, agglomeration between particles may occur, and poor dispersion may occur. On the other hand, if the average particle diameter of the particles exceeds 5㎛, the surface roughness characteristics of the film may be deteriorated, thereby causing post-processing. Coating defects may occur.

In addition, when particle | grains are contained in a polyester base film, preferable particle content is 0.01 to 5 weight%, More preferably, it is 0.01 to 3 weight%. If the particle content is less than 0.01% by weight, the slipping property of the polyester film may deteriorate and the running characteristics between the rolls may deteriorate. When the content is more than 5% by weight, the surface smoothness of the film may deteriorate.

2. Release layer (20)

The release layer is a cured layer of a release coating liquid which is located on at least one surface of the base film and includes an organopolysiloxane (A) containing a fluorine group and an organo polysiloxane (B) containing no fluorine group.

In the release coating solution of the present invention, the organopolysiloxane (A, B) is a main component of the release coating solution, and the organopolysiloxane (A) and the organopolysiloxane (B) may be present in each molecule, and are connected by one copolymer. It may be. Moreover, these can use any type among addition reaction type | mold, condensation reaction type | mold, and ultraviolet curing siloxane resin, and they do not specifically limit to any one.

In one embodiment, the organopolysiloxane (A) containing a pullulor group includes at least one fluorine-containing substituent of 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 preferable to include at least one.

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

(Formula 1)

Ra 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 a hydroxyl group, a cyano group, or the like. It may be a kenyl group.

Rb is a monovalent hydrocarbon group except for 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 hydroxyl group, a cyano group, and the like. It may be a silyl group or a hydrogen group.

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

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

In one embodiment, the fluoroalkyl group of formula 1 is a formula (2), it is preferred that the fluoroether group has a structure of formula (3).

(Formula 2)

Where n is an integer from 1 to 8 and m is an integer from 1 to 5.

(Formula 3)

Here, p is an integer of 1-5, q is an integer of 0 or 1, r is an integer of 0-2, m is an integer of 1-5, X is an oxygen atom or a single bond.

In one embodiment, the organopolysiloxane (B) not containing a pullulor group may be present in any part of the molecule, alkenyl groups bonded to silicon atoms in one molecule, and preferably include at least two or more. The molecular structure is either selected from linear or branched phases, and a structure in which the linear and branched phases coexist.

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

(Formula 4)

Ra 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 a hydroxyl group, a cyano group, or the like. It may be a kenyl group.

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 a hydroxyl group, a cyano group, and the like. 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 organopolysiloxane (B) is preferably 10 parts by weight to 900 parts by weight relative to 100 parts by weight of the organopolysiloxane (A). If it is less than 10 parts by weight, the compatibility with non-fluorinated solvents is not improved without peeling characteristics, and problems in appearance characteristics such as pinholes occur during coating, and if it exceeds 900 parts by weight, the fluorine atom on the surface is small, when laminating with silicone pressure-sensitive adhesive The problem of not peeling occurs.

In one embodiment, when the surface of the release layer is analyzed by the XPS analyzer, the surface of the release layer preferably contains at least 80 Atomic% of fluorine atoms relative to 100 Atomic% of silicon atoms. When the fluorine atom is less than 80 Atomic%, a problem arises in that the fluorine atom does not peel off when laminated with the silicone pressure sensitive 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, the core of the release layer preferably contains less than 80 Atomic% of fluorine atoms relative to 100 Atomic% of silicon atoms. In the present specification, "deep" means the inside of the release layer in which the surface of the release layer is etched by plasma, and more specifically, when the XPS analysis device analyzes the release, the Atomic% of C (carbon) is 60% from the release layer surface. Refers to a point inside the floor. Since the fluorine atoms in the release layer are more advantageous in peelability as they are located on the surface of the coating layer, when the fluorine atoms in the release layer are more than 80 Atomic%, the specific gravity of the fluorine atoms on the surface of the release layer decreases, so that the content of silicon atoms is relatively increased, so that the bonding with the silicone pressure sensitive adhesive is possible. The problem that does not peel off occurs.

In addition, the release layer has a higher peeling property when the content of the fluorine atom relative to the silicon atom is higher when laminating with the silicone pressure sensitive adhesive, and the peeling property is worse when the content of the silicon atom is higher than the fluorine atom. For this reason, it is preferable that the content ratio of the fluorine atoms to the silicon atoms of the release layer tends to decrease from the surface layer of the release layer to the deeper portion in terms of peelability.

In addition, the release coating liquid may further include hydropolypolysiloxane as a curing agent, and may be any type such as addition type, condensation type, ultraviolet curing type, and is not particularly limited to any one type. The hydropolypolysiloxane may be either linear, branched or cyclic, or a mixture thereof. In addition, the viscosity and molecular weight are not limited, but the compatibility with the organopolysiloxane (A, B) should be good, the hydropolypolysiloxane does not have to contain a fluorine group, but preferably the same fluorine as the organopolysiloxane (A) More preferably, groups are included.

In addition, the amount of the hydropolypolysiloxane used is preferably in the range of 1.0 to 3.0 hydroelectrics bonded to the silicon atom with respect to one total alkenyl group of the organopolysiloxane (A, B). If the number of hydrogen atoms bonded to the silicon atom is less than 1.0 with respect to one alkenyl group of the organopolysiloxane, good curability cannot be obtained. If the number exceeds 3.0, there are many hydrogen atoms remaining in the coating layer after curing. There is a possibility to occur.

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

In addition, the release coating solution is diluted in a solvent so that the total solid content of 0.5 to 10% by weight is coated on at least one side of the base film. In this case, the solvent used in the release coating liquid may be used without limitation as long as it can be applied to the base film by dispersing the solid content of the present invention. 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, such that peeling may not be performed properly between the silicone adhesive layer and the release film. High viscosity of the coating layer may cause leveling non-uniformity may result in poor thickness uniformity of the release layer.

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

In one embodiment, the thickness after drying of the release layer is preferably 0.03 to 2.0 ㎛. If the thickness of the release layer is less than 0.03 μm, the coverage of the release layer may not be good, and thus, when the release layer is laminated with the silicone pressure sensitive adhesive, it may not be peeled off. If the thickness of the release layer exceeds 2 μm, problems such as drying may occur. Since the peeling property is not improved, there is a problem that the cost ratio becomes worse.

In one embodiment, the release film is a peel force of the release layer and the silicone pressure-sensitive adhesive is 0.5gf / 25mm to 20 gf / 25mm at 180 ° peel angle, 0.3mpm peeling speed, preferably 1gf / 25mm to 10 gf / 25mm to be. At this time, if the peeling force is less than 0.5gf / 25mm, the adhesion properties between the release layer and the silicone-based adhesive deteriorates, and a problem may arise that the lamination interface, such as tunneling phenomenon, and if the peeling force exceeds 20 gf / 25mm, the silicone-based adhesive Delamination of the wah is not proper and may cause a process problem.

In one embodiment, the residual adhesion rate of the release film is preferably 85% or more. When the residual adhesion rate is less than 85%, there may be a problem that the release agent is transferred to the adhesive layer due to insufficient curing of the release layer, and the adhesive property of the adhesive deteriorates.

In one embodiment, the release layer preferably has two pinholes / A4 size or less. When the number of pinholes exceeds 2 / A4 size, pinhole defects may occur, such as transfer marks and peeling defects having the same shape on the adhesive layer.

Hereinafter, the configuration and effects of the present invention will be described in more detail with reference to Examples and Comparative Examples. However, this embodiment is intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.

EXAMPLE

Example 1

Organopolysiloxane (B) without fluoro group per 100 parts by weight of organopolysiloxane (A, Dow Chemical, Q2-7785) containing a fluoro group in a polyester film (Toray Advanced Materials, XD500P-30 μm) , 100 parts by weight of Shin-Etsu Silicone, KS-847H), 3 parts by weight of all-hydropolysiloxane (Dow Chemical, Q2-7560), 500 ppm of platinum chelate catalyst (DOW Chemical, SYL-OFF 4000) was added to Heptane solution. By diluting, a release coating solution having a total solid content of 6% by weight was prepared and applied. After the application, a heat treatment was performed in a 150 ° C. hot air dryer for 60 seconds to form a release layer having a thickness of 0.5 μm, thereby preparing a release film.

Example 2

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

Example 3

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

Example 4

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

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 wt% 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 wt% 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 organopolysiloxane (B) was not used in Example 1.

Comparative Example 2

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

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 wt% was prepared in Example 1 to form a release layer having a thickness of 2.5 μm.

Physical properties of the release films according to Examples 1 to 6 and Comparative Examples 1 to 4 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 release layer

1-1. Coating Surface Analysis

The surface of the release film prepared in Examples and Comparative Examples was analyzed with a spot size of 400 μm using an XPS analyzer (ThermoFisher, Model K-ALPHA) to determine the composition for Si, F, C, and O atoms Analyzes are expressed in Atomic% and the results are shown in Table 1 as follows.

1-2. Coating Layer Deep Analysis

After coating the surface of the coating layer of the release film prepared in Examples and Comparative Examples by etching the Ar plasma for 30 seconds under Ion Energy 3000eV conditions 1-1. XPS analysis was performed under the same conditions as the surface analysis of the coating layer. Plasma treatment and XPS analysis were repeated until the Atomic% of C (carbon) was 80% or more. The point where Atomic% of C (carbon) is 60% from the surface of the release layer is expressed as the core and the results of XPS analysis at the core are shown in Table 1 below.

2. Measurement of peeling 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 Preservation of release coated samples for 24 hours at 25 ° C and 65% RH

② After attaching the silicone adhesive tape (Nitto 903UL) to the release coating surface, crimp this sample under the load of 20g / cm ² at 50 ℃ for 24 hours and measure the physical properties.

[Measuring equipment]

cheminstrument AR-1000

[How to measure]

① 180 ° peeling angle, peeling speed 0.3mpm

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

[Measurement data]

Peeling force unit is gf / 25mm and measured value is calculated 5 times to calculate average value

3. Analysis of residual adhesion rate of release film

[Sample preparation]

① Preservation of release-coated measurement samples at 25 ° C and 65% RH for 24 hours

② Attach standard adhesive tape (Nitto 31B) to the release coating surface and compress this sample for 24 hours at 20g / cm ² at room temperature.

③ After collecting the adhesive tape adhered to the silicon surface from above without contamination, adhere it to the flat and clean PET FILM surface, and then reciprocally press once with 2kg tape roller (ASTMD-1000-55T).

[Measuring equipment]

cheminstrument AR-1000

[How to measure]

① 180 ° peeling angle, peeling speed 0.3mpm

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

[Measurement data]

4. Evaluation of coating layer appearance of release film

The coating layer surface appearance 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 having a black bottom, and the number of pinholes having a diameter of 300 μm or more under fluorescent lamps was recorded.

○: 2 or less pinholes / A4 size

△: 3 to 5 pinholes / A4 size

Surface XPS (Atomic%) Deep XPS (Atomic%) Peel force
(gf / 25mm) Residue
Adhesion Rate (%) Exterior
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 in Table 1, the release film prepared in Examples 1 to 6 according to the present invention can be confirmed that the excellent peelability for the silicone-based pressure-sensitive adhesive, the coating appearance characteristics are excellent.

On the other hand, if the composition of the organopolysiloxane of the release layer is not suitable (Comparative Examples 1, 2), or the release layer is not optimized for coating thickness (Comparative Examples 3, 4), the coating appearance properties are poor and the peeling properties are poor. It can confirm that it disappears.

As described above, the present invention provides a release film comprising a release layer which is located by applying a release coating solution containing an organopolysiloxane containing a fluorine group and an organopolysiloxane containing no fluorine group on at least one surface of the base film, Dilution and coating of the coating liquid can be performed without using a fluorine-based solvent, thereby improving workability, and uniform coating can be obtained, thereby improving the peelability and the peeling force variation.

Furthermore, since the amount of organopolysiloxane containing expensive fleurs can be minimized, it is possible to manufacture a product having a high cost-performance ratio and excellent physical properties. 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 thereto, but may be variously modified and implemented by those skilled in the art.

100: fluorine group-containing release film
10: base film
20: release layer

Claims (18)

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 containing an organo polysiloxane (A) containing a fluoro group and an organo polysiloxane (B) not containing a fluoro group,
The release layer has a fluorine atom / silicon atom content ratio decreases from the surface to the deeper,
The surface of the release layer contains 80 Atomic% or more of fluorine atoms compared to 100 Atomic% of silicon atoms as a result of XPS analysis,
The core portion of the release layer contains less than 80 Atomic% fluorine atoms compared to 100 Atomic% silicon atoms as a result of XPS analysis, fluorine group-containing release film. The method of claim 1,
The release coating solution further comprises a hydropolypolysiloxane, fluorine group-containing release film. The method of claim 1,
The organopolysiloxane (A) containing the fluoro group includes at least one fluorine-containing substituent containing at least one of an alkenyl group having 2 to 10 carbon atoms and a fluoroalkyl group or a fluoroether group in one molecule. . The method of claim 1,
The organo polysiloxane (A) containing the fluoro group has the structure of Formula 1,
(Formula 1)

Ra is a monovalent hydrocarbon group or an alkenyl group having 2 to 10 carbon atoms except for an aliphatic unsaturated group having 1 to 10 carbon atoms, and Rb is a monovalent hydrocarbon group or an alkenyl group having 2 to 10 carbon atoms except an aliphatic unsaturated group having 1 to 10 carbon atoms Or a hydrogen group, Rc includes at least one fluorine-containing substituent in at least one fluoroalkyl group or fluoroether group, a monovalent hydrocarbon group other than an aliphatic unsaturated group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and At least 1 type of hydrogen group is contained, and X, Y, Z are the fluorine group containing mold release film which is an integer of 1 or more, respectively. The method of claim 4, wherein
The fluoroalkyl group has the structure of Formula 2,
(Formula 2)

And n is an integer of 1-8, m is an integer of 1-5, The fluorine group containing mold release film. The method of claim 4, wherein
The fluoroether group has a structure of Formula 3,
(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, X is an oxygen atom or a single bond, a fluorine group-containing release film. The method of claim 1,
The organopolysiloxane (B) which does not contain the said fluoro group contains the alkyl group or the C2-C10 alkenyl group in 1 molecule, The fluorine group containing mold release film. The method of claim 1,
The organopolysiloxane (B) not containing the fluoro group has a structure of Formula 4,
(Formula 4)

Ra is a monovalent hydrocarbon group or an alkenyl group having 2 to 10 carbon atoms except for an aliphatic unsaturated group having 1 to 10 carbon atoms, and Rb is a monovalent hydrocarbon group or an alkenyl group having 2 to 10 carbon atoms except an aliphatic unsaturated group having 1 to 10 carbon atoms Or a hydrogen group, X and Y each being an integer of 1 or more, a fluorine group-containing release film. The method of claim 1,
The base film is a polyester base film, polyethylene terephthalate (PET) or polyethylene-2,6-naphthalene dicarboxylate (PEN), fluorine group-containing release film. The method of claim 1,
The organopolysiloxane (B) not containing the fluoro group is 10 to 900 parts by weight based on 100 parts by weight of the organopolysiloxane (A) containing the fluoro group, fluorine group-containing release film. The method of claim 2,
The hydroelectric bond to the silicon atom of the hydropolypolysiloxane is a fluorine group-containing release film, containing 1.0 to 3.0 hydroelectric with respect to one of the total alkenyl groups of the organopolysiloxane (A, B). The method of claim 1,
The organopolysiloxane (A) and the organopolysiloxane (B) comprise at least one type of addition reaction type, condensation reaction type and ultraviolet curing type siloxane resin, fluorine group-containing release film. delete delete The method of claim 1,
The thickness after drying of the release layer is 0.03 to 2.0 ㎛, fluorine group-containing release film. The method of claim 1,
The release film is a fluorine group-containing release film, the release force of the release layer and the silicone pressure-sensitive adhesive is 0.5gf / 25mm to 20 gf / 25mm at a 180 ° peel angle, 0.3mpm peel rate. The method of claim 1,
A fluorine group-containing release film, wherein the residual adhesion rate of the release film is 85% or more. The method of claim 1,
The release layer is a fluorine group-containing release film, the number of pinholes 2 / A4 size or less.

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