KR102400408B1 - Release film for waterproof sheet and preparing method thereof - Google Patents

Abstract

The present invention relates to a release film for a waterproof sheet which comprises: a base film layer; an adhesion reinforcement unit formed on a lower surface of the base film layer and comprising at least one hole exposing a part of the lower surface of the base film layer; and a release film layer formed at the bottom of the adhesion reinforcement unit to fill the hole of the adhesion reinforcement unit, wherein the adhesive force between the base film layer and the release film layer is improved so that the release film layer is not easily peeled off from the base film layer and the peel force to the waterproof sheet is maintained well.

Description

Release film for waterproof sheet and manufacturing method thereof {Release film for waterproof sheet and preparing method thereof}

The present invention relates to a release film for a waterproof sheet and a method for manufacturing the same, and more particularly, by strengthening the adhesive force between the base film layer and the release film layer constituting the release film, peeling between the base film layer and the release film layer , to a release film for a waterproof sheet capable of preventing damage to the release film layer, and a manufacturing method thereof.

The release film is a thin film that can be easily peeled off and removed from the product when necessary while protecting the product from external foreign substances or light impact by being attached to the surface of the product that needs protection.

Such a release film is sometimes used to protect the adhesive layer of a sheet having an adhesive layer, and is also used to protect the surface of various products such as electronic products, semiconductors, automobiles, and displays.

In this way, the release film is stably attached to the surface of the product until it is peeled off, and when necessary, it should be easily peeled off from the product without damage to the product or the release film.

In order to impart these properties, the release film may be prepared by applying and curing a silicone release agent or a fluorine release agent that functions as a protective layer and forms a release layer on a base film having no adhesive force.

When the release film is manufactured in this way, the release layer and the base film are separated by static electricity during peeling, and the release layer is attached to the product surface. In order to prevent this, in general, antistatic treatment is essential carried out together

On the other hand, the waterproofing sheet is a waterproofing layer having waterproof performance such as asphalt, urethane, epoxy, etc. and an adhesive layer laminated or integrally formed in the form of a sheet, and the adhesive layer is protected by a release film until construction. By adhering to the construction surface, it is characterized by simple and quick waterproof construction.

At this time, in order to protect the adhesive layer, the release film attached to the adhesive layer is damaged by the solvent contained in the adhesive layer or the waterproof layer, or the release layer has adhesive strength over time, so it is not easily peeled from the product, rather, the release layer The base film and the base film are peeled off so that a part of the release layer remains in the product, or a part of the adhesive layer is attached to the release layer and peels off from the waterproof sheet.

Accordingly, it is possible to secure stable physical properties of the release layer while excellent adhesion between the base film and the release layer forming the release film, and to prevent damage to the release layer or damage to the adherend surface such as the adhesive layer during peeling. It is necessary to develop a release film for sheets.

Registered Patent No. 10-1714901 (Registered on Mar. 3, 2017)

An object of the present invention is to provide a release film for a waterproof sheet with improved strength, durability, heat resistance and peel strength of the release film and a method for manufacturing the same.

One embodiment of the present invention for achieving the object as described above, the base film layer; Doedoe formed on the lower surface of the base film layer, to expose a portion of the lower surface of the base film layer, the adhesive reinforcement formed in the form of a mesh network, dots, patterns or patterns; and a release film layer formed at the lower end of the adhesive reinforcement part to fill the hole formed by the lower surface of the adhesive reinforcement part and the base film layer, wherein the base film layer is based on 100 parts by weight of high density polyethylene (HDPE), EPDM (ethylene propylene diene terpolymer) 15 to 58 parts by weight, DCP (dicumyl peroxide) 5 to 12 parts by weight, 1-8 parts by weight of vinyl triethoxysilane, and 5 to 22 parts by weight of carbon filler, waterproof sheet for release film. It relates to a release film for a waterproof sheet, comprising a.

The base film layer may include high density polyethylene (HDPE), ethylene propylene diene terpolymer (EPDM), dicumyl peroxide (DCP), vinyltriethoxysilane, and carbon filler.

The adhesive reinforcing part may include a first silicone resin and a silicone pressure-sensitive adhesive.

The release film layer may include a second silicone resin obtained by reacting polydimethyl siloxane, dimethyl diphenyl polysiloxane, and alkoxy silane.

Another embodiment of the present invention relates to a method for manufacturing a release film for a waterproof sheet. Specifically, based on 100 parts by weight of high density polyethylene (HDPE), 15 to 58 parts by weight of EPDM (ethylene propylene diene terpolymer), 5 to 12 parts by weight of DCP (dicumyl peroxide), 1-8 parts by weight of vinyl triethoxysilane, and Preparing a base film layer comprising 5 to 22 parts by weight of carbon filler; forming an adhesive reinforcement in the form of a mesh, dot, pattern or pattern so that a portion of the lower surface of the base film layer is exposed, and a portion of the lower surface of the base film layer is exposed; and applying a release composition to cover the lower surface of the adhesive reinforcement part and the base layer, followed by drying to form a release film layer.

In this case, the adhesion reinforcing part includes a first silicone resin and a silicone pressure-sensitive adhesive, and the release film layer may include a second silicone resin obtained by reacting polydimethyl siloxane, dimethyl diphenyl polysiloxane, and alkoxy silane.

The release film for a waterproof sheet of the present invention has excellent adhesion between the base film layer and the release film layer, and can prevent the release film layer from being peeled off from the base film layer or the release film layer being damaged.

In addition, the release film for a waterproof sheet of the present invention can prevent damage to the release film when manufacturing, attaching, and peeling the release film because it has excellent strength, durability, and heat resistance.

In addition, the peeling force to the adherend surface is excellent and the peeling force change rate according to the peeling speed change is small, so that it can be easily peeled regardless of the peeling speed.

1 is a view showing a cross-section of a release film according to an embodiment of the present invention.

Before describing in detail through preferred embodiments of the present invention, terms or words used in the present specification and claims should not be construed as being limited to conventional or dictionary meanings, and meanings consistent with the technical spirit of the present invention and should be interpreted as a concept.

Throughout this specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

Throughout this specification, "%" used to indicate the concentration of a specific substance is (weight/weight)%, solid/liquid (weight/volume)%, and liquid, unless otherwise specified. /liquid means (volume/volume)%.

Hereinafter, an embodiment of the present invention will be described. However, the scope of the present invention is not limited to the following preferred embodiments, and those skilled in the art can implement various modified forms of the contents described herein within the scope of the present invention.

1 is a view showing a cross-section of a release film for a waterproof sheet according to an embodiment of the present invention.

The release film 10 for a waterproof sheet according to an embodiment of the present invention includes a base film layer 11; an adhesion reinforcement part 12 formed on the lower surface of the base film layer 11 and including at least one hole (H) exposing a portion of the lower surface of the base film layer 11; and a release film layer 13 formed at the lower end of the adhesive reinforcement 12 to fill the hole H of the adhesive reinforcement 12 .

The base film layer 11 is a central layer forming the strength of the release film 10 for a waterproof sheet, and has excellent tensile strength, durability, weather resistance and elasticity, and an adhesive reinforcing part 12 and a release film layer 13 It has excellent adhesion to silicone resin, which is the main component of Accordingly, damage to the release film 10 can be prevented when the release film 10 is wound, unwound, adhered, and peeled off, and in particular, the base film layer 11, which is a side effect that occurs when peeling the release film 10 It is possible to minimize peeling and lifting between the release film layer 13 and the release film layer 13 .

The base film layer 11 is preferably formed to a thickness of 20 to 350 μm to ensure sufficient strength and elasticity, but if it is less than 20 μm, it is difficult to secure sufficient strength, so it may be difficult to implement a function as a central layer, 350 If it exceeds ㎛, there is a problem in that the resistance to bending is weakened due to the decrease in elasticity, so that the release film 10 is pushed or peeled from the waterproof sheet when winding or unwinding the waterproof sheet to which the release film 10 is attached. Therefore, it is preferable to be formed in the above-described thickness range.

As such, the base film layer 11 is required to ensure sufficient strength, elasticity and weather resistance, and resistance to heat exposed when forming the adhesive reinforcing part 12 and the release film layer 13 is required, so strength, elasticity , HDPE (high density polyethylene) with excellent weather resistance and heat resistance is the main component.

Specifically, the base film layer 11 includes HDPE, ethylene propylene diene terpolymer (EPDM), dicumyl peroxide (DCP), vinyltriethoxysilane and carbon filler, and more specifically, with respect to 100 parts by weight of HDPE. , 15 to 38 parts by weight of EPDM, 5 to 12 parts by weight of DCP, 1 to 8 parts by weight of vinyltriethoxysilane, and 5 to 22 parts by weight of carbon filler.

The HDPE is a polymer having excellent strength, tensile performance, heat resistance and weather resistance, and is added to secure excellent basic physical properties of the base film layer 11 .

The EPDM is added to improve the impact strength of the base film layer 11, and as EPDM is added, the elasticity of the base film layer 11 is slightly lowered, but the impact strength is remarkably improved. Durability can be significantly improved.

To this end, EPDM is preferably included in an amount of 15 to 38 parts by weight based on 100 parts by weight of HDPE, when it is included in less than 15 parts by weight, a sufficient impact strength improvement effect cannot be obtained, and when it exceeds 38 parts by weight, the impact strength is significantly improved, but the elasticity is excessively lowered, and the compatibility with HDPE is lowered due to an excessive content of EPDM, and a phenomenon of layer separation occurs.

The DCP is a component added to ensure compatibility between HDPE and EPDM, and is included in an amount of 5 to 12 parts by weight based on 100 parts by weight of HDPC. In the case of exceeding the part, not only compatibility is not further improved, but due to an excessive DCP content in the base film layer 11, there may be a problem in that the physical properties of the base film layer 11 are rather deteriorated.

The vinyl triethoxysilane is a component added to improve the bonding strength between the HDPE and EPDM components in the base film layer 11 and the inorganic filler, and the bonding strength with the inorganic filler without impairing the physical properties of the base film layer 11 . It is preferable to include 1 to 8 parts by weight based on 100 parts by weight of HDPE in order to improve the

The carbon filler is a component added to improve the hardness and strength of the base film layer 11, and nano-sized graphene, carbon nanotubes, carbon black, etc. may be used as the carbon filler. In addition, since the antistatic performance is given to the base film layer 11 by the carbon filler, the release film layer 13 and the base film layer 11 are separated by static electricity during peeling, and thus the release film layer 13 is It is possible to prevent the problem of adhesion to the waterproof sheet.

In this case, a carbon filler having a particle size of 200 to 800 nm may be used in order to uniformly mix the carbon filler, prevent aggregation of the carbon filler, and prevent protrusion to the surface of the base film layer 11 .

Carbon filler may be included in an amount of 5 to 22 parts by weight based on 100 parts by weight of HDPE, and when it is included in less than 5 parts by weight, the effect of improving hardness and strength of the base film layer 11 is insignificant, and sufficient antistatic performance is not secured. However, when it exceeds 22 parts by weight, the hardness of the base film layer 11 is excessively increased to deteriorate the tensile properties, so it is preferable to be included within the above-described weight range.

The surface roughness, ie, roughness, of the lower surface of the base film layer 11 may be 20 to 70 μm, and with such high surface roughness, the adhesive strength between the adhesive reinforcement part 12 and the release film layer 13 is increased. The improved adhesive reinforcement part 12 or the release film layer 13 may not be easily separated from the base film layer 11 .

To this end, the corona discharge treatment may be performed on the lower surface of the base film layer 11 at a voltage of 2 to 7 kW for 0.3 to 1.5 seconds.

The adhesive reinforcing part 12 is formed on the lower surface of the base film layer 11 , and performs a function of strengthening the adhesive strength between the release film layer 13 and the base film layer 11 .

The adhesion reinforcing part 12 is formed on the lower surface of the base film layer 11 and includes at least one hole (H) exposing a portion of the lower surface of the base film layer 11 .

As an example, the adhesion reinforcing part 12 may be formed in the form of a mesh network including a plurality of holes (H). It may be formed in a shape, and as long as it includes a hole (H) exposing a portion of the lower surface of the base film layer 11, the present invention is not limited thereto, and may be formed in various shapes.

The adhesive reinforcing part 12 formed in this way has very good adhesive performance and forms a strong adhesive force to the base film layer 11, and at the same time, as will be described later, because it contains the same silicone polymer as the release film layer 13 as a main component. Since the adhesive strength to the release film layer 13 is very high, the adhesion reinforcing part 12 acts as an anchor for the release film layer 13, so that the base film layer 11 of the release film layer 13 is It is possible to significantly improve the adhesion to

The adhesive reinforcement part 12 may include a first silicone resin and a silicone adhesive.

Specifically, the adhesive reinforcing part 12 includes 15 to 38 parts by weight of a silicone adhesive based on 100 parts by weight of the first silicone resin. In addition, if necessary, a solvent may be further included, and in this case, the amount or type of the solvent is not particularly limited.

The first silicone resin is obtained by reacting a first silicone composition including polyorganosiloxane and a silane compound, and has excellent heat resistance and tensile strength, and forms the main skeleton of the adhesion reinforcing part 12 .

At least one of linear organosiloxane and cyclic organosiloxane may be used as the polyorganosiloxane, and preferably, linear organosiloxane and cyclic organosiloxane are mixed in a weight ratio of 1:0.3 to 1.2 and used. This is because, in this case, both the strength and the formability of the adhesive reinforcing part 12 can be secured.

The linear organosiloxane is hexamethyl disiloxane, 2,5-dichloro-1,1,3,3,5-hexamethyl trisiloxane, 1,3-dimethyltetramethoxy disiloxane, 1,1,1,3 , at least one selected from the group consisting of 5,5,5-heptamethoxy disiloxane, 3-(heptafluoropropyl)trimethyl siloxane, octamethyl trisiloxane, decamethyl tetrasiloxane and dodeca ethylpentasiloxane may include

The cyclic organosiloxane may include at least one of hexamethyl cyclo trisiloxane, octamethyl cyclo tetrasiloxane, decamethyl cyclo pentasiloxane, and dodecamethyl cyclo hexasiloxane.

The silane compound is added to induce a crosslinking reaction of the first silicone resin to further improve strength and adhesion of the first silicone resin.

The silane compound may be included in the first silicone resin in an amount of 5 to 22% by weight, and when it is included in less than 5% by weight, a sufficient degree of crosslinking is not achieved, so the degree of improvement in strength and adhesion is insignificant, and when it exceeds 22% by weight is preferably included within the above-mentioned weight range, since adhesiveness and elasticity are deteriorated due to excessive crosslinking reaction.

Preferably, trimethyl (trifluoromethyl) silane may be used as the silane compound, and trimethyl (trifluoromethyl) silane not only has excellent crosslinking performance but also further improves the heat resistance of the adhesion reinforcing part 12 to improve the processing process There is an advantage in that it is possible to more effectively prevent damage to the adhesive reinforcing part 12 due to heat.

The first silicone composition may include a catalyst for inducing a curing reaction of the polyorganosiloxane, for example, a metal catalyst, specifically, a platinum catalyst may be used as the catalyst, but is not limited thereto.

The silicone pressure-sensitive adhesive is a component added to improve the adhesive force of the adhesive reinforcing part 12, and may be MQ resin. MQ resin is a silicone compound having a three-dimensional network three-dimensional molecular structure including monofunctional siloxane units (hereinafter, “M units”) and tetrafunctional siloxane units (hereinafter, “Q units”), and has excellent adhesion. and high viscosity, and the MQ resin may further include other difunctional siloxane units or trifunctional siloxane units.

In the above, "M unit" means a unit represented by (R ₃ SiO _1/2 ), "Q unit" means a unit represented by the formula SiO _4/2 , where R is a silicon atom (Si) It means a functional group that is bound.

The content of the silicone adhesive is preferably 15 to 38 parts by weight based on 100 parts by weight of the first silicone resin. When the content of the silicone adhesive is less than 15 parts by weight, the effect of improving the adhesive performance by the silicone adhesive is insignificant, and 38 parts by weight When it exceeds, the viscosity increases excessively, and when forming the adhesive reinforcement part 12 , the air bubbles introduced into the interface between the base film layer 11 and the adhesive reinforcement part 12 are not released to the outside, but pores are formed as they are. Therefore, since there is a problem in that the adhesive force between the base film layer 11 and the adhesion reinforcing part 12 is rather reduced, it is preferable to be included within the above-described weight range.

The release film layer 13 includes a second silicone resin obtained by reacting a second silicone composition comprising polydimethyl siloxane, dimethyl diphenyl polysiloxane and alkoxy silane to provide an appropriate peeling force to the release film 10 .

The release film layer 13 is formed at the lower end of the adhesive reinforcement part 12 , and at this time, the release film layer 13 is formed to fill the hole H of the adhesive reinforcement part 12 . Accordingly, as shown in FIG. 1 , the hole H of the adhesive reinforcing part 12 is formed in a concave shape, and a convex portion is formed in the release film layer 13 to fill the concave hole H.

Accordingly, a portion of the release film layer 13 is in contact with and adheres to the lower surface of the base film layer 11 , and the remaining portion is in contact with and adheres to the adhesive reinforcing unit 12 . Since the main material of each of the base film layer 11 and the release film layer 13 is a different type of polymer, it is difficult to form an adhesive strength higher than a predetermined strength. When the part 12 is formed, the release film layer 13 may be strongly adhered to the adhesion reinforcing part 12 .

In addition, since the static electricity generated in the release film layer 13 can be removed through the base film layer 11 through the region where the release film layer 13 and the base film layer 11 directly contact each other, through the above-described structure The function as an anchor of the adhesive reinforcement part 12 and the antistatic performance of the base film layer 11 can be effectively expressed.

The release film layer 13 is preferably formed in a thickness range of 1 to 10 μm in order to secure its own strength, adhesive strength, and provide appropriate peeling force. At this time, since the adhesive reinforcing part 12 has a sticky property, it is preferable to be formed thinner than the thickness of the release film layer 13 so that the surface of the adhesive reinforcing part 12 is completely covered by the release film layer 13 . .

The release film layer 13 may be formed by applying a release composition including a second silicone resin, a solvent, and an additive to the lower surface of the base film layer 11 on which the adhesion reinforcing part 12 is formed, followed by drying.

The release composition may include 10 to 40 parts by weight of a solvent and 1 to 10 parts by weight of an additive based on 100 parts by weight of the second silicone resin.

The second silicone resin is a component added to provide an appropriate peeling force to the release film layer 13, and the release film layer 13 is attached to the waterproof sheet by the second silicone resin and can be easily peeled off if necessary. can

The second silicone resin may be obtained by reacting two or more siloxane compounds having different molecular weights.

Specifically, the second silicone resin may be obtained by reacting polydimethyl siloxane, dimethyl diphenyl polysiloxane and alkoxy silane, wherein the polydimethyl siloxane has a weight average molecular weight of 3,000 to 50,000 g/mol, and dimethyl diphenyl The polysiloxane may have a weight average molecular weight of 1,000 to 5,000 g/mol.

When reacting them to obtain the second silicone resin, a catalyst may be added to initiate and accelerate the reaction. In this case, various well-known catalysts such as a metal catalyst, a metal oxide catalyst, and a complex oxide catalyst may be used as the catalyst, preferably Alternatively, a highly reactive platinum catalyst may be used.

Preferably, the weight average molecular weight of the second silicone resin is 85,000 to 120,000 g/mol. When the weight average molecular weight of the second silicone resin is within this range, the surface tension of the release film layer 13 is not too high or low. Therefore, appropriate strength and peeling force can be implemented in the release film layer 13 .

Specifically, the second silicone resin may be obtained by reacting 12 to 30 parts by weight of dimethyl diphenyl polysiloxane and 5 to 15 parts by weight of alkoxy silane with respect to 100 parts by weight of polydimethylsiloxane.

The polydimethylsiloxane expresses the basic physical properties of a silicone resin, has excellent strength and weather resistance, has an appropriate adhesive strength, and is adhered to the adherend, and is easily peeled off when necessary.

As the polydimethyl siloxane, a high molecular weight polydimethyl siloxane having a weight average molecular weight of 30,000 to 50,000 g/mol may be used. The second silicone resin having high strength, elasticity, and thermal stability may be prepared.

More preferably, polydimethylsiloxane having both ends capped with hydroxyl groups may be used as polydimethylsiloxane, and hydrogen bonds are formed by hydroxyl groups at both ends in the second silicone resin, and polymer chains are entangled with each other to form a network structure The strength of the second silicone resin itself is increased by forming , and thus the release film layer 13 is more effectively prevented from being damaged when the release film 10 is peeled off.

The dimethyl diphenyl polysiloxane can prevent damage to the release film layer 13 during processing by improving the heat resistance of the second silicone resin, and improve the adhesion of the release film layer 13 to the base film layer 11 Thus, when the release film 10 is separated from the waterproof sheet, it is possible to prevent the problem that the release film layer 13 is peeled from the base film layer 11 and adheres to the waterproof sheet.

The dimethyl diphenyl polysiloxane may be included in an amount of 12 to 30 parts by weight based on 100 parts by weight of polydimethyl siloxane. The effect of preventing the peeling problem is insignificant, and when it exceeds 30 parts by weight, the hardness of the release film layer 13 is excessively lowered, so that the shape of the release film layer 13 cannot be maintained and easily damaged by an external impact. Since there is a problem that is, it is preferable to be included within the above-mentioned weight range.

The dimethyl diphenyl polysiloxane preferably has a weight average molecular weight of 1,000 to 5,000 g/mol. As described above, since dimethyl diphenyl polysiloxane has a significantly lower molecular weight than poly dimethyl siloxane, the viscosity of the second silicone resin increased by poly dimethyl siloxane can be significantly lowered, and accordingly, uniform mixing of each component and reaction becomes possible. In addition, when the second silicone resin is prepared by reacting the siloxane compound having a significantly different molecular weight as described above, the elasticity and tensile properties of the second silicone resin are remarkably improved. Damage to the film layer 13 can be more effectively prevented.

The alkoxy silane acts as a crosslinking agent during the second silicone resin formation reaction to form a network structure of the second silicone resin more firmly, and accordingly, the strength of the release film layer 13 itself and the adhesive force to the base film layer 11 . can improve As such, as the alkoxysilane is added, the adhesive force of the release film layer 13 itself increases, but the strength also increases, so that when the release film 10 is peeled off, the release film layer 13 is not easily damaged and the adherend surface is It can be easily separated from the waterproof sheet.

Such alkoxy silanes are preferably 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, methyl (3-glycidoxypropyl) dimethoxysilane, methyl (3-glycidoxy Propyl) at least one of diethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, and 3-(3,4-epoxycyclohexyl)propyl trimethoxysilane may be used.

Alkoxy silane may be included in an amount of 5 to 15 parts by weight based on 100 parts by weight of polydimethyl siloxane. When it is included in an amount of less than 5 parts by weight, the above-described effect is insignificant, and when it exceeds 15 parts by weight, the elasticity of the second silicone resin is This is lowered, and there is a problem that the release film layer 13 is attached to the waterproof sheet, which is the adherend surface, due to an increase in adhesive force while insignificant improvement in strength, so it is preferable to be included within the above-described weight range.

The solvent disperses the second silicone resin, uniformly mixes each component included in the release composition, and lowers the viscosity of the release composition so that it can be applied in a desired shape and thickness.

When the content of the solvent is less than 10 parts by weight, this effect is not obtained, and when it exceeds 40 parts by weight, the viscosity is excessively reduced, so that the shape is not maintained when applied to the base film layer 11 on which the adhesion reinforcing part 12 is formed. Since there is a problem of dripping, it is preferable to be included within the above-mentioned weight range.

As such a solvent, an organic solvent may be used, and preferably, acetone, dimethyl carbonate, t-butyl acetate, etc., which are solvents exempted from the regulation of volatile organic compounds, may be used.

Among them, in the case of acetone and dimethyl carbonate, acetone and dimethyl carbonate have strong volatility, and drying proceeds excessively quickly during operation, resulting in poor workability. desirable.

The additive is a component added to improve the physical properties of the release composition, and in order to secure the basic physical properties of the release film layer 13 while obtaining the effect of improving the physical properties by the additive, the additive is based on 100 parts by weight of the second silicone resin It may be included in 1 to 10 parts by weight.

As the additive, a heat stabilizer, an antifoaming agent, a dispersing agent, a fragrance, a pigment and a filler may be used.

The heat stabilizer is a component added to improve the thermal stability of the release composition, and is added to prevent denaturation or damage of the release composition due to heat applied when the release film layer 13 is formed. As such a heat stabilizer, for example, dibutyltin dioxide or dioctyltin oxide may be used.

The antifoaming agent is a component added to remove air bubbles in the release composition to form the release film layer 13 having a smoother, more uniform shape and uniform physical properties. Fatty acid ester type, alcohol type, phosphoric acid ester type, metal soap type, silicone type defoaming agent, etc. can be used as such an antifoaming agent.

The dispersant is a component added to uniformly mix each component in the release composition, and any known dispersant may be used without particular limitation. For example, an acrylic dispersant, a urethane-based dispersant, a polycarbonate-based dispersant, a polyester-based dispersant, and a polyolefin-based dispersant may be used, but is not limited thereto.

The pigment is a component added to impart color to the release composition, for example, lead chromate salt, titanium dioxide, calcium carbonate, barium sulfate, aluminum silicate, talc, graphite, carbon black, iron oxide green, iron oxide red and metal oxide or Fillers coated with these may be used, but are not limited thereto.

The perfume is a component added to suppress the characteristic odor of the second silicone resin included in the release composition, and various commonly used perfumes or aromatic substances may be used.

The filler is a component added to improve the strength of the release film layer 13, and includes calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, talc, mica, glass fiber, silica. , diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, graphite, carbon fiber, and the like, various kinds of fillers commonly used may be used.

At this time, in order to prevent phenomena such as aggregation of the filler, protrusion to the outside of the release film layer 13, desorption, and the like, the particle size of the filler is preferably formed in the range of 50 to 300 nm.

Hydroxytyrosol may be additionally added to the release composition, and in this case, may be added in an amount of 1 to 5 parts by weight based on 100 parts by weight of the silicone resin. When hydroxytyrosol is added to the release composition, the heat resistance, water resistance, and strength of the release film layer 13 are improved, so that the durability of the release film layer 13 is improved.

When the content of hydroxytyrosol is less than 1 part by weight, it is difficult to obtain the above-mentioned effects, and when it exceeds 5 parts by weight, the peeling properties of the release film layer 13 may be poor due to hydroxytyrosol, so the above-mentioned It is preferably included within one weight range.

On the other hand, another embodiment of the present invention relates to a method for manufacturing a release film for a waterproof sheet, and since the release film for a waterproof sheet according to an embodiment of the present invention can be manufactured according to the manufacturing method of this embodiment, overlapping A description is omitted.

The manufacturing method of the release film 10 for a waterproof sheet according to the present embodiment, including HDPE (high density polyethylene), EPDM (ethylene propylene diene terpolymer), DCP (dicumyl peroxide), vinyl triethoxysilane and carbon filler Preparing the base film layer 11; forming an adhesion reinforcing part 12 to be adhered to the lower surface of the base film layer 11 so as to expose a portion of the lower surface of the base film layer 11; and forming a release film layer 13 by applying and drying a release composition to cover the lower surface of the adhesive reinforcement part 12 and the base film layer 11 .

The step of preparing the base film layer 11 is based on 100 parts by weight of HDPE, 15 to 38 parts by weight of EPDM, 5 to 12 parts by weight of DCP, 1 to 8 parts by weight of vinyltriethoxysilane, and 5 to 22 parts by weight of carbon filler. This is a step of processing the composition including parts by weight into a film having a thickness of 20 to 350 μm.

In this way, the corona discharge treatment may be additionally performed on the base film layer 11 processed in the form of a film if necessary. Specifically, corona discharge treatment may be performed on the lower surface of the base film layer 11 , and as the corona discharge treatment is performed in this way, the roughness of the lower surface of the base film layer 11 on which the release film layer 13 will be formed increases, and accordingly, when forming the adhesive reinforcement part 12 or the release film layer 13 in a later step, it can be more strongly adhered.

The corona discharge treatment may be performed for 0.3 to 1.5 seconds at a voltage of 2 to 7 kW, and when it is performed less than the voltage range or less than the time range, it is difficult to form sufficient illuminance, and it is difficult to form a sufficient illuminance, exceed the voltage range or the time If the corona discharge treatment is performed for a longer time than the range, since there is a risk that the base film layer 11 itself may be damaged, the corona discharge treatment is preferably performed within the range satisfying the above-described treatment conditions.

Next, in the step of forming the adhesion reinforcing part 12, an adhesive composition comprising 15 to 38 parts by weight of a silicone adhesive with respect to 100 parts by weight of the first silicone resin is applied to at least a partial area of the lower surface of the base film layer 11 and drying step.

At this time, the adhesive composition may be applied in the form of a mesh network, dots, or various patterns or patterns to form a hole (H) exposing a portion of the lower surface of the base film layer 11, and the adhesive composition applied in this way is dried by hot air to a predetermined can be formed in the form of

Next, a step of forming the release film layer 13 by applying a release composition to the lower end of the base film layer 11 on which the adhesive reinforcement part 12 is formed and drying is performed is performed.

The release composition contains 10 to 40 parts by weight of a solvent and 1 to 10 parts by weight of an additive based on 100 parts by weight of the second silicone resin, and the second silicone resin is polydimethylsiloxane, dimethyl diphenyl polysiloxane, and alkoxysilane as described above. It can be obtained by reacting

Application of the release composition is performed using various painting tools such as rollers, sprays, brushes, etc., or by immersing only the lower surface of the base film layer 11 on which the adhesive reinforcement part 12 is formed in a container containing the release composition, It can be carried out by various coating methods used for coating the composition in the art, such as by disposing the lower surface of the base film layer 11 to face upward and then applying the release composition using a bar coater.

As described above, the release film layer 13 can be formed by applying the release composition to the lower surface of the base film layer 11 on which the adhesion reinforcing part 12 is formed and then drying it.

Preferably, a hot air drying method may be applied as the drying method, and the temperature of the hot air may be 80 to 120 °C. If it exceeds, the base film layer 11, the adhesive reinforcement part 12, and the release film layer 13 may be damaged due to excessive heat, so it is preferable to dry with hot air at the above-mentioned temperature.

Hereinafter, specific actions and effects of the present invention will be described through an embodiment of the present invention. However, this is presented as a preferred example of the present invention, and the scope of the present invention is not limited according to the embodiments.

[Production Example]

First, with respect to 100 parts by weight of HDPE, a mixture of 22 parts by weight of EPDM, 8 parts by weight of DCP, 5 parts by weight of vinyltriethoxysilane and 15 parts by weight of graphene powder (average particle size 350-400 nm) as a carbon filler is heat-pressed. After preparing a base film layer having a thickness of about 50 μm, corona discharge was performed on the lower surface of the base film layer for 0.8 seconds at a voltage of 5 kW to surface-treat, thereby forming a roughness of the lower surface of the base film layer to about 40 μm.

Next, an adhesion reinforcing agent containing 100 parts by weight of the first silicone resin and 23 parts by weight of the MQ resin, which is a silicone adhesive, was applied to the lower surface of the base film layer to have a mesh network shape having a thickness of 7.5 μm, and dried to form an adhesion reinforcing part.

At this time, as the first silicone resin, 92 wt% of a mixture of hexamethyl disiloxane and decamethyl cyclopentasiloxane in a weight ratio of 1:0.8 and 8 wt% of trimethyl (trifluoromethyl) silane were reacted using a platinum catalyst. The obtained one was used, and MQ resin was used as the silicone pressure-sensitive adhesive.

Next, a release composition comprising 18 parts by weight of t-butyl acetate as a solvent and 8 parts by weight of an additive based on 100 parts by weight of a second silicone resin having a weight average molecular weight of about 100,000 g/mol on the lower surface of the base film layer on which the adhesion reinforcing layer is formed was applied to a thickness of 10 μm and dried with hot air at about 95° C. to form a release film layer, thereby preparing a release film for a waterproof sheet of Example 1.

At this time, as the second silicone resin, dimethyl diphenyl polysiloxane having a weight average molecular weight of about 3,000 g/mol with respect to 100 parts by weight of polydimethyl siloxane capped at both ends with hydroxyl groups having a weight average molecular weight of about 40,000 g/mol A silicone resin obtained by reacting 14 parts by weight and 8 parts by weight of 3-glycidoxypropyl trimethoxysilane as an alkoxy silane under a platinum catalyst was used.

In addition, as additives, 4 parts by weight of dibutyltin dioxide, 2 parts by weight of a polyester-based dispersant, 1 part by weight of calcium carbonate as a pigment, and a fragrance were used.

[Experimental Example 1]

The same release film as in Example 1 was prepared, but the content of dimethyl diphenyl polysiloxane used to prepare the second silicone resin included in the release film layer was changed as shown in Table 1 below. In Table 1, the content of dimethyl diphenyl polysiloxane means a weight ratio with respect to 100 parts by weight of polydimethyl siloxane capped at both ends with hydroxyl groups.

Next, the tear strength of each Example and Comparative Example was measured by the method of ASTM D 1004.

In addition, after preparing 5 samples of each Example and Comparative Example, respectively, the peeling force in a room at about 26°C and a relative humidity of 55% was measured based on FINAT test method no.10 using a 1-inch TESA7475 tape. Specifically, the room temperature peel strength, which is the force required for peeling at an angle of 180°, peeling speed of 0.3 m/min, and 5 m/min, was measured, and Table 1 shows the average values thereof. In addition, when the release film layer was damaged even in one sample during peeling, "X" was indicated.

Dimethyl diphenyl polysiloxane (parts by weight) tear strength
(kg _f /cm) peel strength
(g _f /in, 0.3 m/min) peel strength
(g _f /in, 5 m/min) Comparative Example 1 0 72 20.8 43.1 Comparative Example 2 8 121 13.6 18.0 Example 1 14 219 9.3 14.5 Example 2 20 228 10.0 17.8 Example 3 28 236 9.6 19.2 Comparative Example 3 33 244 9.5 X

Referring to the results of Table 1, when dimethyl diphenyl polysiloxane is added, it can be seen that the tear strength and peel strength are improved. These results were particularly pronounced in Examples 1 to 3 and Comparative Example 3.

However, in Comparative Example 3, the release film layer was damaged when the peeling rate was increased, and when the content of dimethyl diphenyl polysiloxane was excessive, the adhesive strength was excessively increased and the strength of the release film layer was decreased, so that the release film during peeling It was found that layer damage was induced.

Therefore, from the results of this experiment, dimethyl diphenyl polysiloxane was included in the production of the second silicone resin included in the release film layer to improve the tear strength and peel strength of the release film, but both ends were capped with hydroxyl groups. It was confirmed that it is preferably included in an amount of 12 to 30 parts by weight, more preferably 14 to 28 parts by weight, based on 100 parts by weight of dimethyl siloxane.

[Experimental Example 2]

The same release film as that of the release film of Example 1 was prepared, but by further adding hydroxytyrosol in the content shown in Table 2 to the release composition used for preparing the release film layer. In Table 2, the content of hydroxytyrosol means a weight ratio with respect to 100 parts by weight of the second silicone resin.

Thereafter, the tear strength of each release film, the peel strength when peeled at a peeling rate of 0.3 m/min, and the peel strength after aging were measured, and the results are shown in Table 2.

Peel strength after aging was measured by performing a peel test based on FINAT test method no. After measurement using each of 5 samples, the average value was calculated and described in Table 2, and when the release film layer was damaged during peeling, it was marked with "X".

hydroxy tyrosol
(parts by weight) tear strength
(kg _f /cm) Room temperature peel strength
(g _f /in, 26°C) high temperature peel strength
(g _f /in, 85℃) Example 1 0.0 219 9.3 26.8 Example 4 1.0 250 9.8 12.0 Example 5 2.5 261 10.5 13.6 Example 6 5.0 266 10.9 14.1 Example 7 6.5 269 X X

Referring to the results of Table 2, it was found that the tear strength was improved when hydroxytyrosol was added, and the peel strength under severe conditions was not significantly different from that at room temperature. However, when the content of hydroxytyrosol is excessive as in Example 7, damage to the release film layer appears during peeling, and it can be seen that the durability of the release film layer is reduced. .

Therefore, it could be confirmed from the results of this experiment that it is preferable to add hydroxytyrosol to the release composition for forming the release film layer, and in particular, it is more preferable to include 1 to 5 parts by weight based on 100 parts by weight of the second silicone resin. could see that

[Experimental Example 3]

The same release film as the release film of Example 1 was prepared, but the release films of Examples and Comparative Examples were prepared by changing the content of the silicone adhesive when forming the adhesive reinforcing part as shown in Table 3 below. In Table 3, the content of the silicone pressure-sensitive adhesive means a weight ratio with respect to 100 parts by weight of the first silicone resin.

Next, the peel strength was measured at room temperature in the same manner as in Experimental Example 1, but the peel strength was measured while changing the peeling speed to 0.3 m/min, 5 m/min, 15 m/min, and 30 m/min. is shown in Table 3. In addition, when the release film was damaged even in one sample during peeling, it was marked with "X".

sample No. silicone adhesive
(parts by weight) Peeling rate (m/min) 0.3 5 15 30 # One 0 9.6 14.1 X X # 2 7 9.4 14.7 X X #3 15 9.7 14.6 17.2 21.0 # 4 23 9.3 14.5 16.8 20.3 #5 30 9.5 14.5 17.1 20.5 #6 38 9.7 14.8 17.0 20.4 #7 44 9.3 X X X

Referring to the results of Table 3, in the case of Samples 3 to 6, it was confirmed that the peeling strength increased with a smaller width as the peeling speed increased. However, in Samples 1, 2 and 7, the peeling speed was increased In some cases, the release film was found to be damaged. Specifically, in the case of samples 1 and 2, there was a problem that a part of the release film layer remained on the TESA7475 tape, and in the case of sample 7, a part of the release film layer and a part of the adhesive reinforcement part remained on the TESA7475 tape. .

In the case of Samples 1 and 2, it seems that the above-mentioned results appeared because the effect of reinforcing the adhesion by the adhesion reinforcing part was insignificant. It is judged to be the result that appeared because the dense adhesion was not made between the part and the base film layer.

Therefore, it could be confirmed from the results of this experiment that it is preferable to include a silicone adhesive in the adhesive reinforcement part formed to improve the adhesion of the release film layer to the base film layer, and the content is 100 parts by weight of the first silicone resin. It was confirmed that 15 to 38 parts by weight is more preferable.

The present invention is not limited to the specific embodiments and descriptions described above, and without departing from the gist of the present invention claimed in the claims, any person skilled in the art to which the invention pertains can implement various modifications and such modifications shall fall within the protection scope of the present invention.

10: release film 11: base film layer
12: adhesive reinforcement 13: release film layer

Claims (5)

base film layer;
Doedoe formed on the lower surface of the base film layer, to expose a portion of the lower surface of the base film layer, the adhesive reinforcement formed in the form of a mesh network, dots, patterns or patterns; and
and a release film layer formed at the bottom of the adhesive reinforcement part to fill the hole formed by the lower surface of the adhesive reinforcement part and the base film layer;
The base film layer, based on 100 parts by weight of high density polyethylene (HDPE), EPDM (ethylene propylene diene terpolymer) 15 to 58 parts by weight, DCP (dicumyl peroxide) 5 to 12 parts by weight, vinyl triethoxysilane 1-8 Containing 5 to 22 parts by weight and carbon filler,
The release film for a waterproof sheet, characterized in that the roughness of the lower surface of the base film layer is 20 ~ 70㎛. delete The method of claim 1,
The adhesive reinforcing part, a release film for a waterproof sheet, characterized in that it contains a first silicone resin and a silicone pressure-sensitive adhesive. The method of claim 1,
The release film layer, polydimethyl siloxane, dimethyl diphenyl polysiloxane, and a second silicone resin obtained by reacting alkoxy silane, the release film for a waterproof sheet characterized in that it contains. In the method for manufacturing the release film for a waterproof sheet according to any one of claims 1, 3 and 4,
Based on 100 parts by weight of high density polyethylene (HDPE), 15 to 58 parts by weight of EPDM (ethylene propylene diene terpolymer), 5 to 12 parts by weight of DCP (dicumyl peroxide), 1-8 parts by weight of vinyltriethoxysilane, and 5 parts by weight of carbon filler Preparing a base film layer comprising ~ 22 parts by weight;
corona discharge treatment on the lower surface of the base film layer;
forming an adhesive reinforcing part in the form of a mesh network, dots, patterns or patterns so that a portion of the lower surface of the base film layer is exposed; and
After applying a release composition to cover the lower surface of the adhesive reinforcement part and the base layer, drying to form a release film layer;
The adhesive reinforcing part includes a first silicone resin and a silicone adhesive,
The release film layer, polydimethyl siloxane, dimethyl diphenyl polysiloxane and a second silicone resin obtained by reacting alkoxy silane, characterized in that it contains a release film for a waterproof sheet.

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