KR20220087127A - Composition for silicone release coating and release film comprising same - Google Patents

Abstract

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

Description

Composition for silicone release coating and release film comprising 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 that is excellent in minimum aging and exhibits an antistatic effect, and a release film comprising the same.

The release film is a process film for cast film such as urethane resin, acrylic resin, vinyl chloride resin, etc., protective film for adhesive layer such as adhesive tape, adhesive sheet, and adhesive film, and electronic parts such as ceramic green sheet and printed circuit board. It is used as a process film for manufacture. Generally, as a release film, the thing in which the release layer which consists of a silicone type or a non-silicone type release agent was formed on the surface of base films, such as a polyester film, is main.

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 and removed from the pressure-sensitive adhesive layer, and the liquid crystal cell After pasting, when the role of the surface protection film is finished in the post process, it is also peeled off and removed.

In addition, it is mainly used during the manufacturing process of OLED.

Usually, the release film is peeled off after the resin sheet is molded, when the adhesive film is used, or after the production of electronic components, but when peeled, static electricity is easily charged. Therefore, when storing resin sheets in stacks, there is a problem in 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 and adheres The floor was becoming a cause of contamination.

Further, in the case of ceramic green sheets, thinning is progressing along with the miniaturization and capacity increase of ceramic capacitors. However, as the thinning progresses, peeling charging is large in conventional release films, and thus electrostatic disturbance is a major problem. From these problems, in recent years, the antistatic function has come to be calculated|required by the release film.

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

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

As described above, the silicone release film does not have a problem in peeling stability due to change over time, and it is necessary to develop a silicone release film capable of exhibiting a charging effect.

KR 10-0965378 B1

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

Another object of the present invention relates to a composition for a silicone release coating that has excellent minimum aging, and does not cause tearing when the release film is peeled off, even when stored for a long time in a state 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 static electricity generation after peeling of the release film. It relates to a one-component silicone release coating composition that does not need to form an antistatic layer, and a release film comprising the same.

In order to achieve the above object, the composition for a silicone release coating according to an embodiment of the present invention is a solvent; Polydimethylsiloxane represented by the following formula (1); CNT dispersion; retardant; crosslinking agent; and catalysts:

[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 each independently hydrogen, halogen, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 24 of an alkynyl group, a substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, a 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 a 20 cycloalkenyl group, a substituted or unsubstituted heteroaralkyl group having 3 to 30 carbon atoms and a substituted or unsubstituted heteroalkenyl group 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 polydimethylsiloxane represented by Formula 1 may include at least one vinyl group as a substituent.

The crosslinking agent may be a compound represented by the following Chemical Formula 2:

[Formula 2]

here,

R ₁₁ to R ₁₉ are the same as or different from each other, and each independently hydrogen, halogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, or a substituted or unsubstituted C2-C24 of an alkynyl group, a substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, a 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 a 20 cycloalkenyl group, a substituted or unsubstituted heteroaralkyl group having 3 to 30 carbon atoms and a substituted or unsubstituted heteroalkenyl group 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 retarder 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-butyne-3-oxy)silane, tributylamine, tetramethylethylenediamine, benzotriazole, triphenylphosphine, sulfur-containing compound, hydroperoxy compound, 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 the dispersant based on 100 parts by weight of the solvent.

Silicone release film according to another embodiment of the present invention is 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 is a solvent, polydimethylsiloxane represented by the following formula (1); CNT dispersion, retarder and crosslinking agent uniformly dispersed main agent; And the catalyst is mixed before coating on one side of the base film to prepare a coating composition, and then a release layer can be formed by applying it to one side of the base film:

[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 each independently hydrogen, halogen, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 24 of an alkynyl group, a substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, a 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 a 20 cycloalkenyl group, a substituted or unsubstituted heteroaralkyl group having 3 to 30 carbon atoms and a substituted or unsubstituted heteroalkenyl group 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” refers to a monovalent substituent derived from a saturated hydrocarbon having 1 to 40 carbon atoms in a straight or branched chain. 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 or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon double bonds. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.

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

As used herein, "aralkyl" refers to an aryl-alkyl group wherein aryl and alkyl are as described above. Preferred aralkyls include lower alkyl groups. Non-limiting examples of suitable aralkyl groups include benzyl, 2-phenethyl and naphthalenylmethyl. Binding to the parent moiety is through an alkyl.

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

In the present invention, “heteroaryl” refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 6 to 30 carbon atoms. In this case, one or more carbons in the ring, preferably 1 to 3 carbons, are 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 further, 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, and carbazolyl, and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like, but is not limited thereto.

In the present invention, “heteroaralkyl group” refers to an aryl-alkyl group substituted with a heterocyclic group.

In the present invention, “cycloalkyl” refers to 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 at least one carbon in the ring, preferably 1 to 3 carbons, is N, O, S or Se substituted with a hetero atom such as Examples of such heterocycloalkyl include, but are not limited to, morpholine and piperazine.

As used herein, "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 position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is not limited, 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, deuterium, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a heteroalkyl group having 2 to 30 carbon atoms, a carbon number 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 heteroarylamine group having 2 to 24 carbon atoms, but is not limited thereto.

The present invention has excellent minimum aging property, and even when stored for a long time in a state of being laminated with an adhesive layer, a tear phenomenon does not occur when the release film is peeled, and it exhibits an antistatic effect, thereby preventing the generation of static electricity after peeling of the release film As can be done, when the release film is manufactured, the silicone release coating composition is applied to form a release layer, so that it can be provided as 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 of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

The composition for a silicone release coating according to an embodiment of the present invention includes a solvent; Polysiloxane represented by the following formula (1); CNT dispersion; retardant; crosslinking agent; and catalysts:

[Formula 1]

here,

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

R ₁ to R ₁₀ are the same as or different from each other, and each independently hydrogen, halogen, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 24 of an alkynyl group, a substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, a 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 a 20 cycloalkenyl group, a substituted or unsubstituted heteroaralkyl group having 3 to 30 carbon atoms and a substituted or unsubstituted heteroalkenyl group 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 Formula 1 may include at least one vinyl group as a substituent. The polysiloxane may be combined with Si-H in a crosslinking agent to form a release layer, as will be described later.

Conventionally, the composition for release coating using polysiloxane includes a vinyl group and is disclosed for binding with a crosslinking agent. However, none of the reaction with Si-H in the cross-linking agent occurred, so a residual Si-H bond was present.

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

That is, the release film should have no change in releasability in a high-temperature and high-humidity environment, but the Si-H bond remaining in the release layer showed a change in releasability in a high-temperature and high-humidity environment, causing a release defect.

Accordingly, in the present invention, in the bonding between the polysiloxane and the crosslinking agent, the residual Si-H is minimized to improve stability over time.

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

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 are each independently an integer from 1 to 1000,

R ₂₀ to R ₂₆ are the same or different from each other, and each independently represents hydrogen, halogen, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, or a substituted or unsubstituted C 2 to C 24 of an alkynyl group, a substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, a 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 a 20 cycloalkenyl group, a substituted or unsubstituted heteroaralkyl group having 3 to 30 carbon atoms, and a substituted or unsubstituted heteroalkenyl group having 1 to 20 carbon atoms.

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

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

The crosslinking agent may be a compound represented by the following Chemical Formula 2:

[Formula 2]

here,

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

R ₁₁ to R ₁₉ are the same as or different from each other, and each independently hydrogen, halogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, or a substituted or unsubstituted C2-C24 of an alkynyl group, a substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, a 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 a 20 cycloalkenyl group, a substituted or unsubstituted heteroaralkyl group having 3 to 30 carbon atoms and a substituted or unsubstituted heteroalkenyl group 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.

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 from 1 to 1000.

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

Accordingly, in the present invention, as the crosslinking agent is used as the compound represented by Formula 4, when provided as a release layer, the crosslinking density is maintained to secure physical properties, and the residual Si-H in the release layer is minimized to minimize the lapse of time. can indicate gender.

In addition, since the polysiloxane additionally includes a vinyl group in the side chain at one end in addition to both ends, it is possible to form a release layer having a high crosslinking density on the surface adjacent to the base layer, thereby providing stability over time during peeling, light peeling properties can be implemented.

That is, the release film is used in the OLED display panel, and in order to protect the OCA (Optical Clear Adhesive), it is put into the manufacturing process in a 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 to the OLED layer occurs 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 by using the silicone release coating composition of the present invention, it can exhibit super light peeling properties when manufactured as a release film, so when used in OCA film Even in the process of removing the release film, there is no damage to the OLED.

The retarder is included to prevent pre-curing or gelation before processing, 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-hexen-1-yne, 3-ethyl-3 -Butene-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.

The catalyst may be a platinum-based catalyst, a palladium-based catalyst or a rhodium-based catalyst for the purpose of accelerating the polymerization reaction, and is preferably a platinum-based catalyst, but is not limited to the above examples Or the content can be used all within the range commonly used in the field of release film.

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

A method of imparting an antistatic function to the 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 technique, since two coating layers are formed on the base film, two application steps are required, and there is a problem that the cost of the process is high and the production efficiency is also low. As another proposed technique, a technique for 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. Sufficient releasability may not be obtained. In addition, although a conductive polymer dispersed in a solvent is used, there are few solvents in which the conductive polymer can be dispersed. Since it is necessary to use , there is a problem in handling properties, and when a surfactant is used, there is also a problem in that the surfactant is transferred from the coating layer (bleeding).

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

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

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

The CNTs are carbon nanotubes, 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 forming the wall. It is known that there is a difference in the antistatic effect depending on the number of walls, so single-walled carbon nanotubes can exhibit the best antistatic effect.

However, single-walled carbon nanotubes may be expensive compared to multi-walled carbon nanotubes, and production cost may be a problem. Accordingly, in the present invention, a CNT dispersion capable of exhibiting 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 the 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 may be selected from the group consisting of mixtures thereof. Preferably, it may be selected from anionic surfactants SDS, NaDDBS, cationic surfactants CTAB, nonionic TWEEN, TRITION, amphoteric surfactants Tego5, and SAZM Z-3-18, 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 adding CNTs and a dispersing agent to a solvent, and uniformly mixing using an ultrasonic disperser, and it is possible to provide a CNT dispersion having excellent dispersibility when used by mixing within the above range. As the dispersion process proceeds by stirring using the disperser, the CNTs in the dispersion are cut, and the average diameter is cut to 50 to 100 μm and uniformly dispersed. The CNTs are MWCNTs, which are included in the form of bundles, but are cut by a disperser and have an average diameter of 50 to 100 μm, and are uniformly mixed in the dispersion by the dispersant, thereby exhibiting an antistatic effect.

The silicone release coating composition of the present invention is based on 100 parts by weight of the solvent, 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 retarder, and 1 to 1 to a catalyst. It may be included in 5 parts by weight. It will be said that it is possible to provide a release film that exhibits minimum aging characteristics, light peeling characteristics and excellent antistatic properties after manufacturing as a release film when mixed within the above range.

Silicone release film according to another embodiment of the present invention is 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 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); CNT dispersion, retarder and crosslinking agent uniformly dispersed main agent; And the catalyst is mixed before coating on one surface of the base film to prepare a coating composition, and then applied to one surface of the base film.

[Formula 1]

here,

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

R ₁ to R ₁₀ are the same as or different from each other, and each independently hydrogen, halogen, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 24 of an alkynyl group, a substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, a 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 a 20 cycloalkenyl group, a substituted or unsubstituted heteroaralkyl group having 3 to 30 carbon atoms and a substituted or unsubstituted heteroalkenyl group 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 polysiloxane is cross-linked with a cross-linking agent, and the cross-linking reaction proceeds by a catalyst. Accordingly, the catalyst is mixed with the main chain immediately before being applied to one side 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, air knife coating method, etc. can be adopted, and the drying method after coating is mainly hot air. 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 the mixture was prepared as a dispersion for 20 to 30 hours using a homogenizer. Then, 0.5 parts by weight of a dispersing agent mixed with NaDDBS and dispersed PVP in a weight ratio of 1:1 was 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 μm.

Preparation 2

Preparation 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 base material. After preparing a solvent mixture in which methyl ethyl ketone (MEK) and toluene were mixed in 1:1 parts by weight, the release coating composition was mixed at 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 one surface of the polyester film to a thickness of 1 μm, 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 are each independently 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 crosslinking agent One 5 7 10 15 CNT dispersion 60 70 75 80 90 catalyst 0.5 One 3 5 10

(unit parts by weight)

Example 6

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

Example 7

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

Example 8

It was prepared in the same manner as in Example 3, except that 0.1 parts by weight of the dispersant was mixed in the preparation of the CNT dispersion.

Example 9

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

Example 10

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

Example 11

During the preparation of the CNT dispersion, a dispersion was prepared for 40 hours using a homogenizer, and the CNTs were prepared in the same manner as in Example 3, except that the average diameter was cut to 10 to 30 μm.

Example 12

During the preparation of the CNT dispersion, a dispersion was prepared for 5 hours using a homogenizer, and the CNTs were prepared in the same manner as in Example 3, except that the average diameter was 1,000 to 2,000 μm.

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 cut to a size of 25mmХ15cm to prepare a sample. Thereafter, using SHIMADZU's AGS-X, it was measured at an angle of 180 degrees at a peeling rate of 300 mm/min.

After the measurement sample was stored 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 the sample was compressed at room temperature under a load of 20 g/cm ² for 24 hours. The tape adhered to the coating surface of the coating layer was collected without contamination, and then adhered to the PET film surface with a flat and clean surface, followed by reciprocating compression once with a 2 kg tape roller (ASTMD-1000-55T). Peel force was measured as follows and the residual adhesion rate was calculated. Using SHIMADZU's AGS-X, it measured at the angle of 180 degree|times at the rate of 300 mm/min of peeling speed|rate.

Measured data: Residual adhesive rate (%) = [Peel force of the adhesive tape peeled after adhesion to the coated surface / Peel force of the adhesive tape not in contact with the 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 experimental results, it can be confirmed that Examples 1 to 4 exhibit light peeling properties, and in particular, Examples 2 to 4 have excellent residual adhesion.

Experimental Example 2

Measuring change over time

An adhesive tape (Nitto 31B) was placed on the coated surface of the release layer and reciprocated twice using a 2Kg rubber roll, and then cut into a size of 25mmХ15cm to prepare a sample. After applying a load of 70 g/cm 2 to the prepared sample and leaving it for 72 hrs at a temperature of 60° C. and a humidity of 90%, 180 degree peeling evaluation was performed using a Peel Tester (SHIMADZU, AGS-X).

Average release force change over time: Average value measured continuously over a range of 10 cm.

Deviation of release force over time: It shows 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 average release force 24 12 13 11 48 Deviation of release force 2.1 One 0.9 1.2 5

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

Experimental Example 3

Antistatic property evaluation

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

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

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

In order for the antistatic effect to appear in the release film, the CNTs should be uniformly dispersed, and in Examples 6 to 8 and 10 to 12, the CNTs were not uniformly dispersed, and the surface resistance exceeded 10 ¹² Ω / ㅁ, It was confirmed that the antistatic property was not exhibited. On the other hand, it was confirmed that Examples 3 and 9 exhibited excellent antistatic properties to the extent that SWCNTs were used. This means that even when MWCNTs are used, antistatic properties can be exhibited by improving dispersibility by using a dispersant.

Although 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 by those skilled in the art using the basic concept of the present invention as defined in the following claims are also provided. is within the scope of the

Claims (7)

menstruum;
Polysiloxane represented by the following formula (1);
CNT dispersion;
retardant;
crosslinking agent; and
comprising a catalyst;
It is capable of forming a release layer with excellent light peeling and minimum aging properties.
Compositions for silicone release coatings:
[Formula 1]

here,
n and m are the same as or different from each other, and are each independently an integer from 1 to 1000,
R ₁ to R ₁₀ are the same as or different from each other, and each independently represents hydrogen, halogen, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, or a substituted or unsubstituted C 2 to C 24 of an alkynyl group, a substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms An aryl group, a substituted or unsubstituted unsubstituted heteroarylalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 3 to 20 carbon atoms It is selected from the group consisting of a 20 cycloalkenyl group, a substituted or unsubstituted heteroaralkyl group having 3 to 30 carbon atoms, and a substituted or unsubstituted heteroalkenyl group 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. According to claim 1,
The polysiloxane represented by Formula 1 includes at least one vinyl group as a substituent
A composition for silicone release coating. According to claim 1,
The crosslinking agent is a compound represented by the following formula (2)
Compositions for silicone release coatings:
[Formula 2]

here,
o and p are the same as or different from each other, and are each independently an integer from 1 to 1000,
R ₁₁ to R ₁₉ are the same as or different from each other, and each independently hydrogen, halogen, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C2-C30 alkenyl group, or a substituted or unsubstituted C2-C24 of an alkynyl group, a substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, a 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 a 20 cycloalkenyl group, a substituted or unsubstituted heteroaralkyl group having 3 to 30 carbon atoms and a substituted or unsubstituted heteroalkenyl group 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 retarder 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-butyne-3-oxy)silane, tributylamine, tetramethylethylenediamine, benzotriazole, triphenylphosphine, sulfur-containing compound, hydroperoxy compound, maleic acid derivative-1 -ethynylcyclohexanol, 3-methyl-1-penten-3-ol and mixtures thereof
A composition for silicone release coating. According to claim 1,
The CNT dispersion is to contain 0.3 to 0.5 parts by weight of CNT and 0.3 to 0.5 parts by weight of the dispersant based on 100 parts by weight of the solvent
A composition for silicone release coating. base film; and
It includes a release layer formed on one surface of the base film,
The release layer is formed by coating the composition for a silicone release coating according to any one of claims 1 to 5
silicone release film. 7. The method of claim 6,
The release layer is a solvent, polydimethylsiloxane represented by the following formula (1); CNT dispersion, retarder and crosslinking agent uniformly dispersed main agent; And the catalyst is 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 to form a release layer
Silicone Release Film:
[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 each independently hydrogen, halogen, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 24 of an alkynyl group, a substituted or unsubstituted heteroalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, a 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 a 20 cycloalkenyl group, a substituted or unsubstituted heteroaralkyl group having 3 to 30 carbon atoms and a substituted or unsubstituted heteroalkenyl group 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.