WO2020189882A1

WO2020189882A1 - Antistatic silicone release film

Info

Publication number: WO2020189882A1
Application number: PCT/KR2019/018281
Authority: WO
Inventors: 이정환; 안병철; 김길중
Original assignee: 도레이첨단소재 주식회사
Priority date: 2019-03-20
Filing date: 2019-12-23
Publication date: 2020-09-24
Also published as: KR102232851B1; JP2024038254A; JP2022529574A; CN111716832A; CN111716832B; KR20200113042A

Abstract

The present invention provides an antistatic silicone release film which does not have a side effect caused by an electrostatic discharge when being peeled from an adhesive, as the film has an excellent antistatic function, and which has a stable release characteristic, as the film has excellent adhesion to a base material of a hardening layer, and the hardening layer has a high degree of crosslinking.

Description

Antistatic silicone release film

The present invention relates to an antistatic silicone release film, and more particularly, with an excellent antistatic function, there is no side effect due to static electricity when peeling from an adhesive, and the adhesion of the cured layer to the substrate is excellent, and the degree of crosslinking of the cured layer is high. It relates to an antistatic silicone release film having stable release characteristics.

At present, as the industrialization of semiconductors, electrical electronics, and displays increases rapidly, the use of synthetic resins or synthetic fibers in these fields is rapidly increasing, and accordingly, a static electricity problem in the processing process has emerged.

In the field of release films, which are generally used for the function of protecting an adhesive layer, the demand for an antistatic function is steadily increasing. Conventionally, an antistatic function was given to the adhesive to solve problems such as contamination and poor peeling caused by static electricity generated when the release film was separated from the adhesive layer, but due to incompatibility between the antistatic component and the adhesive component There was a difficulty in implementing sufficient antistatic performance. Therefore, in recent years, in addition to the pressure-sensitive adhesive, there are many cases where an antistatic function is provided to the release layer.

On the other hand, the release properties required for the release film for use in the field of precision materials include a peeling force in an appropriate range according to the type and use of the adhesive, and a high residual adhesive rate so that the release layer is transferred to the adhesive layer and does not degrade the function of the adhesive layer. Solvent resistance so that the release layer is not damaged by the organic solvent used in the pressure-sensitive adhesive, and high adhesion between the release layer and the substrate are required so that the release layer is not removed due to friction in the processing process. In addition, as the release film is also used for the pressure-sensitive adhesive carrier film due to the thinning of the pressure-sensitive adhesive layer, stable release properties with little change with temperature and time must be secured.

In addition, conventional antistatic technologies 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. In addition, a method of manufacturing an antistatic release film by including a metal in a silicone composition by applying such antistatic technology has been used.

However, these conventional techniques are disadvantageous in terms of economy and have limitations in implementing sufficient antistatic performance, and there is a problem in that a uniform coating layer is not formed. In addition, when the antistatic composition uses an ionic compound, there is a problem that the curing reaction of the silicone release composition is hindered and stable release properties are not secured, and the adhesion between the antistatic release layer and the substrate decreases, so that the release layer is removed or the adhesive There was a problem that performance was degraded.

In addition, in order to impart an antistatic function to such a release layer, it is mainly manufactured by an offline manufacturing process in which the antistatic layer and the release layer are separately coated. Therefore, during the coating process by each process, there is a problem that a lot of quality problems occur due to foreign substances and scratches, and a lot of manufacturing costs occur.

Accordingly, the present inventors confirmed that an antistatic silicone release film can be prepared in a single coating process by mixing a conductive polymer resin having excellent compatibility and a binder compound having excellent reactivity in a silicone release coating composition for producing a release film. The present invention has been completed.

(Patent Document 1) Korean Patent Application Publication No. 10-2015-0104477

The present invention has been devised to solve the above problems and meet conventional requirements, and an object of the present invention is to have excellent antistatic properties through an in-line manufacturing process, so that a release film for semiconductors, electric and electronic applications, and displays When used as, it is intended to provide an antistatic silicone release film that can reduce side effects such as product contamination and poor peeling due to static electricity when peeling from the adhesive.

Another object of the present invention is that it has excellent peel strength and a high level of residual adhesion, so that it can be appropriately used for a purpose without deteriorating the performance of the pressure-sensitive adhesive layer, and by configuring a dense cured layer, the durability of the cured layer and It is intended to provide an antistatic silicone release film having excellent solvent resistance, high adhesion between the cured layer and the substrate, and less change in physical properties with temperature and time, and thus has stable release properties.

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

The above object includes a base film and a cured layer of an antistatic silicone release composition positioned on at least one surface of the base film, wherein the cured layer includes an intensity ratio of silicon ions exhibiting silicone release properties and sulfur ions exhibiting antistatic properties ( Si ^{^-} / S ^-) it is containing less than one antistatic region 10 and greater than the silicone release area, is achieved by the antistatic silicone release film.

Here, the intensity ratio of the cured layer (Si ^{^-} / S ^-) is at the boundary with the remotest top of the base film 10 to 10,000, characterized in that 0.001 to 1 at the boundary between the bottom of the base film.

Preferably, the thickness ratio of the antistatic region and the silicon release region satisfies Equation 1 below,

(Equation 1)

1/10 <AV / RV <1/3,

Here, AV is the thickness of the antistatic region, and RV is the thickness of the silicon release region.

Preferably, the antistatic silicone release composition is characterized in that it comprises alkenylpolysiloxane, hydroelectric polysiloxane, a conductive polymer resin, a binder compound, and a platinum chelate catalyst.

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

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

Preferably, the ionic surfactant is characterized by containing 0.01 parts by weight to 5 parts by weight based on 100 parts by weight of alkenylpolysiloxane.

Preferably, the binder compound is characterized in that it contains a silane-based compound and a non-silane-based polyfunctional compound.

Preferably, the silane-based compound is at least one of epoxy silane-based, amino silane-based, vinyl silane-based, methacryloxy silane-based, and isocyanate silane-based compound, and the non-silane-based polyfunctional compound is an epoxy-based polyfunctional compound having an epoxy functional group. It is characterized in that it is a compound.

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

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

Preferably, the conductive polymer resin has an average particle diameter of 10 to 90 nm, and is characterized in that it is an aqueous dispersion containing polyanions and polythiophene or an aqueous dispersion containing polyanions and polythiophene derivatives.

Preferably, the antistatic silicone release composition is characterized in that it contains 0.5 to 15% by weight of solids.

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

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 peel 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.

In addition, the above object includes a base film, a cured layer of an antistatic silicone release composition located on one side of the base film, and a silicone release layer located on the other side of the base film, wherein the cured layer is silicone exhibiting silicone release characteristics. and ion intensity ratio of sulfur ion that indicates the antistatic property (Si ^{^-} / S ^-) is containing less than one antistatic region 10 and greater than the silicone release area, is achieved by the antistatic silicone release film.

According to the present invention, since it has antistatic performance, it is possible to solve problems such as contamination due to static electricity generated when the release film is separated from the pressure-sensitive adhesive layer and poor peeling.

Furthermore, by providing excellent peeling force and high level of residual adhesion, it can be appropriately used according to the purpose without deteriorating the function of the pressure-sensitive adhesive layer. Also, the durability of the cured layer is excellent, so that it has solvent resistance to organic solvents. It has a high adhesion to and has the effect of less dropping of the hardened layer due to friction.

Furthermore, by configuring a dense hardened layer, it has an effect such as having stable release properties with little change over temperature and 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 by those skilled in the art from the following description.

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

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

3 is a cross-sectional view of an antistatic silicone release film according to 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. These examples are only illustratively presented to illustrate the present invention in more detail, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited by these examples. .

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. Also, although methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present invention, suitable methods and materials are described herein.

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

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

First, an antistatic silicone release film according to an 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 Figure 1, the antistatic silicone release film according to an embodiment of the present invention, the antistatic silicone release film 100 according to an aspect of the present invention is located on at least one side of the base film 110 and the base film. It includes a cured layer 120 of the antistatic silicone 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 realized at the same time by inline coating the antistatic silicone release composition on the base film once in the manufacture of the release film. It is characterized.

The antistatic silicone release composition forming the cured layer 120 of the antistatic silicone release film according to an embodiment of the present invention may include an alkenylpolysiloxane, a hydroelectric polysiloxane, a conductive polymer resin, a binder compound, and a platinum chelate catalyst. have. In addition, in one embodiment, the antistatic silicone release composition may further include an ionic surfactant having both a cation and an anion.

In one embodiment, the alkenylpolysiloxane may have a structure represented by Formula 1 below.

[화학식 1][Formula 1]

Here, m and n are each independently an integer of 10 to 500. In this case, m and n do not mean block bonds, but they only mean that the sum of each unit is m and n.

Therefore, each unit in Formula 1 is a random bond or a block bond. In addition, R1, R2, R3 are each an alkyl or alkenyl group selected from -CH ₃ , -CH=CH ₂ , -CH ₂ CH=CH ₂ , -CH ₂ CH ₂ CH ₂ CH ₂ CH=CH ₂ , and alkenyl The group may be present in any part of the molecule, but it is preferred that at least two groups are present.

In one embodiment, the hydroelectric polysiloxane may have a structure represented by Formula 2 below.

[화학식 2][Formula 2]

Here, a is an integer of 1 to 200, b is an integer of 1 to 400. In this case, a and b do not mean a block combination, they just mean that the sum of each unit is a and b. Therefore, in Formula 2, each unit is a random bond or a block bond.

The alkenyl polysiloxane represented by Formula 1 and the hydroelectric polysiloxane represented by Formula 2 may be linear, branched, radial, or cyclic, and mixtures thereof may be used. In addition, the mixing ratio of alkenylpolysiloxane and hydropre-polysiloxane is preferably 2.5 to 7.5 parts by weight of hydropre-polysiloxane based on 100 parts by weight of alkenylpolysiloxane. If the amount of hydropre-polysiloxane is less than 2.5 parts by weight, the amount of unreacted alkenylpolysiloxane cannot be sufficiently cured and thus stable release properties cannot be realized.If it exceeds 7.5 parts by weight, the amount of unreacted hydropolysiloxane increases. This is because the peeling characteristics may deteriorate.

In one embodiment, the antistatic silicone release composition is a conductive polymer resin to impart antistatic performance, and the conductive polymer resin contains a polyanion and a polythiophene-containing water dispersion or a polyanion and a polythiophene derivative. It is preferable that it is an aqueous dispersion.

Polyanions are acidic polymers, such as high molecular carboxylic acid, high molecular weight sulfonic acid, and polyvinyl sulfonic acid. Examples of the polymeric carboxylic acid include polyacrylic acid, polymethacrylic acid, and polymaleic acid, and examples of the polymeric sulfonic acid include polystyrenesulfonic acid, but are not limited thereto.

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

In addition, it is preferable that the conductive polymer resin exhibits stable antistatic performance by using an aqueous dispersion having an average particle diameter of 10 to 90 nm. When the average particle diameter of the conductive polymer resin exceeds 90 nm, it is not uniformly distributed inside the cured layer, so that the deviation of the surface resistance becomes very large, and the antistatic performance cannot be properly implemented. In addition, when the average particle diameter of the conductive polymer resin is less than 10 nm, as the molecular weight decreases, the antistatic performance cannot be realized when the molecular weight is increased by more than a specific distance between molecules, and the smaller the average particle diameter during in-line stretching, the smaller the average particle diameter, the lower the antistatic performance.

The conductive polymer resin preferably contains 1 to 10 parts by weight based on 100 parts by weight of alkenylpolysiloxane. This is because when the content of the conductive polymer resin is less than 1 part by weight compared to 100 parts by weight of alkenylpolysiloxane, the surface resistance properties are deteriorated due to insufficient antistatic properties, and when the content of the conductive polymer resin exceeds 10 parts by weight, the release properties due to the curing disturbance of the silicone decrease .

In one embodiment, the antistatic silicone release composition derives stable release properties and antistatic properties by controlling the crosslinking density, improves the compatibility of the conductive polymer resin to realize uniform antistatic properties, and improves the solvent resistance of the cured layer and A binder compound may be included to improve durability and increase 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, it is preferable that the binder compound has a weight ratio of 2 to 20 of the non-silane-based polyfunctional compound to the silane-based compound. The silane-based compound is at least one of an epoxy silane-based, amino silane-based, vinyl silane-based, methacryloxy silane-based, and isocyanate silane-based compound, and the non-silane-based polyfunctional compound may be an epoxy-based polyfunctional compound having an epoxy functional group. .

The epoxy-based polyfunctional compound is preferable because the epoxy-based compound is excellent in compatibility and stretchability with a conductive polymer. In other words, the compatibility differs according to the content of N, C, and O, and the alkenyl group is attached to the functional group of the conductive polymer, resulting in improved stretchability due to the swelling effect. The epoxy-based polyfunctional compound has at least one functional group selected from the group consisting of amino, hydroxy, aldehyde, ester, vinyl, acrylic, imide, cyano, and isocyanate, and 3 or more It is preferable to have a functional group.

It is preferable that the binder compound contains 5 to 20 parts by weight of the binder compound based on 100 parts by weight of the alkenylpolysiloxane. If the content of the binder compound is less than 5 parts by weight, the cured layer has a low adhesion to the substrate, and the cured layer is peeled off, or the compatibility of the conductive polymer resin is poor, resulting in a problem of uneven antistatic performance. This is because when it exceeds 20 parts by weight, it affects the peeling force and residual adhesion, resulting in a problem of deteriorating release properties.

In one embodiment, the antistatic silicone release composition includes a platinum chelate catalyst, which performs a function of helping the addition reaction of Formulas 1 and 2, and the platinum chelate catalyst in the antistatic silicone release composition contains 1 ppm to 1,000 ppm. It is desirable.

In one embodiment, the antistatic silicone release composition may further include an ionic surfactant having both a cation (cationic group) and an anion (anion 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 containing an anionic group.

In the case of applying a nonionic surfactant that does not have an anionic group, it is difficult to properly control the surface tension of the antistatic silicone release composition, so it does not show sufficient wettability in the process of being applied to the base film, so the appearance of the antistatic silicone release film is defective. There are many problems that are recognized, and in particular, when a silicone-based nonionic surfactant containing siloxane is applied, the surface tension of the antistatic release composition is not properly controlled, and compatibility with the conductive polymer resin is also insufficient. Since there is a problem of causing appearance defects by forming aggregates, it is preferable to use an ionic surfactant having both a cation and an anion in the present invention in order to solve this problem.

In addition, the surfactant according to the present invention is an ionic surfactant having an anionic group selected from sulfo-, phosphor-, or carboxyl- groups among ionic surfactants containing anionic groups, that is, anionic groups derived from sulfonic acid, phosphorous acid or carboxylic acid. By applying an antistatic release composition containing an activator, it is possible to secure optimal wettability to the base film while maintaining compatibility with alkenylpolysiloxane, hydroelectric polysiloxane, and conductive polymer resin. In the embodiment of the present invention, dioctyl sulfosuccinate sodium salt and dioctyl phosphosuccinate sodium salt are used as ionic surfactants, but the present invention is not limited thereto.

The ionic surfactant may include 0.01 parts by weight to 5 parts by weight based on 100 parts by weight of alkenylpolysiloxane, and preferably 0.05 to 1 part by weight. This is because when the content of the ionic surfactant is less than 0.01 parts by weight, the content is not sufficient to serve as a surfactant, so the effect of improving the appearance of the antistatic silicone release film does not appear, and the content of the ionic surfactant exceeds 5 parts by weight. In this case, there is a problem that the interaction with the pressure-sensitive adhesive is promoted, resulting in an increase in peeling force, which exhibits unstable release properties.

In one embodiment, the antistatic silicone release composition is preferably diluted to contain 0.5 to 15% by weight of solid content, and then coated on a polyester base film. When the solid content of the antistatic silicone release composition is less than 0.5% by weight, a uniform cured layer cannot be obtained, so stable release properties and antistatic properties cannot be obtained, and when it exceeds 15% by weight, blocking between films occurs. , There is a problem in that adhesion to the substrate of the coating composition is deteriorated, causing a problem of silicone transfer, and poor coating appearance.

In addition, the solvent of the antistatic silicone release composition is not limited in type as long as it can be applied on the polyester base film by dispersing the solid content of the present invention, but is preferably coated in the state of an aqueous coating solution containing water as the main medium.

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

The antistatic silicone release film according to an embodiment of the present invention preferably has a surface tension of 1.0 to 1.5 times the surface tension of the base film compared to the cured layer. At this time, if the surface tension of the base film compared to the cured layer is less than 1.0 times, the wettability of the coating solution is deteriorated, and when it exceeds 1.5 times, the coating solution is agglomerated, causing appearance defects.

In addition, for the purpose of improving coating properties and improving transparency to the antistatic silicone release composition used in the present invention, it may further contain a suitable organic solvent to a degree that does not impair the effects of the present invention, and the preferred organic solvent is Isopropyl alcohol, butyl cellosolve, ethyl cellosolve, acetone, methanol, ethanol, and the like can be used. However, if a large amount of organic solvent is contained in the coating composition, there is a risk of explosion in drying, stretching and heat treatment processes when applied to the in-line coating method, so the content of the organic solvent is 10% by weight or less in the coating composition, more preferably It is preferable to limit it to 5% by weight or less.

In addition, 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. When the thickness of the base film is less than 15 μm, the degree of deformation due to external force increases, and thus the use as a carrier film is not satisfied, and when the thickness of the film exceeds 300 μm, there is a problem of inferior economy.

In addition, the thickness of the cured layer 120 according to an embodiment of the present invention is preferably 0.01 to 10㎛. This means that when the thickness of the cured layer is less than 0.01 μm, a uniform cured layer may not be formed, and when the thickness of the cured layer exceeds 10 μm, blocking between one surface and the rear surface of the polyester base film 110 on which the cured layer 120 is located. Because it can occur.

In addition, in the present invention, in order to distinguish between the antistatic region and the peeling region, which are similar in shape to the antistatic release film obtained through two coats of the offline method, compatibility with the conductive polymer resin and silicone is achieved through the application of an ionic surfactant. It is possible to achieve the technical goal by securing excellent wettability and distinguishing between the antistatic area and the silicon release area (peelable area).

A hardened layer, according to one embodiment of the present invention are silicon ions representing a silicone release characteristic is intensity (Intensity or counts) the ratio of ^{^{^{(Si - - / S) -}}} - sulfur ion (S) representing the antistatic (Si) An antistatic region less than 1 and a silicon release region greater than 10 may be included. This intensity ratio can be measured by TOF-SIMS, and is a relative ratio value of silicon ions and sulfur ions in a single cured layer.

Preferably, the intensity ratio of the cured layer (Si ^{^-} / S ^-) is at the boundary with the remotest top of the base film 10 to 10,000, preferably from 0.001 to 1 at the boundary between the bottom of the base film. Due to this, excellent antistatic properties and silicone release properties can be simultaneously implemented in a single cured layer. Preferably, the intensity ratio at the top may be 100 to 5,000, which is realized in a stacked form of silicon ions exhibiting silicon release characteristics and sulfur ions exhibiting antistatic characteristics, such as a phase-separated structure. I can.

In addition, it is preferable that the thickness ratio of the antistatic region and the silicone release region of the cured layer satisfies Equation 1 below, where AV is the thickness of the antistatic region, and RV is the thickness of the silicone release region.

(Equation 1)

1/10 <AV / RV <1/3

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

In addition, the cured layer according to an embodiment of the present invention satisfies the following conditions 1 to 3 at the same time, but RF is the peel force (g/inch) of the cured layer, SA is the residual adhesion rate (%) of the cured layer, and SR Is preferably the surface resistance (Ω/sq) of the cured layer.

(1) 5 ≤ RF ≤ 30

(2) 80 ≤ SA ≤ 100

(3) 10^4 ≤ SR ≤ 10^10

From Figure 2, which is a cross-sectional view of an antistatic silicone release film according to another embodiment of the present invention, the antistatic silicone release film 200 according to another embodiment of the present invention is located on one side of the base film 210 and the base film. The cured layer 230 of the above-described antistatic silicone release composition may be positioned on the other side from the cured layer 220 of the above-described antistatic silicone release composition. In this case, the coating composition for constituting the cured layer 230 may not include a peel force control agent.

In addition, from Fig. 3, 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 300 according to another embodiment of the present invention includes a base film 310 and one side of the base film. A silicone release layer 330 may be positioned on one side different from the cured layer 320 of the above-described antistatic silicone release composition positioned at. In this case, the coating composition for configuring the silicone release layer 330 may not include a conductive polymer resin.

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

[실시예][Example]

[실시예 1][Example 1]

In order to form an antistatic silicone release layer on one side of the corona-treated polyester base film (Toray Advanced Materials, Excell-50㎛), based on 100 parts by weight of alkenylpolysiloxane (manufactured by Dow Corning) as a solid content, hydroelectric polysiloxane ( Dow Corning's product) 3 parts by weight, 2.5 parts by weight of a conductive polymer resin (a water dispersion containing 0.5% by weight of poly3,4-ethylenedioxythiophene and 0.8% by weight of polystyrenesulfonic acid (molecular weight Mn=150,000), an average particle diameter of 50 nm), Antistatic silicone release composition by mixing 10 parts by weight of an epoxy-based binder compound (manufactured by Esprix Technology), 50 ppm of a platinum chelate catalyst (manufactured by Dow Corning), and 0.2 parts by weight of an ionic surfactant (dioctyl sulfosuccinate sodium salt) in water Was prepared.

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

[실시예 2][Example 2]

An antistatic silicone release film was prepared in the same manner as in Example 1, except that 10 parts by weight of a conductive polymer resin were mixed with respect to 100 parts by weight of alkenylpolysiloxane.

[실시예 3][Example 3]

An antistatic silicone release film was prepared in the same manner as in Example 1, except that 2 parts by weight of a conductive polymer resin were mixed with respect to 100 parts by weight of alkenylpolysiloxane.

[실시예 4][Example 4]

An antistatic silicone release film was prepared in the same manner as in Example 1, except that 7 parts by weight of a conductive polymer resin was mixed with respect to 100 parts by weight of alkenylpolysiloxane.

[실시예 5][Example 5]

An antistatic silicone release film was prepared in the same manner as in Example 1, except that 5 parts by weight of a conductive polymer resin were mixed with respect to 100 parts by weight of alkenylpolysiloxane.

[실시예 6][Example 6]

An antistatic silicone release film was prepared in the same manner as in Example 1, except that 1 part by weight of the conductive polymer resin was mixed with respect to 100 parts by weight of alkenylpolysiloxane.

[실시예 7][Example 7]

An antistatic silicone release film was prepared through the same procedure as in Example 1, except that dioctyl phospho succinate sodium salt was used as the ionic surfactant.

[실시예 8][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 phospho succinate sodium salt were mixed as an ionic surfactant.

[실시예 9][Example 9]

An antistatic silicone release film was prepared in the same manner as in Example 1, except for mixing 15 parts by weight of an epoxy-based binder compound.

[실시예 10][Example 10]

An antistatic silicone release film was prepared in the same manner as in Example 1, except that 20 parts by weight of the epoxy-based binder compound were mixed.

[실시예 11][Example 11]

An antistatic silicone release film was prepared in the same manner as in Example 1, except for diluting in water so that the solid content of the prepared antistatic silicone release composition was 2.5% by weight.

[비교예][Comparative Example]

[비교예 1][Comparative Example 1]

An antistatic silicone release film was prepared in the same manner as in Example 1, except that 0.5 parts by weight of a conductive polymer resin was mixed with respect to 100 parts by weight of alkenylpolysiloxane.

[비교예 2][Comparative Example 2]

An antistatic silicone release film was prepared in the same manner as in Example 1, except that 15 parts by weight of a conductive polymer resin was mixed with respect to 100 parts by weight of alkenylpolysiloxane.

[비교예 3][Comparative Example 3]

An antistatic silicone release film was prepared through the same procedure as in Example 1, except that 0.2 parts by weight of a silicone-based surfactant (manufactured by Dow Corning) was used as a surfactant.

[비교예 4][Comparative Example 4]

An antistatic silicone release film was prepared in the same manner as in Example 1, except that the binder mixture was not mixed.

[비교예 5][Comparative Example 5]

An antistatic silicone release film was prepared in the same manner as in Example 1, except that the conductive polymer resin was not mixed.

[비교예 6][Comparative Example 6]

An antistatic silicone release film was prepared in the same manner as in Example 1, except for mixing 25 parts by weight of the epoxy-based binder compound.

Physical properties were measured through the following experimental examples using the release films according to Examples 1 to 11 and Comparative Examples 1 to 6, and the results are shown in Table 1 below.

[실험예][Experimental Example]

1. 대전방지 영역과 박리 영역(실리콘 이형 영역)의 두께 측정1. Thickness measurement of antistatic area and peeling area (silicon release area)

The total thickness of the cured layer is measured using an ellipsometer (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 region was calculated according to Equation 2 below.

[Equation 2]

Antistatic area = Total thickness of cured layer (Elipsometer measurement)-Silicone coating layer thickness (XRF measurement)

2. 경화층 내의 2. In the hardened layer SiSi -이온과 S-이온의 Of -ion and S-ion Intensity(counts)비Intensity(counts) ratio ( ( SiSi -/S-)측정-/S-) measurement

Flight type secondary ion mass spectrometry; It was measured by TOF-SIMS (Time of Flight Secondary Ion Mass Spectrometry; ION-TOF, Germany).

Measurement conditions were conducted in negative mode with the energy intensity of Ar-cluster 5KeV.

3. 대전방지 특성3. Antistatic characteristics

After installing the sample in an environment with a temperature of 23° C. and a humidity of 50% RH using a surface resistance meter (Mitsubishi, MCP-T600), the surface resistance of the cured layer was measured according to JIS K7194.

4. 박리력 측정4. Peel force measurement

After attaching the release film to the cold-rolled stainless steel plate with the hardened layer on top with double-sided adhesive tape, place the adhesive tape (TESA 7475) on the release layer, press it with a 2 kg compression roller, and leave it at room temperature for 1 to 7 days and then peel off. The force was measured.

Peel force was measured using AR-1000 (Chem-Instrument) at a peel angle of 180° and a peel rate of 0.3 mpm, and the average value (g/inch) was calculated by measuring five times, and rounded to the first decimal place.

5. 잔류접착률 측정5. Measurement of residual adhesion rate

An adhesive tape (Nitto 31B) was placed on the cured layer, pressed with a 2 kg compression roller, left at room temperature for 30 minutes, and then peeled off the adhesive tape from the cured layer, and then attached to the cold-rolled stainless steel plate, and the peel force was measured.

In addition, for comparison, an adhesive tape (Nitto 31B), which has not been used, was attached to the cold-rolled stainless steel plate, and then the peel force was measured.

Peel force was measured using AR-1000 (Chem-Instrument) at a peel angle of 180° and a peel rate of 0.3 mpm, and the average value was calculated by measuring five times.

The residual adhesion rate was calculated according to Equation 3 below.

[Equation 3]

Residual adhesion rate = Peeling force of the adhesive tape peeled from the cured layer / Peeling force of the adhesive tape that has not been used x 100 (%)

6. 결점 면적 측정6. Defect area measurement

The area of the foaming defect was measured relative to the area of the release film sample of 5cm X 5cm. The longest length of the foamy defects in the 5cm X 5cm release film sample was measured and the area was calculated with a circle, and then the area (cm ² ) of the foamable defects was calculated by summing the whole.

The degree of foaming defects (coating appearance) was evaluated by calculating the area ratio of foaming defects according to Equation 4 below, and the following criteria.

[Equation 4]

Foaming defect area ratio (%) = Foaming defect area/ 25cm ² X 100(%)

◎: 0% or more and less than 1%

○: 1% or more and less than 2%

△: 2% or more and less than 5%

X: 5% or more

7. 내용제성 측정7. Solvent resistance measurement

The resistance of the film surface to a solvent was measured.

For the measurement, after soaking the cotton swab with isopropyl alcohol and maintaining the angle of the swab at 45 degrees, the cured layer was reciprocated 10 times with a load of 100 g, and the solvent resistance state of the coated surface was evaluated based on the following criteria.

◎: Excellent

○: Good

△: Normal

X: Not met

8. 밀림성 측정8. Elevation measurement

After rubbing the hardened layer back and forth 5 times with the thumb, it was visually checked and evaluated according to the following criteria.

◎: No change after evaluation (No smear)

○: Slightly smeared, but no problem in use

△: The hardened layer is smeared as if oil is pushed.

Ｘ: The hardened layer clumps and falls off (Rub-off)

구분division	대전방지영역:박리영역(nm)Antistatic area: peeling area (nm)	최상부~최하부(Si^-/S^-)The top-bottom (Si ^{^-} / S ^-)	표면저항(Ω/sq)Surface resistance (Ω/sq)	박리력 (g/inch)Peel force (g/inch)	잔류접착률 (%)Residual adhesion rate (%)	외관Exterior	내용제성Solvent resistance	밀림성Jungle
실시예1Example 1	15:8015:80	1,250~0.011,250~0.01	1 x 10⁷ 1 x 10 ⁷	1616	9797	○○	◎◎	◎◎
실시예2Example 2	26:8026:80	800~0.2800~0.2	1 x 10⁴ 1 x 10 ⁴	1010	8585	○○	◎◎	○○
실시예3Example 3	12:8012:80	900~0.5900~0.5	1 x 10⁸ 1 x 10 ⁸	1414	9797	○○	◎◎	◎◎
실시예4Example 4	23:8023:80	950~0.1950~0.1	1 x 10⁵ 1 x 10 ⁵	1111	8888	○○	◎◎	◎◎
실시예5Example 5	25:8025:80	1,000~0.11,000~0.1	1 x 10⁶ 1 x 10 ⁶	1515	9696	○○	◎◎	◎◎
실시예6Example 6	10:8010:80	9,000~0.0019,000~0.001	1 x 10⁹ 1 x 10 ⁹	1818	9898	○○	◎◎	◎◎
실시예7Example 7	15:8015:80	1,250~0.051,250~0.05	1 x 10⁷ 1 x 10 ⁷	1616	9595	○○	◎◎	◎◎
실시예8Example 8	15:8015:80	1,250~0.011,250~0.01	1 x 10⁷ 1 x 10 ⁷	1414	9696	◎◎	◎◎	◎◎
실시예9Example 9	20:8020:80	1,100~0.21,100~0.2	1 x 10⁶ 1 x 10 ⁶	1313	9292	○○	◎◎	◎◎
실시예10Example 10	23:8023:80	950~0.1950~0.1	1 x 10⁵ 1 x 10 ⁵	99	9494	○○	◎◎	◎◎
실시예11Example 11	7.5:407.5:40	800~0.5800~0.5	1 x 10⁹ 1 x 10 ⁹	2121	9292	○○	◎◎	◎◎
비교예1Comparative Example 1	8:808:80	12,000~0.000112,000~0.0001	1 x 10¹¹ 1 x 10 ¹¹	1818	9797	○○	◎◎	◎◎
비교예2Comparative Example 2	40:8040:80	500~1.2500~1.2	1 x 10⁴ 1 x 10 ⁴	88	6868	XX	XX	XX
비교예3Comparative Example 3	분리 불가Inseparable	1,250~0.011,250~0.01	1 x 10⁸ 1 x 10 ⁸	8080	9292	XX	○○	◎◎
비교예4Comparative Example 4	2:802:80	20,000~0.000120,000~0.0001	1 x 10¹² 1 x 10 ¹²	1616	9696	○○	◎◎	◎◎
비교예5Comparative Example 5	0:800:80	∞~0∞~0	1 x 10¹² 1 x 10 ¹²	1515	9494	○○	◎◎	◎◎
비교예6Comparative Example 6	50:8050:80	1,000~0.11,000~0.1	1 x 10⁵ 1 x 10 ⁵	88	7272	XX	XX	XX

As can be seen from Table 1, the antistatic silicone release film according to Examples 1 to 11 of the present invention has almost no defects, so the coating appearance is excellent, the cured layer has excellent sliding properties, and the surface resistance and peeling force are in an appropriate range. It can be seen that it has a value of and is also excellent in residual adhesion rate. In the case of the antistatic silicone release film according to Example 8 of the present invention, it can be seen that the appearance and physical properties are the most excellent.

In addition, in the release films according to Examples 1 to 11 and Comparative Examples 1 to 6, the thickness ratio of the antistatic region and the silicon release region in the cured layer layer and the uppermost and lowermost silicon ions and sulfurDepending on the ratio of ions, it can be seen that the surface resistance value, which is the antistatic property, and the peel force, the residual adhesion rate, and the appearance, which are release properties, have a correlation 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 properties are excellent according to the increase in the content of the binder based on the conductive polymer having the same physical properties.

In addition, in Examples 10 and 11 of the present invention, even if the absolute contents of the conductive polymer and the alkenylsiloxane are changed, it can be confirmed that the release properties are also excellent as long as the ratio of the antistatic effect and the peeling area does not change significantly.

On the other hand, in the case of the release film according to Comparative Examples 1 and 2, it can be seen that the content of the conductive polymer resin is too small or too large, so that the surface resistance, which is an antistatic property, is excessively increased, or the residual adhesion rate, which is a release property, is too low .

In addition, when the release film according to Comparative Example 3 does not contain an ionic surfactant, it can be seen that the coating appearance is poor and the peel strength properties are deteriorated.

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

In addition, in Comparative Example 6, when there are too many binder compounds, it can be confirmed that the surface resistance properties are improved, but the release properties are fatally deteriorated.

As described above, the antistatic silicone release film according to the present invention may be appropriately applied for a desired purpose, but is not limited thereto. In addition, the present invention can provide an excellent quality antistatic silicone release film for use in the field of precision materials, which has an appropriate range of peeling force and a high level of residual adhesion, so that the function of the pressure-sensitive adhesive layer is not reduced. It can be appropriately used according to the purpose without the need.

In addition, the antistatic silicone release film according to the present invention has excellent durability of the cured layer, excellent solvent resistance to organic solvents, high adhesion to the substrate, and less detachment of the cured layer due to friction. In addition, it can be seen that by having excellent antistatic performance, it has an effect of solving problems such as contamination phenomenon and defective peeling caused by static electricity.

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

Claims

Base film,

Including a cured layer of an antistatic silicone release composition located on at least one side of the base film,

The cured layer is intensity of sulfur ion showing a silicon ion and antistatic property represents the silicone release characteristics ratio (Si - / S -) have, antistatic silicone release containing less than one antistatic region and 10 more than the silicone release zone film.
The method of claim 1,

Intensity ratio of the cured layer (Si - / S -) is the base film and the boundary with the most distant from the top is from 10 to 10,000, and 0.001 to 1 of, antistatic silicone release film in the boundary between the bottom of the base film of.
The method of claim 1,

The thickness ratio of the antistatic region and the silicon release region satisfies Equation 1 below,

(Equation 1)

1/10 <AV / RV <1/3,

Here, AV is the thickness of the antistatic region, RV is the thickness of the silicon release region, antistatic silicone release film.
The method of claim 1,

The antistatic silicone release composition comprises an alkenylpolysiloxane, a hydroelectric polysiloxane, a conductive polymer resin, a binder compound, and a platinum chelate catalyst.
The method of claim 4,

The antistatic silicone release composition includes 2.5 to 7.5 parts by weight of the hydroelectric polysiloxane, 1 to 10 parts by weight of the conductive polymer resin, 5 to 20 parts by weight of the binder compound, and 10 ppm of the platinum chelate catalyst based on 100 parts by weight of the alkenylpolysiloxane Containing to 1,000ppm, antistatic silicone release film.
The method of claim 4,

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

The ionic surfactant is an ionic surfactant having an anionic group selected from sulfo-, phosphor-, or carboxyl- groups, an antistatic silicone release film.
The method of claim 6,

The ionic surfactant comprises 0.01 parts by weight to 5 parts by weight based on 100 parts by weight of the alkenyl polysiloxane, antistatic silicone release film.
The method of claim 4,

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

The silane-based compound is at least one or more of an epoxy silane-based, amino silane-based, vinyl silane-based, methacryloxy silane-based, and isocyanate silane-based compound,

The non-silane-based polyfunctional compound is an epoxy-based polyfunctional compound having an epoxy functional group, antistatic silicone release film.
The method of claim 9,

The epoxy-based polyfunctional compound has any one or more functional groups selected from the group consisting of amino, hydroxy, aldehyde, ester, vinyl, acrylic, imide, cyano, and isocyanate, and 3 in one molecule. An antistatic silicone release film having the above functional groups.
The method of claim 8,

The weight ratio of the non-silane-based polyfunctional compound to the silane-based compound is 2 to 20, antistatic silicone release film.
The method of claim 4,

The conductive polymer resin has an average particle diameter of 10 to 90 nm, an aqueous dispersion containing polyanions and polythiophene, or an aqueous dispersion containing polyanions and polythiophene derivatives, an antistatic silicone release film.
The method of claim 1,

The antistatic silicone release composition comprises 0.5 to 15% by weight of solids, antistatic silicone release film.
The method of claim 1,

The surface tension of the base film compared to the cured layer is 1.0 to 1.5 times, the antistatic silicone release film.
The method according to any one of claims 1 to 14,

The thickness of the base film is 15 to 300㎛, the thickness of the cured layer is 0.01 to 10㎛, antistatic silicone release film.
The method according to any one of claims 1 to 14,

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 peel force of the cured layer (g/inch), SA is the residual adhesion rate (%) of the cured layer, and SR is the surface resistance (Ω/sq) of the cured layer, an antistatic silicone release film.
Base film,

A cured layer of an antistatic silicone release composition positioned on one side of the base film,

Including a silicone release layer located on the other side of the base film,

The cured layer is intensity of sulfur ion showing a silicon ion and antistatic property represents the silicone release characteristics ratio (Si - / S -) have, antistatic silicone release containing less than one antistatic region and 10 more than the silicone release zone film.