KR102512223B1 - Composition for silicone release coating and release film comprising same - Google Patents

Abstract

The present invention relates to a composition for silicone release coating and a release film comprising the same, which has excellent minimum aging properties and does not cause tearing when the release film is peeled off even when stored for a long time in a state in which it is laminated with an adhesive layer. It exhibits an antistatic effect and can prevent generation of static electricity after peeling of the release film. When manufacturing the release film, a release layer is formed by applying a composition for silicone release coating, so a separate antistatic layer is required. It can be provided in a one-component form without

Description

Composition for silicone release coating and a release film comprising the same

The present invention relates to a composition for a silicone release coating and a release film comprising the same, and more particularly, to a composition for a silicone release coating having excellent minimum age and exhibiting an antistatic effect, and a release film comprising the same.

The release film is a process film for cast film formation such as urethane resin, acrylic resin, and vinyl chloride resin, a protective film for an adhesive layer such as an adhesive tape, an adhesive sheet, and an adhesive film, and electronic components such as ceramic green sheets and printed circuit boards. It is used as a process film for manufacturing. As a release film, generally, the release layer which consists of a silicone type or non-silicone type release agent is formed on the surface of base film, such as a polyester film, as the main thing.

The release film is used in the manufacture of a liquid crystal display device (LCD), and specifically, in the process of attaching a polarizing plate to a liquid crystal cell, the release film is first peeled off from the pressure-sensitive adhesive layer and removed from the liquid crystal cell. After attaching, when the role of the surface protection film is finished in the post-process, it is also peeled off.

In addition, it is mainly used in the manufacturing process even when manufacturing OLED.

Usually, the release film is peeled off after forming the resin sheet, when using the adhesive film, or after manufacturing the electronic component, but when peeled off, static electricity is easily charged. Therefore, in the case of stacking and storing resin sheets, there is a problem that the resin sheets are repulsed or stuck to each other due to electrical repulsion or attraction, and in the case of an adhesive film, foreign matter such as dust adheres to the adhesive layer, causing adhesion. The layer was becoming a cause of contamination.

In addition, in the case of ceramic green sheets, thinning is progressing with the miniaturization and capacity increase of ceramic capacitors. However, when the thinning is progressing, peeling electrification is large in the conventional release film, and the resulting electrostatic disturbance has become a major problem. Due to these problems, in recent years, release films have been required to have an antistatic function.

In addition, while the conventional silicone release film is stored for a long time in a state of being laminated with the adhesive layer, the unreacted functional groups of the silicone resin in the silicone release layer and the unreacted functional groups in the components of the adhesive layer react slowly, or the polymer of the adhesive layer and the silicone release film Due to the entanglement of the polymer of the layer, a tearing phenomenon may occur when the silicone release film is peeled off, or it may cause damage to the adhesive layer.

In addition, due to the transfer of polymers and unreacted compounds of the silicone release layer to the adhesive layer, a quality problem in which adhesive strength is reduced may occur.

As described above, it is necessary to develop a silicone release film that has no problem in peeling stability due to change with time and can exhibit an electrification effect.

KR 10-0965378 B1

An object of the present invention relates to a composition for silicone release coating and a release film comprising the same.

Another object of the present invention relates to a composition for silicone release coating that has excellent minimum aging properties and does not cause tearing when the release film is peeled off even when stored for a long time in a state in which it is laminated with an adhesive layer, and a release film comprising the same .

Another object of the present invention is to exhibit an antistatic effect and to prevent generation of static electricity after peeling of the release film, by applying a composition for silicone release coating to form a release layer when preparing the release film, It relates to a one-component silicone release coating composition that does not require the formation of an antistatic layer and a release film comprising the same.

In order to achieve the above object, a composition for silicone release coating according to an embodiment of the present invention includes a solvent; polydimethylsiloxane represented by Formula 1 below; CNT dispersion; retardants; cross-linking agent; and a catalyst:

[Formula 1]

here,

n and m are integers from 1 to 1000;

R ₁ to R ₁₀ are the same as or different from each other, and are each independently hydrogen, halogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted carbon atom having 2 to 24 carbon atoms. Alkynyl group, substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, substituted or unsubstituted aryl group having 5 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms Aryl group, substituted or unsubstituted unsubstituted heteroarylalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 3 to 20 carbon atoms It is selected from the group consisting of 20 cycloalkenyl groups, substituted or unsubstituted heteroaralkyl groups having 3 to 30 carbon atoms, and substituted or unsubstituted heteroalkenyl groups having 1 to 20 carbon atoms,

At least one of R ₁ to R ₁₀ is a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms.

Polydimethylsiloxane represented by Chemical Formula 1 may include at least one vinyl group as a substituent.

The crosslinking agent may be a compound represented by Formula 2 below:

[Formula 2]

here,

R ₁₁ to R ₁₉ are the same as or different from each other, and are each independently hydrogen, halogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted carbon atom having 2 to 24 carbon atoms. Alkynyl group, substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, substituted or unsubstituted aryl group having 5 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms Aryl group, substituted or unsubstituted unsubstituted heteroarylalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 3 to 20 carbon atoms It is selected from the group consisting of 20 cycloalkenyl groups, substituted or unsubstituted heteroaralkyl groups having 3 to 30 carbon atoms, and substituted or unsubstituted heteroalkenyl groups having 1 to 20 carbon atoms,

At least three or more of R ₁₁ , R ₁₄ to R ₁₅ , R ₁₈ and R ₁₉ are substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms.

The retardant is 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynyl cyclohexanol, 1,5-hexadiyne, 1,6-heptadiyne, 3,5-dimethyl-1-hexene-1-yne, 3-ethyl-3-butene-1-yne, 3-phenyl-3-butene- 1-phosphorus, 1,3-divinyltetramethyldisiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, 1,3-divinyl-1,3-diphenyldimethyldisiloxane, and methyl Tris(3-methyl-1-butyn-3-oxy)silane, tributylamine, tetramethylethylenediamine, benzotriazole, triphenylphosphine, sulfur-containing compounds, hydroperoxy compounds, maleic acid derivative-1 -ethynylcyclohexanol, 3-methyl-1-penten-3-ol, and mixtures thereof.

The CNT dispersion may include 0.3 to 0.5 parts by weight of CNT and 0.3 to 0.5 parts by weight of a dispersant based on 100 parts by weight of the solvent.

A silicone release film according to another embodiment of the present invention includes a base film; and a release layer formed on one surface of the base film, wherein the release layer is formed by applying the silicone release coating composition.

The release layer may include a solvent, polydimethylsiloxane represented by Formula 1 below; a CNT dispersion, a retardant and a crosslinking agent are uniformly dispersed; And a catalyst may be mixed before coating on one side of a base film to prepare a coating composition, and then applied to one side of the base film to form a release layer:

[Formula 1]

here,

n and m are integers from 1 to 1000;

R ₁ to R ₁₀ are the same as or different from each other, and are each independently hydrogen, halogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted carbon atom having 2 to 24 carbon atoms. Alkynyl group, substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, substituted or unsubstituted aryl group having 5 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms Aryl group, substituted or unsubstituted unsubstituted heteroarylalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 3 to 20 carbon atoms It is selected from the group consisting of 20 cycloalkenyl groups, substituted or unsubstituted heteroaralkyl groups having 3 to 30 carbon atoms, and substituted or unsubstituted heteroalkenyl groups having 1 to 20 carbon atoms,

At least one of R ₁ to R ₁₀ is a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms.

In the present invention, “alkyl” means a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like.

In the present invention, “alkenyl” refers to a monovalent substituent derived from a straight-chain or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon double bond. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, and 2-butenyl.

In the present invention, “alkynyl” refers to a monovalent substituent derived from a straight-chain or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond. Examples thereof include, but are not limited to, ethynyl and 2-propynyl.

As used herein, "aralkyl" refers to an aryl-alkyl group where aryl and alkyl are defined above. Preferred aralkyls include lower alkyl groups. Non-limiting examples of suitable aralkyl groups include benzyl, 2-phenethyl and naphthalenylmethyl. Attachment to the parent moiety is via an alkyl.

In the present invention, "aryl" means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms in a single ring or a combination of two or more rings. In addition, a form in which two or more rings are simply attached to each other (pendant) or condensed may be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, fluoryl, dimethylfluorenyl, and the like.

In the present invention, “heteroaryl” means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 6 to 30 carbon atoms. At this time, at least one carbon, preferably 1 to 3 carbons in the ring is substituted with a heteroatom such as N, O, S or Se. In addition, a form in which two or more rings are simply attached to each other or condensed may be included, and furthermore, a form condensed with an aryl group may be included. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl ( polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carbazolyl and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl and the like, but are not limited thereto.

In the present invention, "heteroaralkyl group" means an aryl-alkyl group substituted with a heterocyclic group.

In the present invention, “cycloalkyl” means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.

In the present invention, “heterocycloalkyl” means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 carbon atoms, and one or more carbons in the ring, preferably 1 to 3 carbons, are N, O, S or Se is substituted with a heteroatom such as Examples of such heterocycloalkyl include, but are not limited to, morpholine, piperazine, and the like.

In this specification, "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited as long as the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and when two or more are substituted , Two or more substituents may be the same as or different from each other. The substituent is hydrogen, heavy hydrogen, cyano group, nitro group, halogen group, hydroxyl group, alkyl group having 1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms, alkynyl group having 2 to 24 carbon atoms, heteroalkyl group having 2 to 30 carbon atoms, carbon atoms An aralkyl group having 6 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heteroarylalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamine group having 1 to 30 carbon atoms, It may be substituted with one or more substituents selected from the group consisting of an arylamine group having 6 to 30 carbon atoms, an aralkylamine group having 6 to 30 carbon atoms, and a hetero arylamine group having 2 to 24 carbon atoms, but is not limited to the above examples.

The present invention is excellent in minimum aging, and even when stored for a long time in a state in which it is laminated with an adhesive layer, no tearing occurs when the release film is peeled off, and exhibits an antistatic effect, preventing static electricity generation after peeling the release film What can be done, when preparing a release film, by applying a composition for silicone release coating to form a release layer, it can be provided in a one-component type without the need to form a separate antistatic layer.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

A composition for silicone release coating according to an embodiment of the present invention includes a solvent; polysiloxane represented by Formula 1 below; CNT dispersion; retardants; cross-linking agent; and a catalyst:

[Formula 1]

here,

n and m are the same as or different from each other, and each independently represents an integer from 1 to 1000;

R ₁ to R ₁₀ are the same as or different from each other, and are each independently hydrogen, halogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted carbon atom having 2 to 24 carbon atoms. Alkynyl group, substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, substituted or unsubstituted aryl group having 5 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms Aryl group, substituted or unsubstituted unsubstituted heteroarylalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 3 to 20 carbon atoms It is selected from the group consisting of 20 cycloalkenyl groups, substituted or unsubstituted heteroaralkyl groups having 3 to 30 carbon atoms, and substituted or unsubstituted heteroalkenyl groups having 1 to 20 carbon atoms,

At least one of R ₁ to R ₁₀ is a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms.

Specifically, the polysiloxane represented by Chemical Formula 1 may include at least one vinyl group as a substituent. As will be described later, the polysiloxane may be combined with Si—H in a crosslinking agent to form a release layer.

A composition for release coating using a conventional polysiloxane includes a vinyl group and is bonded to a crosslinking agent. However, no reaction with Si-H in the cross-linking agent occurred, and Si-H bonds remained.

Due to the mixing of the crosslinking agent and non-reaction with the polysiloxane, Si-H remaining in the release layer may be a cause of change over time.

That is, the release film should have no change in release property in a high temperature and high humidity environment, but Si-H bonds remaining in the release layer show a change in release property in a high temperature and high humidity environment, causing release defects.

Therefore, in the present invention, it is intended to increase the stability over time by minimizing the residual Si-H in the bond between the polysiloxane and the crosslinking agent.

Specifically, the polysiloxane represented by Formula 1 may include at least one vinyl group as a substituent, and more preferably may include a polysiloxane having vinyl groups as substituents at both ends and having vinyl groups substituted at side chains.

More specifically, the compound represented by Formula 1 may be a compound represented by Formula 3 below:

[Formula 3]

here,

q and r are the same as or different from each other, and each independently represents an integer from 1 to 1000;

R ₂₀ to R ₂₆ are the same as or different from each other, and are each independently hydrogen, halogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted carbon atom having 2 to 24 carbon atoms. Alkynyl group, substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, substituted or unsubstituted aryl group having 5 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms Aryl group, substituted or unsubstituted unsubstituted heteroarylalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 3 to 20 carbon atoms It may be selected from the group consisting of 20 cycloalkenyl groups, substituted or unsubstituted heteroaralkyl groups having 3 to 30 carbon atoms, and substituted or unsubstituted heteroalkenyl groups having 1 to 20 carbon atoms.

As described above, when the vinyl group is included as a substituent, bonding occurs between the vinyl group and Si-H of the crosslinking agent, and after forming the release layer, the residual of Si-H in the release layer can be minimized. Compared to polysiloxane in which vinyl groups are substituted at both ends, as the side chain additionally includes a vinyl group, bonding with a crosslinking agent may be increased, thereby exhibiting minimum aging characteristics.

The polysiloxane included in the present invention is a polysiloxane having a narrow molecular weight distribution, and is characterized by having a PDI (Mw/Mn) of 1.7 to 2. As the PDI value increases, it means that a polymer having a wide range of molecular weight distribution is used, and when manufactured as a release film, it is impossible to implement ultra-thin characteristics. That is, it will be said that it is possible to manufacture a release film capable of implementing ultra-thin characteristics using polysiloxane having PDI within the above range.

The crosslinking agent may be a compound represented by Formula 2 below:

[Formula 2]

here,

o and p are the same as or different from each other, and each independently represents an integer from 1 to 1000;

R ₁₁ to R ₁₉ are the same as or different from each other, and are each independently hydrogen, halogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted carbon atom having 2 to 24 carbon atoms. Alkynyl group, substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, substituted or unsubstituted aryl group having 5 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms Aryl group, substituted or unsubstituted unsubstituted heteroarylalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 3 to 20 carbon atoms It is selected from the group consisting of 20 cycloalkenyl groups, substituted or unsubstituted heteroaralkyl groups having 3 to 30 carbon atoms, and substituted or unsubstituted heteroalkenyl groups having 1 to 20 carbon atoms,

At least three or more of R ₁₁ to R ₁₉ are substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms.

More specifically, the crosslinking agent may be a compound represented by Formula 4 below:

[Formula 4]

here,

s and t are the same as or different from each other, and are each independently an integer of 1 to 1000.

As described above, when the hydrogen atoms bonded to silicon atoms in the crosslinking agent increase, the crosslinking density in the release layer increases, and physical properties of the release layer can be enhanced. However, when the number of hydrogen atoms bonded to silicon atoms increases, , there is a problem that the minimum timeliness is not secured.

Therefore, in the present invention, as the compound represented by Formula 4 is used as a crosslinking agent, when provided as a release layer, physical properties are maintained by maintaining the crosslinking density, and residual Si-H in the release layer is minimized to minimize the elapsed time. gender can be indicated.

In addition, the polysiloxane further includes a vinyl group in the side chain of one end in addition to both ends, so that a release layer having a high crosslinking density can be formed on the surface close to the substrate layer, providing stability over time during peeling, and easy peeling properties can be implemented.

That is, the release film is used for the OLED display panel, and in order to protect the OCA (Optical Clear Adhesive), it is put into the manufacturing process in the form attached to one side of the OCA, and then the release film attached to the OCA must be removed. , In this case, when the release film exhibits high adhesive strength, damage occurs to the OLED layer during the removal process of the release film.

In order to prevent this problem, it is necessary for the release film to exhibit light peeling properties, and when using the composition for silicone release coating of the present invention, when manufactured as a release film, it can exhibit ultralight peeling properties, when used in an OCA film Even in the process of removing the release film, there is no damage to the OLED.

The retardant is included to prevent pre-curing or gelling before processing, and 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, 3,5-dimethyl-1 -Hexyn-3-ol, 1-ethynyl cyclohexanol, 1,5-hexadiyne, 1,6-heptadiyne, 3,5-dimethyl-1-hexene-1-yne, 3-ethyl-3 -buten-1-yne, 3-phenyl-3-butene-1-yne, 1,3-divinyltetramethyldisiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, 1,3- Divinyl-1,3-diphenyldimethyldisiloxane, methyltris(3-methyl-1-butyn-3-oxy)silane, tributylamine, tetramethylethylenediamine, benzotriazole, triphenylphosphine, sulfur-containing compounds, hydroperoxy compounds, maleic acid derivatives-1-ethynylcyclohexanol, 3-methyl-1-penten-3-ol, and mixtures thereof.

For the purpose of accelerating the polymerization reaction, the catalyst may generally be a platinum-based catalyst, a palladium-based catalyst, or a rhodium-based catalyst, preferably a platinum-based catalyst, but is not limited to the above examples, and other types of catalysts in addition to the catalysts exemplified above Alternatively, the content can be used within the commonly used range in the release film field.

As a method of imparting an antistatic function to the release film, for example, an antistatic layer made of a cationic antistatic agent is provided on one side of a base film, and the release layer is formed on the other side. Conventionally, it is often used to impart an antistatic function to a release film, and although it can exhibit a certain antistatic effect, it cannot sufficiently prevent static electricity from being charged to the release film.

A method of imparting an antistatic function to a release film by forming an antistatic layer between the base film and the release layer has also been proposed. In the case of the proposed technology, since two coating layers are formed on the base film, two application steps are required, and there is a problem that the cost required for the process is high and the production efficiency is also low. As another proposed technique, a technique of imparting antistatic properties and releasability to a base film with a single coating layer using a conductive polymer has been proposed.

However, since the coating layer formed using a conductive polymer is not crosslinked by a curable resin or a crosslinking agent, it is easily dissolved in a solvent, and when a resin film, pressure-sensitive adhesive layer, ceramic slurry, etc. containing a solvent comes into contact with the coating layer, Sufficient releasability may not be obtained. In addition, although a conductive polymer dispersed in a solvent is used, since the type of solvent capable of dispersing the conductive polymer is small, when preparing a coating agent forming the coating layer, the solvent of the coating agent is limited, or a dispersant (surfactant) It is necessary to use, and there is a problem in handling, and when a surfactant is used, there is also a problem in that the surfactant bleeds from the coating layer.

Accordingly, as described above, the release film exhibiting an antistatic effect has a problem in that the antistatic effect is low or the economical efficiency is low due to manufacturing procedures.

The present invention is characterized in that a CNT dispersion is mixed in order to exhibit an antistatic effect.

In the silicone release coating composition containing the CNT dispersion, when the CNT dispersion is uniformly distributed in the release coating composition and cured to form a release layer on one surface of the base film, the release layer can exhibit an antistatic effect. Therefore, it can be provided as a one-component silicone release coating composition.

The CNT is a carbon nanotube, and may be selected from the group consisting of single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, and mixtures thereof. In general, CNTs are classified into single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes according to the number of bonds constituting the wall. It is known that there is a difference in antistatic effect depending on the number of walls, and single-walled carbon nanotubes can exhibit the best antistatic effect.

However, due to the high price of single-walled carbon nanotubes compared to multi-walled carbon nanotubes, production cost may be a problem. Therefore, in the present invention, a CNT dispersion that can exhibit an excellent antistatic effect using multi-walled carbon nanotubes can be used.

The CNT dispersion may include 0.3 to 0.5 parts by weight of CNT and 0.3 to 0.5 parts by weight of a dispersant based on 100 parts by weight of the solvent.

The dispersant includes surfactants, coupling agents, block copolymers, monomers, oligomers, vinyls, lactics, caprolactones, silicones, waxes, silanes, fluorines, ethers, alcohols, esters and It may be selected from the group consisting of mixtures thereof. Preferably, anionic surfactants such as SDS and NaDDBS, cationic surfactants CTAB, nonionic TWEEN, TRITION, and amphoteric surfactants Tego5 and SAZM Z-3-18 may be selected, more preferably NaDDBS , dispersed PVP, Tego5, SDS, and mixtures thereof.

The solvent may be selected from the group consisting of water, alcohol, cellusolve, ketone, amide, ester, ether, aromatic, hydrocarbon, and mixtures thereof.

The CNT dispersion may be prepared by putting CNTs and a dispersing agent in a solvent and uniformly mixing them using an ultrasonic disperser. When mixed within the above range, it is possible to provide a CNT dispersion with excellent dispersibility. As the dispersion process proceeds by stirring using the disperser, the CNTs in the dispersion are cut to have an average diameter of 50 to 100 nm and are uniformly dispersed. The CNTs are MWCNTs, which are included in the form of bundles, but are cut by a disperser to have an average diameter of 50 to 100 nm, and are uniformly mixed in the dispersion by the dispersant, thereby exhibiting an antistatic effect.

The silicone release coating composition of the present invention contains 40 to 60 parts by weight of polysiloxane, 5 to 10 parts by weight of a crosslinking agent, 70 to 80 parts by weight of a CNT dispersion, 0.05 to 0.5 parts by weight of a retardant, and 1 to 10 parts by weight of a catalyst, based on 100 parts by weight of a solvent. 5 parts by weight. When mixed and used within the above range, after being prepared as a release film, it will be possible to provide a release film that exhibits minimum aging characteristics, light peeling characteristics and excellent antistatic properties.

A silicone release film according to another embodiment of the present invention includes a base film; and a release layer formed on one surface of the base film, wherein the release layer is formed by applying the composition for silicone release coating according to an embodiment of the present invention.

When applying the coating composition of the present invention, a solvent, polysiloxane represented by the following formula (1); a CNT dispersion, a retardant and a crosslinking agent are uniformly dispersed; and a catalyst are mixed before coating on one side of the base film to prepare a coating composition, and then applied to one side of the base film.

[Formula 1]

here,

n and m are the same as or different from each other, and each independently represents an integer from 1 to 1000;

R ₁ to R ₁₀ are the same as or different from each other, and are each independently hydrogen, halogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted carbon atom having 2 to 24 carbon atoms. Alkynyl group, substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, substituted or unsubstituted aryl group having 5 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms Aryl group, substituted or unsubstituted unsubstituted heteroarylalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 3 to 20 carbon atoms It is selected from the group consisting of 20 cycloalkenyl groups, substituted or unsubstituted heteroaralkyl groups having 3 to 30 carbon atoms, and substituted or unsubstituted heteroalkenyl groups having 1 to 20 carbon atoms,

At least one of R ₁ to R ₁₀ is a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms.

The cross-linking of the polysiloxane with a cross-linking agent occurs, and the cross-linking is carried out by a catalyst. When the release coating composition is prepared, when the catalyst is mixed, it becomes impossible to produce a release layer. Accordingly, the catalyst is mixed with the main chain immediately before application on one surface of the base film and applied to the base film to form a release layer.

As a method of applying the release coating composition to the base film, known methods such as gravure roll coating method, slot die coating method, reverse roll coating method, and air knife coating method may be employed. As a drying method after coating, hot air is mainly used. A drying method is used. The higher the curing temperature during drying, the shorter the curing time. Preferably, drying conditions within 1 to 5 minutes under a temperature of 80 to 180 ° C are suitable.

Preparation Example 1

Preparation of CNT dispersion

100 parts by weight of alcohol and 0.5 parts by weight of MWCNT were mixed, and a dispersion was prepared for 20 to 30 hours using a homogenizer. Thereafter, 0.5 parts by weight of a dispersant in which NaDDBS and dispersed PVP were mixed in a weight ratio of 1:1 were mixed and mixed for 1 hour using a homogenizer to prepare a CNT dispersion. The CNTs in the CNT dispersion have an average diameter of 50 to 100 nm.

Preparation Example 2

Manufacture of silicone release film

Toluene, polysiloxane represented by the following formula 5, 1-ethynyl cyclohexanol, a crosslinking agent represented by the following formula 4, and a CNT dispersion were mixed to prepare a main material.

A silicone release coating composition was prepared by mixing a platinum catalyst and a solvent with the above subject. After preparing a solvent mixture in which methyl ethyl ketone (MEK) and toluene were mixed at 1:1 parts by weight, the release coating composition was mixed in a solid content of 5% by weight with respect to the solvent mixture, and a coating solution was prepared. The coating solution was applied to a thickness of 1 μm on one side of a polyester film and cured at 160° C. for 3 minutes to prepare a release film.

[Formula 4]

[Formula 5]

here,

s, t, x, and y are the same as or different from each other, and each independently represents an integer from 1 to 1000;

The PDI of the compound represented by Formula 5 is 1.7.

The content of the silicone release coating composition is shown in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Example 5 menstruum 100 100 100 100 100 polysiloxane 30 40 50 60 70 retardant 0.01 0.05 0.1 0.5 One cross-linking agent One 5 7 10 15 CNT dispersion 60 70 75 80 90 catalyst 0.5 One 3 5 10

(unit weight parts)

Example 6

The CNT dispersion was prepared in the same manner as in Example 3, except that only NaDDBS was used as a dispersant.

Example 7

The CNT dispersion was prepared in the same manner as in Example 3, except that only dispersed PVP was used as a dispersing agent.

Example 8

The CNT dispersion was prepared in the same manner as in Example 3, except that the dispersant was mixed in an amount of 0.1 part by weight.

Example 9

The CNT dispersion was prepared in the same manner as in Example 3, except that the dispersant was mixed in an amount of 0.3 parts by weight.

Example 10

The CNT dispersion was prepared in the same manner as in Example 3, except that the dispersant was mixed in an amount of 0.7 parts by weight.

Example 11

When preparing the CNT dispersion, a homogenizer was used to prepare the dispersion for 40 hours, and the CNT was prepared in the same manner as in Example 3, except that the average diameter was cut to 10 to 30 μm.

Example 12

When preparing the CNT dispersion, a homogenizer was used to prepare the dispersion for 5 hours, and the CNT was prepared in the same manner as in Example 3, except that the average diameter was 1,000 to 2,000 nm.

Experimental Example 1

Evaluation of light peeling characteristics and residual adhesion rate

To measure the peel force, a standard adhesive tape (Nitto 31B) was attached to the coated surface of the release layer and then cut into a size of 25mmХ15cm to prepare a sample. Thereafter, using SHIMADZU's AGS-X, the peeling rate was measured at an angle of 180 degrees at a speed of 300 mm/min.

After storing the sample for measurement at 25° C. and 65% RH for 24 hours, a standard adhesive tape (Nitto 31B) was attached to the coated surface of the release layer, and then the sample was compressed at room temperature under a load of 20 g/cm ² for 24 hours. After collecting the tape adhered to the coated surface of the coating layer without contamination, it was adhered to a PET film surface with a flat and clean surface, and then reciprocated once with a 2 kg tape roller (ASTMD-1000-55T). The peel force was measured as follows and the residual adhesion rate was calculated. Using SHIMADZU's AGS-X, the peeling rate was measured at an angle of 180 degrees at a rate of 300 mm/min.

Measurement data: Residual adhesion rate (%) = [peel force of adhesive tape peeled after adhesion to coated surface/peel force of adhesive tape not in contact with coated surface] Х 100

Example 1 Example 2 Example 3 Example 4 Example 5 Peel force (gf/in) 4.11 4.24 4.33 5.6 10.21 Residual adhesion rate (%) 88.3 92.2 98.6 94.2 81.1

According to the above experimental results, it can be confirmed that Examples 1 to 4 exhibit light peeling properties, and in particular, Examples 2 to 4 can confirm that the residual adhesion rate is excellent.

Experimental Example 2

Measurement of change over time

An adhesive tape (Nitto 31B) was placed on the coated surface of the release layer, rubbed back and forth twice using a 2Kg rubber roll, and then cut to a size of 25mmХ15cm to prepare a sample. The prepared sample was subjected to a load of 70 g/cm 2 and left for 72 hr in an environment of 60° C. and 90% humidity, and then 180 degree peel peel evaluation was performed using a peel tester (SHIMADZU, AGS-X).

Average change in release force over time: average value measured continuously in the 10cm range.

Variation of release force over time: Indicates the difference between the maximum and minimum values while continuously measuring a range of 10 cm.

Example 1 Example 2 Example 3 Example 4 Example 5 release force average 24 12 13 11 48 release force deviation 2.1 One 0.9 1.2 5

According to the above experimental results, it was confirmed that Example 5 was not excellent in the minimum aging characteristics, and it was confirmed that the minimum aging characteristics were excellent in the range of Examples 2 to 4.

Experimental Example 3

Evaluation of antistatic properties

Antistatic properties of Example 3 and Examples 6 to 10 were evaluated. Based on the ASTM D257 measurement method, it was measured under the conditions of 55% RH, 23 ℃, and applied voltage of 500V.

A release film was prepared in the same manner as in Example 3, except that SWCNT was used as a control and only NaDDBS was used as a dispersant.

control group Example 3 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 surface resistance
(Ω/ㅁ) 10E10 10E9 10E13 10E13 10E14 10E8 10E13 10E13 10E13

In order for the release film to have an antistatic effect, the CNTs should be uniformly dispersed. In Examples 6 to 8 and 10 to 12, the CNTs were not uniformly dispersed, so the surface resistance exceeded 10 ¹² Ω/ㅁ, It was confirmed that the antistatic properties were not exhibited. On the other hand, it was confirmed that Examples 3 and 9 exhibit excellent antistatic properties comparable to those using SWCNTs. This will mean that even if MWCNTs are used, antistatic properties can be exhibited by improving dispersibility by using a dispersant.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concept of the present invention defined in the following claims are also made according to the present invention. falls within the scope of the rights of

Claims (7)

menstruum;
polysiloxane represented by the following formula (5);
CNT dispersion;
retardants;
cross-linking agent; and
contains a catalyst;
A release layer capable of forming a release layer with excellent light peeling and minimal aging
Compositions for silicone release coatings:
[Formula 5]

here,
x and y are the same as or different from each other, and are each independently an integer of 1 to 1000. delete According to claim 1,
The crosslinking agent is a compound represented by Formula 2 below.
Compositions for silicone release coatings:
[Formula 2]

here,
o and p are the same as or different from each other, and each independently represents an integer from 1 to 1000;
R ₁₁ to R ₁₉ are the same as or different from each other, and are each independently hydrogen, halogen, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted carbon atom having 2 to 24 carbon atoms. Alkynyl group, substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, substituted or unsubstituted aryl group having 5 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms Aryl group, substituted or unsubstituted unsubstituted heteroarylalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 3 to 20 carbon atoms It is selected from the group consisting of 20 cycloalkenyl groups, substituted or unsubstituted heteroaralkyl groups having 3 to 30 carbon atoms, and substituted or unsubstituted heteroalkenyl groups having 1 to 20 carbon atoms,
At least three or more of R ₁₁ to R ₁₉ are substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms. According to claim 1,
The retardant is 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynyl cyclohexanol, 1,5-hexadiyne, 1,6-heptadiyne, 3,5-dimethyl-1-hexene-1-yne, 3-ethyl-3-butene-1-yne, 3-phenyl-3-butene- 1-phosphorus, 1,3-divinyltetramethyldisiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, 1,3-divinyl-1,3-diphenyldimethyldisiloxane, and methyl Tris(3-methyl-1-butyn-3-oxy)silane, tributylamine, tetramethylethylenediamine, benzotriazole, triphenylphosphine, maleic acid derivative-1-ethynylcyclohexanol, 3-methyl -1-penten-3-ol and mixtures thereof selected from the group consisting of
A composition for silicone release coating. According to claim 1,
The CNT dispersion comprises 0.3 to 0.5 parts by weight of CNT and 0.3 to 0.5 parts by weight of a dispersant based on 100 parts by weight of solvent.
A composition for silicone release coating. base film; and
Including a release layer formed on one side of the base film,
The release layer is formed by applying the silicone release coating composition according to any one of claims 1 and 3 to 5
silicone release film. According to claim 6,
The release layer may include a solvent, a polysiloxane represented by Formula 5, a CNT dispersion, a retardant, and a crosslinking agent uniformly dispersed therein; And the catalyst is mixed on one side of the base film before coating to prepare a coating composition, and then applied to one side of the base film to form a release layer.
Silicone release film:
[Formula 5]

here,
x and y are the same as or different from each other, and are each independently an integer of 1 to 1000.