Antistatic silicone release film

Abstract

To provide an antistatic silicone release film which has an excellent antistatic function, does not cause a side effect due to an electrostatic phenomenon when peeled from an adhesive, has excellent adhesion to a base material of a cured layer, has a high degree of crosslinking of the cured layer, and has stable release characteristics.SOLUTION: The antistatic silicone release film includes a base material film 110 and a cured layer 120 of an antistatic silicone release composition positioned on at least one surface of the base material film, and the cured layer includes an antistatic region in which an intensity ratio (Si - / S -) of a silicon ion exhibiting a silicone release property to a sulfur ion exhibiting an antistatic property is less than 1 and a silicone release region in which the intensity ratio is more than 10.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an antistatic silicone release film, and more particularly to an antistatic silicone release film that has excellent antistatic properties, is free from side effects caused by static electricity when peeled off from an adhesive, has excellent adhesion between the cured layer and the base, and has a high degree of crosslinking in the cured layer, resulting in stable release properties. [Background technology]

[0002] Currently, with the rapid growth of industrialization in the fields of semiconductors, electrical and electronic equipment, and displays, the use of synthetic resins and synthetic fibers in these fields is increasing rapidly, which has resulted in the emergence of static electricity problems during processing.

[0003] In general, the demand for antistatic properties is increasing even in the field of release films, which are used to protect adhesive layers. Conventionally, antistatic properties have been imparted to adhesives to solve problems such as contamination and poor peeling caused by static electricity when separating a release film from an adhesive layer. However, it has been difficult to achieve sufficient antistatic performance due to incompatibility between the antistatic component and the adhesive component. Therefore, recently, it has become common to impart antistatic properties to the release layer in addition to the adhesive.

[0004] Meanwhile, the release properties required for release films for precision material applications include peel strength within an appropriate range depending on the type and application of the adhesive, a high residual adhesion rate so that the release layer is transferred to the adhesive layer without reducing its functionality, solvent resistance so that the release layer is not damaged by organic solvents used in the adhesive, and high adhesion between the release layer and the substrate so that the release layer does not fall off due to friction during processing. Furthermore, as the adhesive layer becomes thinner, release films can also be used as adhesive carrier films, and stable release properties that change little over time and with temperature must also be ensured.

[0005] Furthermore, conventional antistatic techniques include an internal addition method using an anionic compound, a method of depositing a metal compound, a method of applying conductive inorganic particles, a method of applying a low molecular weight ionic compound, and a method of applying a conductive polymer. These antistatic techniques have been applied to manufacture antistatic release films by incorporating a metal into a silicone composition.

[0006] However, such conventional techniques are disadvantageous from an economical standpoint, have limitations in realizing sufficient antistatic performance, and have problems in that a uniform coating layer is not formed. Furthermore, when the antistatic composition uses an ionic compound, the compound interferes with the curing reaction of the silicone release composition, making it difficult to ensure stable release properties. There are also problems such as a decrease in the adhesive strength between the antistatic release layer and the substrate, resulting in the release layer peeling off or a decrease in the performance of the adhesive.

[0007] In addition, in order to provide such a release layer with an antistatic function, it is generally manufactured by an offline manufacturing process in which the antistatic layer and the release layer are coated separately, which results in many quality issues due to foreign matter and scratches during the coating process in each process, and also in high manufacturing costs.

[0008] Therefore, the present inventors have confirmed that an antistatic silicone release film can be produced in a single coating step by mixing a conductive polymer resin with excellent compatibility and a binder compound with excellent reactivity into a silicone release coating composition for producing a release film, and have completed the present invention. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Korean Patent Publication No. 10-2015-0104477 Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention has been devised to solve the above problems and meet the conventional requirements, and an object of the present invention is to provide an antistatic silicone release film that has excellent antistatic properties through an in-line manufacturing process, and thereby reduces side effects such as product contamination and poor release caused by static electricity when released from an adhesive when used as a release film for semiconductors, electrical and electronic devices, and displays.

[0011] Yet another object of the present invention is to provide an antistatic silicone release film that has excellent peel strength and a high level of residual adhesion, thereby allowing it to be used appropriately for various applications without reducing the performance of the pressure-sensitive adhesive layer, and that has excellent durability and solvent resistance due to the formation of a dense cured layer, has high adhesion between the cured layer and the substrate, and exhibits stable release properties with little change in physical properties over time or temperature.

[0012] The above and other objects and advantages of the present invention will become more apparent from the following description of the preferred embodiment. [Means for solving the problem]

[0013] The object of the present invention is to provide a cured layer of an antistatic silicone release composition, which comprises a substrate film and a cured layer of an antistatic silicone release composition located on at least one surface of the substrate film, the cured layer having an intensity ratio of silicon ions exhibiting silicone release properties to sulfur ions exhibiting antistatic properties (Si - / S - This is achieved by an antistatic silicone release film comprising antistatic areas where R ) is less than 1 and silicone release areas where R ) is greater than 10.

[0014] Here, the intensity ratio of the hardened layer (Si - / S -) is 10 to 10,000 at the top, farthest from the boundary with the base film, and 0.001 to 1 at the bottom, which is the boundary with the base film.

[0015] Preferably, the thickness ratio of the antistatic area to the silicone release area satisfies the following formula 1: [Formula 1] 1 / 10 <AV / RV<1 / 3 where AV is the thickness of the antistatic area and RV is the thickness of the silicone release area.

[0016] Preferably, the antistatic silicone release composition is characterized by comprising an alkenylpolysiloxane, a hydrogenpolysiloxane, a conductive polymer resin, a binder compound, and a platinum chelate catalyst.

[0017] Preferably, the antistatic silicone release composition is characterized by comprising, per 100 parts by weight of alkenylpolysiloxane, 2.5 to 7.5 parts by weight of hydrogenpolysiloxane, 1 to 10 parts by weight of conductive polymer resin, 5 to 20 parts by weight of binder compound, and 10 ppm to 1,000 ppm of platinum chelate catalyst.

[0018] Preferably, the antistatic silicone release composition further comprises an ionic surfactant having both a cation and an anion, wherein the ionic surfactant has an anionic group selected from sulfo-, phosphor-, or carboxyl-groups.

[0019] Preferably, the ionic surfactant is contained in an amount of 0.01 to 5 parts by weight relative to 100 parts by weight of the alkenylpolysiloxane.

[0020] Preferably, the binder compound is characterized by including a silane-based compound and a non-silane-based polyfunctional compound.

[0021] Preferably, the silane-based compound is at least one compound selected from the group consisting of epoxy silanes, amino silanes, vinyl silanes, methacryloxy silanes, and isocyanate silanes, and the non-silane-based polyfunctional compound is an epoxy-based polyfunctional compound having an epoxy functional group.

[0022] Preferably, the epoxy-based polyfunctional compound has one or more functional groups selected from the group consisting of amino-based, hydroxy-based, aldehyde-based, ester-based, vinyl-based, acrylic-based, imide-based, cyano-based, and isocyanate-based functional groups, and is characterized by having three or more functional groups in one molecule.

[0023] Preferably, the weight ratio of the non-silane-based polyfunctional compound to the silane-based compound is 2 to 20.

[0024] Preferably, the conductive polymer resin has an average particle size of 10 to 90 nm and is an aqueous dispersion containing polyanion and polythiophene or an aqueous dispersion containing polyanion and polythiophene derivative.

[0025] Preferably, the antistatic silicone release composition is characterized by having a solids content of 0.5 to 15% by weight.

[0026] Preferably, the surface tension of the substrate film is 1.0 to 1.5 times that of the cured layer.

[0027] Preferably, the thickness of the substrate film is 15 to 300 μm, and the thickness of the cured layer is 0.01 to 10 μm.

[0028] Preferably, the hardened layer satisfies the following conditions 1 to 3 simultaneously: (1) 5≦RF≦30 (2) 80≦SA≦100 (3) 10^4≦SR≦10^10 Here, RF is the peel strength (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.

[0029] The object is also to provide a silicone release film comprising a substrate film, a cured layer of an antistatic silicone release composition located on one side of the substrate film, and a silicone release layer located on the other side of the substrate film, wherein the cured layer has an intensity ratio of silicon ions that exhibit silicone release properties to sulfur ions that exhibit antistatic properties (Si - / S - ) is less than 1 and silicone release areas are greater than 10. [Effects of the Invention]

[0030] According to the present invention, since the release film has antistatic properties, it has the effect of solving problems such as contamination caused by static electricity that occurs when the release film is separated from the adhesive layer and poor peeling.

[0031] Furthermore, by having excellent peel strength and a high level of residual adhesion rate, it can be used appropriately according to the application without reducing the function of the pressure-sensitive adhesive layer, and since the cured layer has excellent durability, it has resistance to organic solvents, and since it has high adhesive strength with the substrate, it has effects such as being less likely to come off due to friction.

[0032] Furthermore, by forming a denser hardened layer, it is possible to obtain effects such as stable release properties that are less susceptible to change with temperature and the passage of time.

[0033] However, the effects of the present invention are not limited to those mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art to which the present invention pertains from the following description. [Brief explanation of the drawings]

[0034] [Figure 1] 1 is a cross-sectional view of an antistatic silicone release film according to one embodiment of the present invention. [Figure 2] FIG. 2 is a cross-sectional view of an antistatic silicone release film according to another embodiment of the present invention. [Figure 3] FIG. 2 is a cross-sectional view of an antistatic silicone release film according to yet another embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0035] The present invention will be described in detail below with reference to the following examples and drawings. It should be obvious to those skilled in the art that these examples are merely provided for illustrative purposes to more specifically explain the present invention, and that the scope of the present invention is not limited by these examples.

[0036] 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, shall control. In addition, 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.

[0037] As used herein, the terms "comprise," "comprising," "include," "including," "containing," "characterized by," "has," "having," or any other variation thereof, are intended to cover an inclusive, but not exclusive, context. For example, a process, method, article, or apparatus that includes a list of elements is not necessarily limited to only those elements and may include other elements not expressly listed or inherent in such process, method, article, or apparatus. Also, unless expressly stated to the contrary, "or" means an inclusive "or" and not an exclusive "or."

[0038] In describing and / or claiming the present invention, the term "copolymer" is used to refer to polymers formed by the copolymerization of two or more monomers. Such copolymers include copolymers, terpolymers, or higher order copolymers.

[0039] 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.

[0040] Referring to FIG. 1, an antistatic silicone release film according to one embodiment of the present invention includes an antistatic silicone release film 100 comprising a substrate film 110 and a cured layer 120 of an antistatic silicone release composition located on at least one surface of the substrate film.

[0041] The cured layer 120 has both antistatic properties and silicone release properties, which are realized simultaneously by in-line coating the antistatic silicone release composition onto the substrate film once during the production of the release film.

[0042] The antistatic silicone release composition forming the cured layer 120 of the antistatic silicone release film according to one embodiment of the present invention can include an alkenyl polysiloxane, a hydrogen polysiloxane, a conductive polymer resin, a binder compound, and a platinum chelate catalyst. In one embodiment, the antistatic silicone release composition can further include an ionic surfactant having both cations and anions.

[0043] In one embodiment, the alkenyl polysiloxane can have the structure shown below:

[0044] [ka]

[0045] In the formula, m and n are each independently an integer of 10 to 500. In this case, m and n do not mean a block bond, but merely mean that the sum of the respective units is m and n.

[0046] Therefore, each unit in Chemical Formula 1 is randomly or block-bonded. R1, R2, and R3 are each an alkyl or alkenyl group selected from -CH3, -CH=CH2, -CH2CH=CH2, and -CH2CH2CH2CH2CH=CH2. The alkenyl group may be present in either part of the molecule, but it is preferable that at least two or more alkenyl groups are present.

[0047] In one embodiment, the hydrogen polysiloxane may have the structure shown below.

[0048] [ka]

[0049] In the formula, a is an integer between 1 and 200, and b is an integer between 1 and 400. In this case, a and b do not mean block bonds, but merely mean that the sum of each unit is a and b. Therefore, each unit in formula 2 is randomly or block-bonded.

[0050] The alkenylpolysiloxane represented by Chemical Formula 1 and the hydrogenpolysiloxane represented by Chemical Formula 2 may be linear, branched, radial, or cyclic, or a mixture thereof may also be used. The mixing ratio of the alkenylpolysiloxane and the hydrogenpolysiloxane is preferably 2.5 to 7.5 parts by weight of the hydrogenpolysiloxane per 100 parts by weight of the alkenylpolysiloxane. If the amount of hydrogenpolysiloxane is less than 2.5 parts by weight, the amount of unreacted alkenylpolysiloxane increases, making it difficult to obtain sufficient curing properties and therefore unable to achieve stable release properties. If the amount exceeds 7.5 parts by weight, the amount of unreacted hydrogenpolysiloxane increases, making it difficult to obtain sufficient curing properties and therefore unable to achieve stable release properties.

[0051] In one embodiment, the antistatic silicone release composition uses a conductive polymer resin to impart antistatic properties, and the conductive polymer resin is preferably an aqueous dispersion containing a polyanion and a polythiophene or an aqueous dispersion containing a polyanion and a polythiophene derivative.

[0052] The polyanion is an acidic polymer, such as a polymeric carboxylic acid or sulfonic acid, polyvinyl sulfonic acid, etc. Examples of polymeric carboxylic acids include polyacrylic acid, polymethacrylic acid, polymaleic acid, etc., and examples of polymeric sulfonic acids include, but are not limited to, polystyrene sulfonic acid.

[0053] In order to provide electrical conductivity, it is preferable that the solid weight ratio of polyanion is in excess relative to the polythiophene or polythiophene derivative. In an embodiment of the present invention, an aqueous dispersion containing 0.5 wt% poly(3,4-ethylenedioxythiophene) and 0.8 wt% polystyrene sulfonic acid is used, but the present invention is not limited to this. Preferably, the weight ratio of polythiophene or polythiophene derivative to polyanion is in the range of more than 1 and less than 5, and more preferably in the range of more than 1 and less than 3.

[0054] Furthermore, it is preferable to use an aqueous dispersion of conductive polymer resin with an average particle size of 10 to 90 nm to ensure stable antistatic performance. If the average particle size of the conductive polymer resin exceeds 90 nm, it will not be uniformly distributed within the cured layer, resulting in a significant deviation in surface resistance and making it difficult to properly achieve antistatic performance. Furthermore, if the average particle size of the conductive polymer resin is less than 10 nm, the molecular weight decreases and the intermolecular distance exceeds a certain level, making it difficult to achieve antistatic performance. Furthermore, the smaller the average particle size, the lower the antistatic performance during in-line stretching.

[0055] The conductive polymer resin is preferably contained in an amount of 1 to 10 parts by weight per 100 parts by weight of the alkenylpolysiloxane. If the amount of the conductive polymer resin is less than 1 part by weight per 100 parts by weight of the alkenylpolysiloxane, the antistatic properties are insufficient and the surface resistance properties are reduced, and if the amount is more than 10 parts by weight, the release properties are reduced due to the interference with the curing of the silicone.

[0056] In one embodiment, the antistatic silicone release composition may include a binder compound to adjust the crosslink density to provide stable release and antistatic properties, increase the compatibility of the conductive polymer resin to provide uniform antistatic properties, improve the solvent resistance and durability of the cured layer, and increase the adhesion between the cured layer and the substrate.

[0057] The binder compound may include a silane-based compound and a non-silane-based multifunctional compound. More specifically, the weight ratio of the silane-based compound to the non-silane-based multifunctional compound is preferably 2 to 20. The silane-based compound may be at least one compound selected from the group consisting of epoxy silanes, amino silanes, vinyl silanes, methacryloxy silanes, and isocyanate silanes, and the non-silane-based multifunctional compound may be an epoxy-based multifunctional compound having an epoxy functional group.

[0058] Epoxy-based polyfunctional compounds are preferred because epoxy-based compounds have excellent compatibility with conductive polymers and excellent stretchability. That is, compatibility varies depending on the N, C, and O content, and the addition of alkenyl groups to the functional groups of the conductive polymer improves stretchability due to the swelling effect. The epoxy-based polyfunctional compound has one or more functional groups selected from the group consisting of amino-based, hydroxy-based, aldehyde-based, ester-based, vinyl-based, acrylic-based, imide-based, cyano-based, and isocyanate-based, and preferably has three or more functional groups in one molecule.

[0059] The binder compound is preferably contained in an amount of 5 to 20 parts by weight per 100 parts by weight of the alkenylpolysiloxane. If the binder compound content is less than 5 parts by weight, the cured layer may peel off due to low adhesion to the substrate, or the compatibility of the conductive polymer resin may decrease, resulting in uneven antistatic performance. If the binder compound content exceeds 20 parts by weight, the peel strength and residual adhesion rate may be affected, resulting in poor release properties.

[0060] In one embodiment, the antistatic silicone release composition contains a platinum chelate catalyst, which functions to facilitate the addition reaction of Chemical Formula 1 and Chemical Formula 2, and the platinum chelate catalyst is preferably present in the antistatic silicone release composition in an amount of 1 ppm to 1,000 ppm.

[0061] In one embodiment, the antistatic silicone release composition may further comprise an ionic surfactant having both a cation (cationic group) and an anion (anionic group) as a surfactant. Such an ionic surfactant may be, for example, an ionic surfactant composed of an ester compound having a dissociable cation and an anionic group.

[0062] When a nonionic surfactant without an anionic group is used, it is difficult to properly adjust the surface tension of the antistatic silicone release composition, and the antistatic silicone release composition does not exhibit sufficient wettability during application to the substrate film, resulting in numerous visible defects in the appearance of the antistatic silicone release film. In particular, when a silicone-based nonionic surfactant containing siloxane is used, not only is the surface tension of the antistatic release composition not properly adjusted, but the compatibility with the conductive polymer resin is also insufficient, resulting in the formation of aggregates, which can cause defects in appearance. In order to solve these problems, it is preferable in the present invention to use an ionic surfactant that has both a cation and an anion.

[0063] Furthermore, the surfactant according to the present invention is an ionic surfactant having an anionic group selected from sulfo-, phosphor-, or carboxyl-groups, i.e., an anionic group derived from sulfonic acid, phosphorous acid, or carboxylic acid, among ionic surfactants having an anionic group, thereby ensuring optimal wettability to the substrate film while maintaining compatibility with alkenyl polysiloxanes, hydrogen polysiloxanes, and conductive polymer resins. In the examples of the present invention, dioctyl sulfosuccinate sodium salt and dioctyl phosphosuccinate sodium salt are used as the ionic surfactant, but the present invention is not limited thereto.

[0064] The ionic surfactant may be included in an amount of 0.01 to 5 parts by weight, and preferably 0.05 to 1 part by weight, based on 100 parts by weight of the alkenylpolysiloxane. This is because if the amount of ionic surfactant is less than 0.01 part by weight, the amount is insufficient to function as a surfactant, and the appearance improvement effect of the antistatic silicone release film is not achieved, and if the amount of ionic surfactant is more than 5 parts by weight, there is a problem that the interaction with the adhesive is promoted, increasing the peel force and exhibiting other unstable release properties.

[0065] In one embodiment, the antistatic silicone release composition is preferably diluted to a solid content of 0.5 to 15 wt % and then coated onto a polyester substrate film. If the solid content of the antistatic silicone release composition is less than 0.5 wt %, a uniform cured layer cannot be obtained, and stable release and antistatic properties cannot be obtained. If the solid content exceeds 15 wt %, blocking occurs between films, which reduces the adhesion of the coating composition to the substrate, causing problems with silicone transfer and resulting in poor coating appearance.

[0066] Furthermore, there are no limitations on the type of solvent for the antistatic silicone release composition, as long as it can disperse the solid components of the present invention and be applied to the polyester substrate film, but it is preferable to coat the composition in the form of an aqueous coating liquid containing water as the main medium.

[0067] The cured layer 120 of the antistatic silicone release film according to one embodiment of the present invention can be formed by applying the above-described antistatic silicone release composition to the substrate film 110 one or more times using a known method such as bar coating, reverse roll coating, or gravure roll coating.

[0068] In an antistatic silicone release film according to an embodiment of the present invention, the surface tension of the cured layer relative to the substrate film is preferably 1.0 to 1.5 times. If the surface tension of the cured layer relative to the substrate film is less than 1.0 times, the wettability of the coating liquid is poor, and if it exceeds 1.5 times, the coating liquid may aggregate, resulting in defects in appearance.

[0069] Furthermore, for the purpose of improving the coatability and transparency of the antistatic silicone release composition used in the present invention, a suitable organic solvent can be further added to the extent that it does not impair the effects of the present invention, and preferred organic solvents include isopropyl alcohol, butyl cellosolve, ethyl cellosolve, acetone, methanol, ethanol, etc. However, if a large amount of organic solvent is added to the coating composition, there is a risk of explosion during the drying, stretching, and heat treatment steps when the composition is applied to an in-line coating method, so it is preferable to limit the content of the organic solvent to 10% by weight or less, and more preferably 5% by weight or less, of the coating composition.

[0070] Furthermore, the substrate film 110 according to an embodiment of the present invention is preferably a polyester substrate film, and preferably has a thickness of 15 to 300 μm. If the thickness of the substrate film is less than 15 μm, it will be subject to large deformation due to external forces, making it unsuitable for use as a carrier film. If the thickness of the film exceeds 300 μm, it will be less economical.

[0071] Furthermore, the thickness of the hardening layer 120 according to an embodiment of the present invention is preferably 0.01 to 10 μm because if the thickness is less than 0.01 μm, a uniform hardening layer may not be formed, and if the thickness exceeds 10 μm, blocking may occur between one side of the polyester substrate film 110 where the hardening layer 120 is located and the rear side.

[0072] In addition, in the present invention, in order to separate the antistatic area and the release area, which are similar in form to the antistatic release film obtained through two coatings using the offline method, the compatibility between the conductive polymer resin and the silicone is ensured by the application of an ionic surfactant, and the excellent wettability and separation of the antistatic area and the silicone release area (release area) can be achieved, thereby achieving the technical goal.

[0073] The hardened layer according to one embodiment of the present invention is formed by the addition of silicon ions (Si - ) and sulfur ions (S - ) Intensity (or counts) ratio (Si - / S - ) is less than 1 and the silicone release area is greater than 10. This intensity ratio can be measured by TOF-SIMS and is the relative proportion of silicon ions and sulfur ions within a single cured layer.

[0074] Preferably, the intensity ratio of the hardened layer (Si - / S - ) is preferably 10 to 10,000 at the top, which is the furthest part from the boundary with the substrate film, and 0.001 to 1 at the bottom, which is the boundary with the substrate film. This allows a single cured layer to simultaneously achieve excellent antistatic properties and silicone release properties. Preferably, the intensity ratio at the top is 100 to 5,000. This allows both properties to be simultaneously achieved by realizing the silicon ions that exhibit silicone release properties and the sulfur ions that exhibit antistatic properties in a layered form, like a phase separation structure.

[0075] Furthermore, it is preferable that 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. [Formula 1] 1 / 10 <AV / RV<1 / 3

[0076] This is because, when the value of the formula 1 is 1 / 10 or less, the surface resistance property decreases, and when it is 1 / 3 or more, the release property decreases.

[0077] Furthermore, it is preferable that the hardened layer according to one embodiment of the present invention simultaneously satisfies the following conditions 1 to 3, where RF is the peel strength (g / inch) of the hardened layer, SA is the residual adhesion rate (%) of the hardened layer, and SR is the surface resistance (Ω / sq) of the hardened layer. (1) 5≦RF≦30 (2) 80≦SA≦100 (3) 10^4≦SR≦10^10

[0078] 2, which is a cross-sectional view of an antistatic silicone release film according to another embodiment of the present invention, antistatic silicone release film 200 according to another embodiment of the present invention can have a substrate film 210, a cured layer 220 of the antistatic silicone release composition described above located on one side of the substrate film, and a cured layer 230 of the antistatic silicone release composition described above located on the other side. In this case, the coating composition for forming cured layer 230 does not need to contain a release force modifier.

[0079] 3, which is a cross-sectional view of an antistatic silicone release film according to yet another embodiment of the present invention, antistatic silicone release film 300 according to yet another embodiment of the present invention may have a substrate film 310, a cured layer 320 of the antistatic silicone release composition described above located on one side of the substrate film, and a silicone release layer 330 located on the other side. In this case, the coating composition for forming silicone release layer 330 may not include a conductive polymer resin.

[0080] The present invention will be described in more detail with reference to the following examples and comparative examples, but the scope of the present invention is not limited to these examples. [Example]

[0081] Example 1 To form an antistatic silicone release layer on one side of a corona-treated polyester substrate film (Toray Advanced Materials Co., Ltd., Excell-50 μm), an antistatic silicone release composition was prepared by mixing 100 parts by weight of alkenylpolysiloxane (Dow Corning Corporation) as solid content, 3 parts by weight of hydrogenpolysiloxane (Dow Corning Corporation), 2.5 parts by weight of conductive polymer resin (aqueous dispersion containing 0.5% by weight of poly-3,4-ethylenedioxythiophene and 0.8% by weight of polystyrene sulfonic acid (molecular weight Mn=150,000), average particle size 50 nm), 10 parts by weight of epoxy binder compound (Esprix Technologies Corporation), 50 ppm of platinum chelate catalyst (Dow Corning Corporation), and 0.2 parts by weight of ionic surfactant (dioctyl sulfosuccinate sodium salt) in water.

[0082] The prepared antistatic silicone release composition was diluted with water to a solids content of 5 wt % and applied to one side of a polyester substrate film, followed by drying at 180°C for 50 seconds to prepare an antistatic silicone release film.

[0083] Example 2 An antistatic silicone release film was produced in the same manner as in Example 1, except that 100 parts by weight of alkenyl polysiloxane was mixed with 10 parts by weight of conductive polymer resin.

[0084] 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 was mixed with 2 parts by weight of conductive polymer resin.

[0085] Example 4 An antistatic silicone release film was produced in the same manner as in Example 1, except that 100 parts by weight of alkenyl polysiloxane was mixed with 7 parts by weight of conductive polymer resin.

[0086] 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 was mixed with 5 parts by weight of conductive polymer resin.

[0087] Example 6 An antistatic silicone release film was produced in the same manner as in Example 1, except that 100 parts by weight of alkenylpolysiloxane was mixed with 1 part by weight of conductive polymer resin.

[0088] Example 7 An antistatic silicone release film was prepared in the same manner as in Example 1, except that dioctylphosphosuccinate sodium salt was used as the ionic surfactant.

[0089] Example 8 An antistatic silicone release film was prepared in the same manner as in Example 1, 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 the ionic surfactant.

[0090] Example 9 An antistatic silicone release film was produced in the same manner as in Example 1, except that 15 parts by weight of an epoxy binder compound was added.

[0091] Example 10 An antistatic silicone release film was produced in the same manner as in Example 1, except that 20 parts by weight of an epoxy binder compound was added.

[0092] 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 to a solids content of 2.5 wt %.

[0093] (Comparative Example) (Comparative Example 1) An antistatic silicone release film was produced in the same manner as in Example 1, except that 100 parts by weight of alkenylpolysiloxane was mixed with 0.5 parts by weight of conductive polymer resin.

[0094] (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 was mixed with 15 parts by weight of conductive polymer resin.

[0095] (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 (a product of Dow Corning) was used as the surfactant.

[0096] Comparative Example 4 An antistatic silicone release film was produced in the same manner as in Example 1, except that no binder mixture was added.

[0097] (Comparative Example 5) An antistatic silicone release film was produced in the same manner as in Example 1, except that no conductive polymer resin was mixed.

[0098] (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 an epoxy binder compound was added.

[0099] Using the release films according to Examples 1 to 11 and Comparative Examples 1 to 6, the physical properties were measured in the following experiments, and the results are shown in Table 1 below.

[0100] (Experimental example) 1. Thickness measurement of the antistatic area and release area (silicone release area) The total thickness of the cured layer is measured using an ellipsometer (Ellipso Technology, Elli-SE).

[0101] The thickness of the silicone coating layer is measured using XRF (Minipal 4, manufactured by Panalytical), and this is taken as the peeled area value.

[0102] The thickness of the antistatic area was calculated using the following formula 2. [Formula 2] Antistatic area = total thickness of cured layer (measured by ellipsometer) - thickness of silicone coating layer (measured by XRF)

[0103] 2.Si in the hardened layer - Ion and S - Ion intensity (counts) ratio (Si - / S - )measurement Measurements were performed using time-of-flight secondary ion mass spectrometry (TOF-SIMS; ION-TOF, Germany).

[0104] The measurement was carried out in negative mode with an Ar-cluster energy intensity of 5 KeV.

[0105] 3. Antistatic properties Using a surface resistance measuring instrument (MCP-T600 manufactured by Mitsubishi Corporation), the sample was placed in an environment of a temperature of 23°C and a humidity of 50% RH, and then the surface resistance of the cured layer was measured in accordance with JIS K7194.

[0106] 4. Peel Force Measurement A release film was attached to a cold-rolled stainless steel plate with double-sided adhesive tape so that the cured layer was facing up, and then adhesive tape (TESA 7475) was placed on the release layer and pressed with a 2 kg pressure roller. The plate was left at room temperature for 1 to 7 days, after which the peel force was measured.

[0107] The peel strength was measured using an AR-1000 (Chem-Instrument) at a peel angle of 180° and a peel speed of 0.3 mpm. The measurement was repeated five times to calculate the average value (g / inch), which was then rounded to the nearest whole number.

[0108] 5. Measurement of residual adhesion rate An 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. The adhesive tape was then peeled off from the cured layer and attached to a cold-rolled stainless steel plate, after which the peel strength was measured.

[0109] For comparison, an adhesive tape (Nitto 31B) that had never been used was attached to a cold-rolled stainless steel plate and the peel strength was measured.

[0110] The peel strength was measured using AR-1000 (Chem-Instrument) at a peel angle of 180° and a peel speed of 0.3 mpm, and the average value was calculated from five measurements.

[0111] The residual adhesion rate was calculated using the following formula 3. [Formula 3] Residual adhesion rate = Peel strength of adhesive tape peeled from cured layer / Peel strength of unused adhesive tape x 100 (%)

[0112] 6. Defect area measurement The area of ​​the bubble defect was measured relative to the area of ​​a 5cm x 5cm release film sample. The longest length of the bubble defect in the 5cm x 5cm release film sample was measured, and the area was calculated by drawing a circle. The total area was then added together to calculate the area of ​​the bubble defect (cm 2 ) was sought.

[0113] The degree of bubble defects (coating appearance) was evaluated by calculating the bubble defect area ratio using the following formula 4 and then evaluating it according to the following criteria. [Formula 4] Bubble defect area ratio (%) = Bubble defect area / 25cm 2 ×100(%) ◎: 0% or more but less than 1% ○: 1% or more but less than 2% △: 2% or more but less than 5% ×: 5% or more

[0114] 7. Solvent resistance measurement The resistance of the top surface of the film to solvents was measured.

[0115] The measurement was carried out by dipping a cotton swab in isopropyl alcohol, then moving the swab back and forth across the cured layer 10 times with a 100g load while maintaining the swab at a 45 degree angle, and then evaluating the solvent resistance of the coating surface according to the following criteria. ◎:Excellent ○: Good △:Normal ×: Unpaid

[0116] 8. Pressure Measurement The hardened layer was rubbed back and forth with the thumb five times, and then inspected with the naked eye and evaluated according to the following criteria. ◎: No change after evaluation (No smear) ○: Slightly smeared, but no problems in use △: The hardened layer smears white, as if oil has been pressed. ×: The hardened layer hardens and falls off (rub-off)

[0117] [Table 1]

[0118] 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, and therefore have excellent coating appearance, excellent pushability of the cured layer, and have surface resistance and peel strength within appropriate ranges, while also having excellent residual adhesion. The antistatic silicone release film according to Example 8 of the present invention was found to have the best appearance and physical properties.

[0119] In addition, it was confirmed that the surface resistance value, which is an antistatic property, and the peel force, residual adhesion rate, and appearance, which are release properties, are correlated and changed depending on the thickness ratio of the antistatic region to the silicone release region in the cured layer and the ratio of silicon ions to sulfur ions in the top and bottom of the release films according to Examples 1 to 11 and Comparative Examples 1 to 6.

[0120] Furthermore, in the case of the antistatic silicone release film according to Example 9 of the present invention, it was confirmed that the surface resistance properties were excellent in response to an increase in the binder content, based on the same content of conductive polymer.

[0121] Furthermore, in Examples 10 and 11 of the present invention, even if the absolute content of the conductive polymer and alkenylsiloxane changes, it can be confirmed that the release properties are also excellent as long as the ratio of the antistatic area to the release area does not change significantly.

[0122] In contrast, in the case of the release films according to Comparative Examples 1 and 2, the content of the conductive polymer resin was either too low or too high, resulting in an excessive increase in the surface resistance, which is an antistatic property, or an excessive decrease in the residual adhesion rate, which is a release property.

[0123] In addition, it can be seen that the release film according to Comparative Example 3, which does not contain an ionic surfactant, has poor coating appearance and poor peel strength properties.

[0124] In addition, it can be seen that the release films according to Comparative Examples 4 and 5 cannot obtain the surface resistance properties if they do not contain an epoxy binder compound or a conductive polymer resin.

[0125] In addition, in Comparative Example 6, it can be confirmed that when the binder compound is excessively large, the surface resistance property improves, but the mold release property is fatally deteriorated.

[0126] As described above, the antistatic silicone release film according to the present invention can be appropriately applied to a desired application, but is not limited thereto. Furthermore, the present invention can provide an antistatic silicone release film of excellent quality for use in applications in the field of precision materials, which has an appropriate range of peel strength and a high level of residual adhesion, so that it can be appropriately used to suit the application without deteriorating the functionality of the pressure-sensitive adhesive layer.

[0127] Furthermore, the antistatic silicone release film of the present invention has excellent durability of the cured layer, excellent resistance to organic solvents, high adhesion to the substrate, and little shedding of the cured layer due to friction. Furthermore, it can be seen that the excellent antistatic properties have the effect of solving problems such as contamination caused by static electricity and poor release.

[0128] In this specification, only a few examples of the various embodiments carried out by the inventors are described, but the technical concept of the present invention is not limited or restricted to these examples, and can be modified and implemented in various ways by those skilled in the art.

Claims

1. A base film; a cured layer of an antistatic silicone release composition located on at least one surface of the substrate film, The cured layer has an intensity ratio of silicon ions that exhibit silicone release properties and sulfur ions that exhibit antistatic properties (Si － / S － 1. An antistatic silicone release film comprising antistatic areas where R 1 is less than 1 and silicone release areas where R 2 is greater than 10.

2. The intensity ratio of the hardened layer (Si － / S － 2. The antistatic silicone release film according to claim 1, wherein the molecular weight of the silicone release film is 10 to 10,000 at the top, farthest from the boundary with the base film, and 0.001 to 1 at the bottom, which is at the boundary with the base film.

3. The thickness ratio of the antistatic area to the silicone release area satisfies the following formula 1: [Formula 1] 1 / 10<AV / RV<1 / 3 10. 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.

4. 2. The antistatic silicone release film according to 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.

5. 5. The antistatic silicone release film according to claim 4, wherein the antistatic silicone release composition comprises, per 100 parts by weight of the alkenylpolysiloxane, 2.5 to 7.5 parts by weight of the hydrogenpolysiloxane, 1 to 10 parts by weight of the conductive polymer resin, 5 to 20 parts by weight of the binder compound, and 10 ppm to 1,000 ppm of the platinum chelate catalyst.

6. The antistatic silicone release composition further comprises an ionic surfactant having both a cation and an anion, 5. 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.

7. 7. The antistatic silicone release film according to claim 6, wherein the ionic surfactant is present in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the alkenylpolysiloxane.

8. The antistatic silicone release film of claim 4 , wherein the binder compound comprises a silane-based compound and a non-silane-based polyfunctional compound.

9. The silane-based compound is at least one compound selected from the group consisting of epoxysilanes, aminosilanes, vinylsilanes, methacryloxysilanes, and isocyanate silanes; 9. The antistatic silicone release film according to claim 8, wherein the non-silane-based multifunctional compound is an epoxy-based multifunctional compound having an epoxy functional group.

10. 10. The antistatic silicone release film according to claim 9, wherein the epoxy-based polyfunctional compound has one or more functional groups selected from the group consisting of amino-based, hydroxy-based, aldehyde-based, ester-based, vinyl-based, acrylic-based, imide-based, cyano-based, and isocyanate-based compounds, and has three or more functional groups in one molecule.

11. 9. The antistatic silicone release film according to claim 8, wherein the weight ratio of the non-silane-based polyfunctional compound to the silane-based compound is 2 to 20.

12. 5. The antistatic silicone release film according to claim 4, wherein the conductive polymer resin has an average particle size of 10 to 90 nm and is an aqueous dispersion containing polyanion and polythiophene or an aqueous dispersion containing polyanion and polythiophene derivative.

13. 10. The antistatic silicone release film of claim 1, wherein the antistatic silicone release composition comprises 0.5 to 15 weight percent solids.

14. 2. The antistatic silicone release film according to claim 1, wherein the surface tension of the substrate film is 1.0 to 1.5 times that of the cured layer.

15. 15. The antistatic silicone release film according to claim 1, wherein the thickness of the base film is 15 to 300 μm, and the thickness of the cured layer is 0.01 to 10 μm.

16. The hardened layer according to any one of claims 1 to 14 satisfies the following conditions 1 to 3 simultaneously: (1) 5≦RF≦30 (2) 80≦SA≦100 (3) 10^4≦SR≦10^10 where RF is the peel force of the cured layer (g / inch), SA is the residual adhesion rate of the cured layer (%), and SR is the surface resistance of the cured layer (Ω / sq).

17. A base film; a cured layer of an antistatic silicone release composition located on one side of the substrate film; a silicone release layer located on the other side of the base film, The cured layer has an intensity ratio of silicon ions that exhibit silicone release properties and sulfur ions that exhibit antistatic properties (Si － / S － 1. An antistatic silicone release film comprising antistatic areas having a ratio of 1 to 1, and silicone release areas having a ratio of 1 to 10.

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