JP2024038254A - Antistatic silicone release film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antistatic silicone release film which has an excellent antistatic function to prevent a side effect caused by an electrostatic phenomenon when being peeled from an adhesive, and which has excellent adhesion to a base material of a hardening layer and realizes a high degree of crosslinking of the hardening layer thereby having a stable release characteristic.

SOLUTION: The antistatic silicone release film comprises a base film 110 and a hardening layer 120 of antistatic silicone release composition located on at least one side of the base film. The hardening layer comprises: an antistatic region where an intensity ratio (Si-/S-) of silicon ions, which represent a silicone release property, to sulfur ions, which represent an antistatic property, is less than 1; and a silicone release region where the intensity ratio exceeds 10.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to an antistatic silicone release film, and more specifically, it has an excellent antistatic function, has no side effects due to static electricity when peeled from an adhesive, and has excellent adhesion to the base of a cured layer. This invention relates to an antistatic silicone release film having a cured layer with a high degree of crosslinking and stable release properties.

Currently, with the rapid increase in industrialization in the semiconductor, electrical and electronic, and display fields, the use of synthetic resins or synthetic fibers in these fields is rapidly increasing, and this has led to the emergence of static electricity problems in the processing process. There is.

In general, there is an increasing demand for antistatic function in the field of release films used to protect adhesive layers. Conventionally, antistatic functions were added to adhesives in order to solve problems such as contamination caused by static electricity generated when separating the release film from the adhesive layer, and poor peeling. It has been difficult to achieve sufficient antistatic performance due to the incompatibility between adhesive components. Therefore, in recent years, in addition to the adhesive, there are many cases in which the release layer is provided with an antistatic function.

On the other hand, the release properties required for release films used in the precision materials field include an appropriate range of peeling force depending on the type of adhesive and application, and the ability to transfer the release layer to the adhesive layer. High residual adhesion rate to avoid deterioration of functionality, solvent resistance to prevent the release layer from being damaged by the organic solvent used in the adhesive, and mold release to prevent the release layer from falling off due to friction during the processing process. High adhesion between the layer and the base material is required. In addition, since the release film is also used as a pressure-sensitive adhesive carrier film due to the thinning of the pressure-sensitive adhesive layer, it is necessary to ensure stable release properties that do not change much over time and temperature.

In addition, conventional antistatic technologies include an internal addition method using anionic compounds, a method of vapor-depositing metal compounds, a method of applying conductive inorganic particles, a method of applying low-molecular ionic compounds, and a method of applying conductive polymers. A method of applying molecules has been used, and a method of manufacturing an antistatic release film by incorporating metal into a silicone composition by applying such antistatic technology has been used.

However, such conventional techniques are disadvantageous in terms of economy, have limitations in achieving sufficient antistatic performance, and have problems in that a uniform coating layer cannot be formed. In addition, when the antistatic composition uses an ionic compound, there is a problem that it interferes with the curing reaction of the silicone mold release composition, making it difficult to ensure stable mold release properties. There have been problems in that the adhesion between the adhesive and the base material is reduced, causing the release layer to fall off, or the performance of the adhesive to be degraded.

Further, in order to impart an antistatic function to such a release layer, the antistatic layer and the release layer are mainly manufactured through an off-line manufacturing process in which the antistatic layer and the release layer are coated separately. Therefore, during coating processing in each process, many quality problems due to foreign objects and scratches occur, resulting in a problem of high manufacturing costs.

Therefore, the present inventors have developed a silicone mold release coating composition for producing a mold release film by mixing a highly compatible conductive polymer resin and a highly reactive binder compound. The present invention was completed by confirming that an antistatic silicone release film could be manufactured using the coating process described above.

Korean Published Patent Information No. 10-2015-0104477

The present invention has been devised to solve the above-mentioned problems and meet the conventional requirements, and an object of the present invention is to provide excellent antistatic properties through an in-line manufacturing process. To provide an antistatic silicone release film that can reduce side effects such as product contamination due to static electricity and poor peeling when peeled from an adhesive when used as a release film for semiconductors, electrical/electronic, and display applications. There is a particular thing.

Still another object of the present invention is to have an excellent peeling force and a high level of residual adhesion rate, so that the adhesive layer can be used appropriately according to the application without deteriorating its performance. By constructing a dense hardened layer, the hardened layer has excellent durability and solvent resistance, and has high adhesion between the hardened layer and the base material, and is stable with little change in physical properties due to temperature and time. An object of the present invention is to provide an antistatic silicone release film having excellent release properties.

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

The above object comprises a base film and a cured layer of an antistatic silicone mold release composition located on at least one side of the base film, the cured layer comprising silicon ions exhibiting silicone mold release properties and an antistatic composition. This is achieved by an antistatic silicone release film comprising an antistatic region with a characteristic sulfur ion intensity ratio (Si ⁻ /S ⁻ ) of less than 1 and a silicone release region with a characteristic sulfur ion intensity ratio of more than 10.

Here, the intensity ratio (Si ^- /S ^- ) of the cured layer is 10 to 10,000 at the top, which is farthest from the boundary with the base film, and 0.001 at the bottom, which is the boundary with the base film. ~1.

Preferably, the thickness ratio of the antistatic region and the silicone release region satisfies the following formula 1,
[Formula 1]
1/10<AV/RV<1/3
where AV is the thickness of the antistatic region and RV is the thickness of the silicone release region.

Preferably, the antistatic silicone mold release composition is characterized by comprising an alkenyl polysiloxane, a hydrogen polysiloxane, a conductive polymer resin, a binder compound and a platinum chelate catalyst.

Preferably, the antistatic silicone mold release composition comprises 2.5 to 7.5 parts by weight of hydrogen polysiloxane, 1 to 10 parts by weight of a conductive polymer resin, and 5 to 20 parts by weight of a binder compound per 100 parts by weight of alkenyl polysiloxane. It is characterized by containing 10 ppm to 1,000 ppm of platinum chelate catalyst.

Preferably, the antistatic silicone mold release composition further comprises an ionic surfactant having both cations and anions, and the ionic surfactant is selected from sulfo-, phosphor-, or carboxyl- groups. It is characterized by being an ionic surfactant having an anionic group.

Preferably, the ionic surfactant is contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the alkenylpolysiloxane.

Preferably, the binder compound is characterized by containing a silane compound and a non-silane polyfunctional compound.

Preferably, the silane-based compound is at least one of epoxysilane-based, aminosilane-based, vinylsilane-based, methacryloxysilane-based, and isocyanate silane-based compounds, and the non-silane-based polyfunctional compound is an epoxy functional group. It is characterized by being an epoxy-based polyfunctional compound having the following properties.

Preferably, the epoxy-based polyfunctional compound is one or more selected from the group consisting of amino, hydroxy, aldehyde, ester, vinyl, acrylic, imide, cyano, and isocyanate. It is characterized by having a functional group, and having three or more functional groups in one molecule.

Preferably, the weight ratio of the non-silane polyfunctional compound to the silane compound is 2 to 20.

Preferably, the conductive polymer resin has an average particle size of 10 to 90 nm and is an aqueous dispersion containing a polyanion and a polythiophene or an aqueous dispersion containing a polyanion and a polythiophene derivative. do.

Preferably, the antistatic silicone mold release composition is characterized by a solids content of 0.5 to 15% by weight.

Preferably, the surface tension of the base film is 1.0 to 1.5 times that of the cured layer.

Preferably, the thickness of the base film is 15 to 300 μm, and the thickness of the cured layer is 0.01 to 10 μm.

Preferably, the cured layer satisfies the following conditions 1 to 3 at the same time,
(1) 5≦RF≦30
(2) 80≦SA≦100
(3) 10^4≦SR≦10^10
Here, RF is the peeling force (g/inch) of the cured layer, SA is the residual adhesion rate (%) of the cured layer, and SR is the surface resistance (Ω/sq) of the cured layer. Features.

Further, the object includes a base film, a cured layer of an antistatic silicone mold release composition located on one side of the base film, and a silicone mold release layer located on the other side of the base film. Yes, the cured layer has an antistatic region where the intensity ratio of silicon ions representing silicone mold release properties to sulfur ions representing antistatic properties (Si ^- /S ^- ) is less than 1 and a silicone release region where the intensity ratio is greater than 10. This is achieved by an antistatic silicone release film comprising a region.

According to the present invention, since it has antistatic properties, it is possible to solve problems such as contamination caused by static electricity and poor peeling that occur when the release film is separated from the adhesive layer.

In addition, by having excellent peeling force and high level of residual adhesion rate, it can be used appropriately according to the application without reducing the function of the adhesive layer, and it also improves the durability of the cured layer. Because of its excellent properties, it has excellent solvent resistance to organic solvents, and has high adhesion to the base material, so it has effects such as less chance of the cured layer falling off due to friction.

Furthermore, by constructing a dense cured layer, it has the effect of having stable mold release properties with little change due to temperature and passage of time.

However, the effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood from the following description by a person having ordinary knowledge in the technical field to which the present invention pertains. It should be understood.

FIG. 1 is a cross-sectional view of an antistatic silicone release film according to an embodiment of the present invention. FIG. 3 is a cross-sectional view of an antistatic silicone release film according to another embodiment of the present invention. FIG. 3 is a cross-sectional view of an antistatic silicone release film according to still another embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to embodiments of the present invention and drawings. It is common knowledge in the art that these examples are merely illustrative to explain the present invention more specifically, and that the scope of the present invention is not limited by these examples. It should be obvious to anyone who has the following.

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, methods and materials suitable are now described.

As used herein, "comprise", "comprising", "include", "including", "containing" ”, “characterized by”, “has”, “having” or any other variations thereof are intended to cover the non-exclusive inclusions. do. For example, a process, method, article, or apparatus that includes an inventory of elements is not necessarily limited to only those elements, is not explicitly listed, or includes other elements inherent in the process, method, article, or apparatus. It can also be included. Also, unless expressly stated to the contrary, "or" means an inclusive or and not an exclusive or.

In describing/describing 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 dipolymers, terpolymers or higher order copolymers.

First, an antistatic silicone 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 view of an antistatic silicone release film according to a preferred embodiment of the present invention.

Referring to FIG. 1, an antistatic silicone release film according to an embodiment of the present invention includes an antistatic silicone release film 100 according to an aspect of the present invention, which is located on a base film 110 and at least one surface of the base film. and a cured layer 120 of an antistatic silicone mold release composition.

The cured layer 120 has antistatic properties and silicone release properties at the same time, and these antistatic properties and silicone release properties are obtained by applying an antistatic silicone release composition to the base film during production of the release film. They are characterized in that they can be realized simultaneously by one inline coating.

The antistatic silicone mold release composition forming the cured layer 120 of the antistatic silicone mold release film according to an embodiment of the present invention includes an alkenyl polysiloxane, a hydrogen polysiloxane, a conductive polymer resin, a binder compound, and a platinum chelate catalyst. can be included. In one embodiment, the antistatic silicone mold release composition may further include an ionic surfactant having both cations and anions.

In one embodiment, the alkenylpolysiloxane can have the structure shown below.

In the formula, m and n are each independently an integer of 10 to 500. At this time, m and n do not mean block combination, but only mean that the sums of units are m and n, respectively.

Therefore, each unit in Chemical Formula 1 is randomly connected or block connected. Furthermore, R1, R2, and R3 are each an alkyl or alkenyl group selected from -CH ₃ , -CH=CH ₂ , -CH ₂ CH=CH ₂ , and -CH ₂ CH ₂ CH ₂ CH ₂ CH=CH _{2 .} Although the alkenyl group may be present in any part of the molecule, it is preferable that at least two or more alkenyl groups are present.

In one embodiment, the hydrogen polysiloxane can have the structure shown below.

In the formula, a is an integer from 1 to 200, and b is an integer from 1 to 400. At this time, a and b do not mean a block combination, but only mean that the sum of the respective units is a and b. Therefore, each unit in Chemical Formula 2 is randomly connected or block connected.

The alkenyl polysiloxane represented by Chemical Formula 1 and the hydrogen polysiloxane represented by Chemical Formula 2 may be linear, branched, radial, or cyclic, and a mixture thereof may also be used. The mixing ratio of alkenylpolysiloxane and hydrogenpolysiloxane is preferably 2.5 to 7.5 parts by weight of hydrogenpolysiloxane per 100 parts by weight of alkenylpolysiloxane. If the amount of hydrogen polysiloxane is less than 2.5 parts by weight, the amount of unreacted alkenyl polysiloxane increases, making it impossible to obtain sufficient curability and, therefore, failing to achieve stable mold release properties. This is because if the amount exceeds 7.5 parts by weight, the amount of unreacted hydrogen polysiloxane increases, resulting in poor release properties.

In one embodiment, the antistatic silicone mold release composition uses a conductive polymer resin to provide antistatic performance, where the conductive polymer resin is an aqueous dispersion containing a polyanion and a polythiophene. Alternatively, it is preferably an aqueous dispersion containing a polyanion and a polythiophene derivative.

The polyanion is an acidic polymer, such as a polymeric carboxylic acid or a polymeric sulfonic acid, polyvinylsulfonic acid, or the like. Examples of polymeric carboxylic acids include polyacrylic acid, polymethacrylic acid, and polymaleic acid, and examples of polymeric sulfonic acids include polystyrene sulfonic acid, but are not limited thereto.

It is preferable that the solid content weight ratio of the polyanion be present in excess of the polythiophene or polythiophene derivative from the viewpoint of imparting conductivity. In the examples of the present invention, an aqueous dispersion containing 0.5% by weight of poly(3,4-ethylenedioxythiophene) and 0.8% by weight of polystyrene sulfonic acid is used, but is not limited thereto. do not have. Preferably, the weight ratio of polyanion to polythiophene or polythiophene derivative is more than 1 and less than 5, more preferably more than 1 and less than 3.

Further, it is preferable that the conductive polymer resin is an aqueous dispersion having an average particle size of 10 to 90 nm so as to exhibit stable antistatic performance. If the average particle size of the conductive polymer resin exceeds 90 nm, it will not be uniformly distributed inside the cured layer, resulting in a very large deviation in surface resistance, making it impossible to properly achieve antistatic performance. In addition, when the average particle size of the conductive polymer resin is less than 10 nm, as the molecular weight decreases, antistatic performance cannot be realized when the distance between molecules exceeds a certain distance, and when in-line stretching, the average particle size decreases. The smaller the value, the lower the antistatic performance.

The conductive polymer resin preferably contains 1 to 10 parts by weight per 100 parts by weight of the alkenylpolysiloxane. If the content of the conductive polymer resin is less than 1 part by weight based on 100 parts by weight of alkenylpolysiloxane, the antistatic properties will be insufficient and the surface resistance physical properties will decrease, and if it exceeds 10 parts by weight, it will be due to curing interference of the silicone. This is because the mold release properties deteriorate.

In one embodiment, the antistatic silicone mold release composition adjusts the crosslinking density to derive stable mold release and antistatic properties, and improves the compatibility of the conductive polymer resin to achieve uniform antistatic properties. However, a binder compound may be included in order to improve the solvent resistance and durability of the cured layer and increase the adhesion between the cured layer and the substrate.

The binder compound may include a silane-based compound and a non-silane-based polyfunctional compound. More specifically, in the binder compound, it is preferable that the weight ratio of the non-silane type polyfunctional compound to the silane type compound is 2 to 20. The silane-based compound is at least one compound selected from epoxysilane-based, aminosilane-based, vinylsilane-based, methacryloxysilane-based, and isocyanate silane-based, and the non-silane-based polyfunctional compound is an epoxy compound having an epoxy functional group. It can be a polyfunctional compound.

Epoxy-based polyfunctional compounds are preferred because epoxy-based compounds have excellent compatibility with conductive polymers and stretchability. That is, the compatibility differs depending on the N, C, and O contents, and the attachment of alkenyl groups to the functional groups of the conductive polymer improves the stretchability due to the swell ring effect. The epoxy-based polyfunctional compound has one or more functional groups selected from the group consisting of amino, hydroxy, aldehyde, ester, vinyl, acrylic, imide, cyano, and isocyanate. It is preferable that one molecule has three or more functional groups.

The binder compound preferably contains 5 to 20 parts by weight per 100 parts by weight of the alkenylpolysiloxane. If the content of the binder compound is less than 5 parts by weight, the adhesion of the cured layer to the base material is low and the cured layer peels, or the compatibility of the conductive polymer resin decreases, resulting in non-uniformity. There is a problem in terms of antistatic performance, and if the content of the binder compound exceeds 20 parts by weight, there is a problem in that the peeling force and residual adhesion rate are affected, resulting in poor mold release properties. It's for a reason.

In one embodiment, the antistatic silicone mold release composition includes a platinum chelate catalyst to perform a useful function in the addition reaction of Formulas 1 and 2, and the platinum chelate catalyst in the antistatic silicone mold release composition is between 1 ppm and 1 ppm. ,000 ppm.

In one embodiment, the antistatic silicone mold release composition may further include an ionic surfactant having both a cation (cation group) and an anion (anion group) as a surfactant. Such an ionic surfactant can be, for example, an ionic surfactant composed of an ester compound having a dissociable cation and containing an anionic group.

When applying a nonionic surfactant that does not have an anionic group, there is a problem that it is difficult to appropriately adjust the surface tension of the antistatic silicone mold release composition, and the process of applying it to the base film is difficult. Since the antistatic silicone release film does not show sufficient wettability, there are many visible defects in the appearance of the antistatic silicone release film.Especially when applying a silicone-based nonionic surfactant containing siloxane, Not only is the surface tension of the anti-mold release composition not properly controlled, but also the compatibility with the conductive polymer resin is insufficient, leading to the formation of aggregates and appearance defects. In order to solve the problem, it is preferable in the present invention to use an ionic surfactant having both cations and anions.

The surfactant according to the present invention also has an anionic group selected from sulfo-, phosphor-, or carboxyl-groups among ionic surfactants containing anionic groups, that is, sulfonic acid, phosphorous acid, or carboxylic acid. By applying an antistatic mold release composition containing an ionic surfactant having anionic groups derived from Optimum wettability for the material film can be ensured. In the examples of the present invention, dioctyl sulfosuccinate sodium salt and dioctyl phosphosuccinate sodium salt are used as the ionic surfactants, but the present invention is not limited thereto.

The ionic surfactant may be included in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 1 part by weight, based on 100 parts by weight of the alkenylpolysiloxane. This is because if the ionic surfactant content is less than 0.01 part by weight, the content is not sufficient to function as a surfactant, so the appearance improvement effect of the antistatic silicone release film appears. First, if the ionic surfactant content exceeds 5 parts by weight, there is a problem of unstable mold release properties such as increased peeling force due to accelerated interaction with the adhesive. be.

In one embodiment, the antistatic silicone mold release composition is preferably diluted to contain 0.5 to 15% by weight of solid powder and then coated on a polyester substrate film. If the solids content of the antistatic silicone mold release composition is less than 0.5% by weight, a uniform cured layer cannot be obtained, and stable mold release and antistatic properties cannot be obtained. If the amount exceeds 15% by weight, a blocking phenomenon occurs between the films, the adhesion of the coating composition to the substrate deteriorates, causing a silicone transfer problem, and the appearance of the coating becomes poor.

Further, the type of solvent for the antistatic silicone mold release composition is not limited as long as it can disperse the solid content of the present invention and coat it on the polyester base film, but preferably water is used as the main solvent. Coating is performed using an aqueous coating liquid as a medium.

The cured layer 120 of the antistatic silicone release film according to an embodiment of the present invention is prepared by coating the base film 110 with the above-mentioned antistatic silicone release composition using a known method such as a bar coating method, a reverse roll coating method, a gravure roll coating method, etc. It can be formed by coating it one or more times by the method described above.

In the antistatic silicone release film according to an embodiment of the present invention, it is preferable that the surface tension of the cured layer is 1.0 to 1.5 times that of the base film. At this time, if the surface tension of the base film relative to the cured layer is less than 1.0 times, the wettability of the coating liquid will be poor, and if it exceeds 1.5 times, the coating liquid will coagulate, resulting in appearance defects. There is a problem with that.

In addition, for the purpose of improving the coating properties and transparency of the antistatic silicone mold release composition used in the present invention, an appropriate organic solvent may be further included in an amount that does not impede the effects of the present invention. Isopropyl alcohol, butyl cellosolve, ethyl cellosolve, acetone, methanol, ethanol, etc. can be used as the solvent. However, if a large amount of organic solvent is included in the coating composition, there is a risk of explosion during the drying, stretching and heat treatment processes when applied to in-line coating methods. It is preferable to limit the content to 10% by weight or less, more preferably 5% by weight or less.

Further, the base film 110 according to an embodiment of the present invention is preferably a polyester base film, and preferably has a thickness of 15 to 300 μm. If the thickness of the base film is less than 15 μm, the degree of deformation due to external force will increase, making it unsuitable for use as a carrier film, and if the thickness of the film exceeds 300 μm, economic efficiency will decline. There is a problem.

Further, the thickness of the hardened layer 120 according to an embodiment of the present invention is preferably 0.01 to 10 μm. This is because if the thickness of the cured layer is less than 0.01 μm, a uniform cured layer may not be formed, and if it exceeds 10 μm, one side and the back of the polyester base film 110 where the cured layer 120 is located. This is because blocking can occur between the two.

In addition, in the present invention, in order to separate the antistatic region and the release region, which have a similar form to the antistatic release film obtained by coating twice in the offline method, an ionic surfactant is applied. Accordingly, technical goals can be achieved by ensuring compatibility between the conductive polymer resin and silicone, and by separating the excellent wettability and antistatic region from the silicone release region (peeling region).

The cured layer according to an embodiment of the present invention has an intensity or counts ratio (Si ⁻ /S − ) of silicon ions (Si ⁻ ) representing silicone mold release characteristics and sulfur ions (S ⁻ ) representing antistatic characteristics ^. ) is less than 1 and a silicone release region is greater than 10. Such an intensity ratio can be measured by TOF-SIMS and is the relative proportion of silicon ions and sulfur ions in a single cured layer.

Preferably, the intensity ratio (Si ⁻ /S ⁻ ) of the cured layer is 10 to 10,000 at the top furthest from the boundary with the base film, and 0.001 at the bottom, which is the boundary with the base film. ˜1 is preferable. This makes it possible to simultaneously achieve excellent antistatic properties and silicone release properties in a single cured layer. Preferably, the intensity ratio at the top may be between 100 and 5,000. This is similar to a phase-separated structure in which silicon ions, which exhibit silicone mold release properties, and sulfur ions, which exhibit antistatic properties, are implemented in a stacked form, thereby realizing both physical properties at the same time.

Furthermore, the thickness ratio between the antistatic region and the silicone release region of the cured layer satisfies the following formula 1, where AV is the thickness of the antistatic region and RV is the thickness of the silicone release region. It is preferable that there be.
[Formula 1]
1/10<AV/RV<1/3

This is because when the value of Formula 1 is 1/10 or less, the surface resistance physical properties are decreased, and when it is 1/3 or more, the mold release physical properties are decreased.

Further, the cured layer according to an embodiment of the present invention satisfies the following conditions 1 to 3 at the same time, RF is the peeling force (g/inch) of the cured layer, and SA is the residual adhesion rate (%) of the cured layer. ), and SR is preferably the surface resistance (Ω/sq) of the hardened layer.
(1) 5≦RF≦30
(2) 80≦SA≦100
(3) 10^4≦SR≦10^10

From FIG. 2, which is a cross-sectional view of an antistatic silicone release film according to another embodiment of the present invention, an antistatic silicone release film 200 according to another embodiment of the present invention has a base film 210 and one side of the base film. The above-mentioned cured layer 220 of the antistatic silicone mold release composition may be located on the other side, and the above-mentioned cured layer 230 of the antistatic silicone mold release composition may be located on the other side. In this case, the coating composition for forming the cured layer 230 may not contain a peel force modifier.

Further, from FIG. 3, which is a cross-sectional view of an antistatic silicone release film according to still another embodiment of the present invention, an antistatic silicone release film 300 according to still another embodiment of the present invention has a base film 310 and a base film 310. A cured layer 320 of the antistatic silicone mold release composition described above may be located on one surface of the material film, and a silicone mold release layer 330 may be located on the other surface. In this case, the coating composition for forming the silicone release layer 330 may not include a conductive polymer resin.

Hereinafter, the structure of the present invention and its effects will be explained in more detail using Examples and Comparative Examples. However, these Examples are for specifically explaining the present invention, and the scope of the present invention is not limited to these Examples.

(Example 1)
In order to form an antistatic silicone release layer on one surface of a corona-treated polyester base film (manufactured by Toray Advanced Materials, Excel-50 μm), 100 parts by weight of alkenyl polysiloxane (manufactured by Dow Corning) was added as a solid content. In contrast, 3 parts by weight of hydrogen polysiloxane (manufactured by Dow Corning), 0.5 parts by weight of conductive polymer resin (poly 3,4-ethylenedioxythiophene) and 0.5 parts by weight of polystyrene sulfonic acid (molecular weight Mn=150,000). 8 wt. An antistatic silicone mold release composition was prepared by mixing 0.2 parts by weight of the agent (dioctyl sulfosuccinate sodium salt) with water.

The prepared antistatic silicone mold release composition was diluted with water so that the solid content was 5% by weight, and then applied to one side of a polyester base film. After coating, it was dried at 180° C. for 50 seconds to produce an antistatic silicone release film.

(Example 2)
An antistatic silicone release film was produced in the same manner as in Example 1, except that 10 parts by weight of the alkenylpolysiloxane and 10 parts by weight of the conductive polymer resin were mixed.

(Example 3)
An antistatic silicone release film was produced in the same manner as in Example 1, except that 100 parts by weight of alkenylpolysiloxane and 2 parts by weight of conductive polymer resin were mixed.

(Example 4)
An antistatic silicone release film was produced in the same manner as in Example 1, except that 7 parts by weight of a conductive polymer resin were mixed with 100 parts by weight of alkenylpolysiloxane.

(Example 5)
An antistatic silicone release film was produced in the same manner as in Example 1, except that 100 parts by weight of alkenyl polysiloxane and 5 parts by weight of conductive polymer resin were mixed.

(Example 6)
An antistatic silicone release film was produced in the same manner as in Example 1, except that 100 parts by weight of alkenyl polysiloxane and 1 part by weight of conductive polymer resin were mixed.

(Example 7)
An antistatic silicone release film was prepared using the same process as in Example 1, except that dioctylphosphosuccinate sodium salt was used as the ionic surfactant.

(Example 8)
The same process as in Example 1 was used except that 0.2 parts by weight of dioctyl sulfosuccinate sodium salt and 0.2 parts by weight of dioctyl phosphosuccinate sodium salt were used as ionic surfactants. An antistatic silicone release film was produced.

(Example 9)
An antistatic silicone release film was produced in the same manner as in Example 1, except that 15 parts by weight of the epoxy binder compound was mixed.

(Example 10)
An antistatic silicone release film was produced in the same manner as in Example 1, except that 20 parts by weight of the epoxy binder compound was mixed.

(Example 11)
An antistatic silicone release film was produced in the same manner as in Example 1, except that the produced antistatic silicone release composition was diluted with water so that the solids content was 2.5% by weight. .

(Comparative example)
(Comparative example 1)
An antistatic silicone release film was produced in the same manner as in Example 1, except that 0.5 parts by weight of a conductive polymer resin was mixed with 100 parts by weight of alkenylpolysiloxane.

(Comparative example 2)
An antistatic silicone release film was produced in the same manner as in Example 1, except that 100 parts by weight of alkenylpolysiloxane and 15 parts by weight of conductive polymer resin were mixed.

(Comparative example 3)
An antistatic silicone release film was prepared in the same manner as in Example 1, except that 0.2 parts by weight of a silicone surfactant (manufactured by Dow Corning) was used as the surfactant.

(Comparative example 4)
An antistatic silicone release film was produced in the same manner as in Example 1, except that the binder mixture was not mixed.

(Comparative example 5)
An antistatic silicone release film was produced in the same manner as in Example 1, except that the conductive polymer resin was not mixed.

(Comparative example 6)
An antistatic silicone release film was produced in the same manner as in Example 1, except that 25 parts by weight of the epoxy binder compound was mixed.

Using the release films of Examples 1 to 11 and Comparative Examples 1 to 6, physical properties were measured in the following experimental examples, and the results are shown in Table 1 below.

(Experiment example)
1. Thickness measurement of antistatic area and release area (silicone release area) The entire thickness of the cured layer is measured using an ellipsometer (Ellipso Technology, Elli-SE).

The thickness of the silicone coating layer is measured using XRF (Panalytical, Minipal 4), and this is taken as the peeling area value.

The thickness of the antistatic area was calculated using Equation 2 below.
[Formula 2]
Antistatic area = total cured layer thickness (ellipsometer measurement) - silicone coating layer thickness (XRF measurement)

2. Measurement of the intensity (counts) ratio (Si ^- /S ^- ) of Si ^- ions and S ^- ions in the hardened layer Time of Flight secondary ion mass spectrometry; TOF-SIMS (ION-TOF, Germany).

The measurement conditions were Ar-cluster energy intensity of 5 KeV and Negative Mode.

3. Antistatic properties After placing the sample in an environment of temperature 23°C and humidity 50% RH using a surface resistance measuring device (manufactured by Mitsubishi, MCP-T600), the surface resistance of the cured layer was measured based on JIS K7194. did.

4. Peel force measurement After attaching a release film to a cold-rolled stainless steel plate with double-sided adhesive tape so that the cured layer is on top, adhesive tape (TESA 7475) was placed on the release layer and pressed with a 2 kg pressure roller. The peel force was measured after the film was left at room temperature for 1 to 7 days.

Peeling force was measured using AR-1000 (Chem-Instrument) at a peeling angle of 180° and a peeling speed of 0.3 mpm, and the average value (g/inch) was calculated by measuring 5 times. The digits were rounded off.

5. Measurement of residual adhesion rate Adhesive tape (Nitto 31B) was placed on the cured layer, pressed with a 2 kg pressure roller and left at room temperature for 30 minutes, then the adhesive tape was peeled from the cured layer and attached to a cold rolled stainless steel plate. The post-peel force was measured.

In addition, for comparison, an adhesive tape (Nitto 31B) that had never been used was attached to a cold rolled stainless steel plate, and then the peel force was measured.

The peeling force was measured using AR-1000 (Chem-Instrument) at a peeling angle of 180° and a peeling speed of 0.3 mpm, and the average value was calculated from 5 measurements.

The residual adhesion rate was calculated using Equation 3 below.
[Formula 3]
Residual adhesion rate = Peeling force of adhesive tape peeled from the cured layer / Peeling force of adhesive tape that has never been used x 100 (%)

6. Defect Area Measurement The area of bubble defects relative to the area of a 5 cm x 5 cm release film sample was measured. After measuring the longest length of the bubble defect in a 5 cm x 5 cm release film sample and calculating the area using a circle, the area (cm ² ) of the bubble defect was determined by adding the whole sample.

The degree of bubble defects (coating appearance) was evaluated by calculating the bubble defect area ratio using Equation 4 below and using the following criteria.
[Formula 4]
Cellular defect area ratio (%) = Area of cellular defect/25cm ² × 100 (%)
◎: 0% or more and less than 1% ○: 1% or more and less than 2% △: 2% or more and less than 5% ×: 5% or more

7. Solvent Resistance Measurement The resistance of the upper surface of the film to solvents was measured.

For the measurement, after soaking a cotton swab in isopropyl alcohol, the cured layer was reciprocated 10 times with a load of 100 g while maintaining the angle of the swab at 45 degrees, and the solvent resistance state of the coated surface was evaluated using the following criteria.
◎: Excellent ○: Good △: Average ×: Unpaid

8. Measurement of Pushability: The hardened layer was stroked back and forth 5 times with the thumb, and then checked with the naked eye and evaluated using the following criteria.
◎: No change after evaluation (No smear)
○: Slightly pressed, but no problem in use (Slightly smear)
△: The hardened layer has a white smear as if the oil was pressed.
×: The hardened layer clumps and starts to fall off (Rub-off)

As can be seen from Table 1, the antistatic silicone release films according to Examples 1 to 11 of the present invention have almost no defects, so the coating appearance is excellent and the cured layer has excellent pressability. It can be confirmed that the surface resistance and peeling force are within appropriate ranges, and the residual adhesion rate is also excellent. It can be confirmed that the antistatic silicone release film according to Example 8 of the present invention has the best appearance and physical properties.

In addition, the thickness ratio of the antistatic region to the silicone mold release region in the cured layer and the ratio of silicon ions and sulfur ions at the top and bottom of the release films according to Examples 1 to 11 and Comparative Examples 1 to 6 It can be confirmed that the surface resistance value, which is an antistatic physical property, and the peeling force, which is a mold release physical property, the residual adhesion rate, and the appearance are correlated and change.

In addition, in the case of the antistatic silicone release film according to Example 9 of the present invention, it can be confirmed that the surface resistance physical properties are excellent as the binder content increases based on the same content of conductive polymer.

Furthermore, in Examples 10 and 11 of the present invention, even if the absolute content of the conductive polymer and alkenylsiloxane changes, if the ratio of the antistatic area to the peeling area does not change significantly, the release properties are also excellent. can be confirmed.

On the other hand, in the case of the release films according to Comparative Examples 1 and 2, the content of the conductive polymer resin is too small or too large, so the surface resistance, which is an antistatic property, increases excessively, or the release properties deteriorate. It can be seen that some residual adhesion rates are excessively reduced.

In addition, it can be confirmed that in the release film according to Comparative Example 3, when the ionic surfactant was not included, the coating appearance was poor and the peel strength properties were poor.

In addition, it can be confirmed that the release films according to Comparative Examples 4 and 5 cannot obtain surface resistance properties when the epoxy binder compound or the conductive polymer resin is not included.

Moreover, in Comparative Example 6, it can be confirmed that when the binder compound is excessively large, the surface resistance physical properties are improved, but the mold release physical properties are fatally deteriorated.

As mentioned above, the antistatic silicone release film according to the present invention can be suitably applied to suit the desired application, but is not limited thereto. In addition, the present invention can provide an antistatic silicone release film of excellent quality for use in the field of precision materials, which has an appropriate range of peeling force and a high level of residual adhesion rate. It can be used appropriately to suit the application without reducing the function of the adhesive layer.

Furthermore, the antistatic silicone release film according to the present invention has excellent durability of the cured layer, excellent solvent resistance to organic solvents, and high adhesion to the base material, which prevents friction. It has the characteristic that the hardened layer does not easily come off. In addition, it can be seen that by having excellent antistatic properties, it is possible to solve problems such as contamination caused by static electricity and poor peeling.

In this specification, only some of the various embodiments carried out by the present inventors are cited and explained; however, the technical concept of the present invention is not limited or limited to these, and the present invention is not limited to these. Of course, it can be modified and implemented in a variety of ways depending on the manufacturer.

Claims (17)

base film,
It includes a cured layer of an antistatic silicone mold release composition located on at least one surface of the base film,
The hardened layer has an antistatic region in which the intensity ratio (Si ⁻ /S ⁻ ) of silicon ions representing silicone mold release characteristics to sulfur ions representing antistatic characteristics is less than 1, and a silicone mold release region in which the intensity ratio is greater than 10. Containing antistatic silicone release film. The intensity ratio (Si ⁻ /S ⁻ ) of the cured layer is 10 to 10,000 at the top, which is farthest from the boundary with the base film, and 0.001 at the bottom, which is the boundary with the base film. The antistatic silicone release film according to claim 1, which is 1 to 1. The thickness ratio of the antistatic region and the silicone mold release region satisfies the following formula 1,
[Formula 1]
1/10<AV/RV<1/3
2. The antistatic silicone release film of claim 1, wherein AV is the thickness of the antistatic region and RV is the thickness of the silicone release region. The antistatic silicone release film of claim 1, wherein the antistatic silicone release composition comprises an alkenyl polysiloxane, a hydrogen polysiloxane, a conductive polymer resin, a binder compound, and a platinum chelate catalyst. The antistatic silicone mold release composition comprises 2.5 to 7.5 parts by weight of the hydrogen polysiloxane, 1 to 10 parts by weight of the conductive polymer resin, and 5 parts by weight of the binder compound based on 100 parts by weight of the alkenyl polysiloxane. 5. The antistatic silicone release film of claim 4, comprising from 20 parts by weight and from 10 ppm to 1,000 ppm of the platinum chelate catalyst. The antistatic silicone mold release composition further includes an ionic surfactant having both cations and anions,
The antistatic silicone release film according to claim 4, wherein the ionic surfactant is an ionic surfactant having an anionic group selected from sulfo-, phosphor-, or carboxyl-groups. The antistatic silicone release film according to claim 6, wherein the ionic surfactant contains 0.01 to 5 parts by weight based on 100 parts by weight of the alkenylpolysiloxane. The antistatic silicone release film according to claim 4, wherein the binder compound includes a silane compound and a non-silane polyfunctional compound. The silane compound is at least one compound selected from epoxysilane, aminosilane, vinylsilane, methacryloxysilane, and isocyanate silane,
The antistatic silicone release film according to claim 8, wherein the non-silane polyfunctional compound is an epoxy polyfunctional compound having an epoxy functional group. The epoxy-based polyfunctional compound has one or more functional groups selected from the group consisting of amino, hydroxy, aldehyde, ester, vinyl, acrylic, imide, cyano, and isocyanate. The antistatic silicone release film according to claim 9, which has three or more functional groups in one molecule. The antistatic silicone release film according to claim 8, wherein the weight ratio of the non-silane polyfunctional compound to the silane compound is from 2 to 20. The conductive polymer resin has an average particle size of 10 to 90 nm and is an aqueous dispersion containing a polyanion and a polythiophene, or an aqueous dispersion containing a polyanion and a polythiophene derivative. antistatic silicone release film. The antistatic silicone mold release film of claim 1, wherein the antistatic silicone mold release composition has a solids content of 0.5 to 15% by weight. The antistatic silicone release film according to claim 1, wherein the surface tension of the base film is 1.0 to 1.5 times that of the cured layer. The antistatic silicone mold release according to any one of claims 1 to 14, wherein the base film has a thickness of 15 to 300 μm, and the cured layer has a thickness of 0.01 to 10 μm. film. The cured layer according to any one of claims 1 to 14 satisfies the following conditions 1 to 3 at the same time,
(1) 5≦RF≦30
(2) 80≦SA≦100
(3) 10^4≦SR≦10^10
Here, RF is the peeling force (g/inch) of the cured layer, SA is the residual adhesion rate (%) of the cured layer, and SR is the surface resistance (Ω/sq) of the cured layer. Prevention silicone release film. base film,
a cured layer of an antistatic silicone mold release composition located on one surface of the base film;
and a silicone release layer located on the other side of the base film,
The cured layer has an antistatic region where the intensity ratio (Si ⁻ /S ⁻ ) of silicon ions representing silicone mold release characteristics to sulfur ions representing antistatic characteristics is less than 1 and a silicone mold release region where the intensity ratio is greater than 10. Antistatic silicone release film, including.

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