KR20200036362A - Composition for release layer and release film comprising cured product of the same - Google Patents

Abstract

The present invention relates to a release film having suitable release peeling force, and to a composition for a release layer capable of implementing the same. The composition for a release layer comprises: a silicon-based resin containing a phenyl group; a silicon-based cross-linking agent; a silane coupling agent; a metal catalyst; and a solvent.

Description

A release film comprising a composition for a release layer and a cured product thereof {COMPOSITION FOR RELEASE LAYER AND RELEASE FILM COMPRISING CURED PRODUCT OF THE SAME}

The present invention relates to a release film comprising a composition for a release layer and a cured product thereof.

Release films are diversified fields such as liquid crystal displays, plasma displays, personal digital assistants and navigation, organic light emitting diodes, polymer light emitting diodes, polarizers, display unit fields, coating fields, adhesive fields, adhesive fields, etc. It is used in. Mainly, the release film may protect the surface of the target article, the surface of the adhesive, the surface of the adhesive, or the like, and may serve as a carrier of the target article. The release film is attached to the target product during the manufacturing process of the target product, transport and storage, but may be removed at the time of manufacture of the final product.

Recently, a paint protection film (PPF) has been used to protect the exterior of automobiles, and the demand for this is increasing. PPF is composed of a base material such as a polyurethane film and an adhesive layer. In order to manufacture PPF, a substrate such as a polyurethane film produced in a sheet form must be laminated with an adhesive layer, and a release film, which is a molding substrate, is used to manufacture the polyurethane film. However, when a base material, such as a polyurethane film used for PPF, is molded on a release film, a tunneling phenomenon such that the base material such as a polyurethane film itself does not have a tack or adhesive force and is quickly peeled from the release film occurs. When this phenomenon occurs, there is a problem that the quality as a PPF product decreases and the difficulty in manufacturing process increases. In addition, in order to prevent such a problem, in the case of forming a substrate on an untreated PET film that has not been subjected to a release treatment, there is a problem that the substrate cannot be easily peeled off and thus difficult to use as a product.

Accordingly, there is a need to develop a release film that is easy to manufacture films such as PPF.

The present invention is to provide a release film having a suitable release peel force and a composition for forming a release layer capable of implementing the same.

However, the problem to be solved by the present invention is not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

One embodiment of the present invention, a silicone-based resin containing a phenyl group; Silicone-based crosslinking agents; Silane coupling agents; Metal catalysts; And a solvent; and the content of the silicone-based crosslinking agent provides a composition for a release layer that is 1.5 parts by weight or more and 4.5 parts by weight or less with respect to 100 parts by weight of the silicone-based resin containing the phenyl group.

In addition, an exemplary embodiment of the present invention, the substrate; And it is provided on one surface of the substrate, and provides a release film comprising a release layer containing a cured product of the composition for the release layer.

The composition for a release layer according to an exemplary embodiment of the present invention has an appropriate release peel force, and can provide a release film suitable for production of films used in various fields.

The release film according to an exemplary embodiment of the present invention has an advantage that is suitable for the production of a film used in various fields, as it possesses an appropriate release peel force.

The effects of the present invention are not limited to the above-described effects, and effects not mentioned will be clearly understood by those skilled in the art from the present specification and the accompanying drawings.

In the present specification, when a part “includes” a certain component, this means that other components may be further included rather than excluding other components unless specifically stated to the contrary.

Throughout this specification, when a member is said to be "on" another member, this includes not only the case where one member abuts another member, but also the case where another member exists between the two members.

Throughout the present specification, the unit “parts by weight” may mean a ratio of weight between each component.

Throughout this specification, “A and / or B” means “A and B, or A or B”.

Throughout this specification, the “weight average molecular weight” and “number average molecular weight” of a compound can be calculated using the molecular weight and molecular weight distribution of the compound. Specifically, tetrahydrofuran (THF) and a compound are prepared in a 1 ml glass bottle to prepare a sample sample having a compound concentration of 1 wt%, and a standard sample (polystyrene, polystryere) and a sample sample are filtered (pore size). Is filtered through 0.45 mm), and injected into a GPC injector to compare the elution time of the sample sample with the calibration curve of the standard sample to obtain the molecular weight and molecular weight distribution of the compound. In this case, Infinity II 1260 (Agilient Co.) can be used as the measuring instrument, the flow rate can be set to 1.00 mL / min, and the column temperature can be set to 40.0 ° C.

Throughout the present specification, the number of moles of hydrogen bonded to silicon and the phenyl group bonded to silicon contained in the silicone-based resin is a graph measured using a nuclear magnetic resonance (NMR) device (Oxford 300 NMR, VARIAN). Can be calculated through

Throughout the present specification, the release peel force of the release layer is attached to the release layer by reciprocating three times with a 2Kg load on a Tesa7475 standard adhesive tape, and stored for a set time at a set temperature, followed by a measuring device (AR-1000, Chem). It may mean an average force for peeling the release layer measured according to the peeling rate using an instrument.

Throughout the present specification, the viscosity of the compound may be a value measured by a Brookfield viscometer (DV-II + PRO Viscometer, Brookfield Co.) at a temperature of 25 ° C.

Hereinafter, the present specification will be described in more detail.

One embodiment of the present invention, a silicone-based resin containing a phenyl group; Silicone-based crosslinking agents; Silane coupling agents; Metal catalysts; And a solvent; and the content of the silicone-based crosslinking agent provides a composition for a release layer that is 1.5 parts by weight or more and 4.5 parts by weight or less with respect to 100 parts by weight of the silicone-based resin containing the phenyl group.

The composition for a release layer according to an exemplary embodiment of the present invention has an appropriate release peel force, and can provide a release film suitable for production of films used in various fields. Specifically, the release film may be applied to a paint protection film (PPF) used as a vehicle exterior protection film.

In the present invention, the release film is used in automotive fields such as automotive exterior protective films, liquid crystal displays, plasma displays, personal digital assistants and navigation, organic light emitting diodes, polymer light emitting diodes, display unit fields such as polarizers, coatings, etc. Used in various fields such as the field of adhesive, the field of adhesive, and the field of adhesive, to protect the surface of the target product, the surface of the adhesive, the surface of the adhesive, etc., to serve as a carrier (carrier) of the target product, or to provide a predetermined film. It may be used as a base film for manufacturing and may mean a film capable of performing a role to be removed from the film. In addition, the release film may mean a film that is attached to the target product in the manufacturing process, transport and storage process of the target product, etc., but is removed during manufacture of the final product.

According to an exemplary embodiment of the present invention, the silicone-based resin containing the phenyl group may be a phenyl group bonded to a radical of a silicone skeleton. In addition, at least one of an unsaturated alkyl group, a saturated alkyl group, and hydrogen may be bound to the radical of the silicone skeleton of the silicone-based resin containing the phenyl group. Specifically, the silicone-based resin containing the phenyl group may contain a phenyl group, an unsaturated alkyl group, a saturated alkyl group and hydrogen.

In addition, the silicon skeleton may include a silicon atom and an oxygen atom, and a covalent bond may be formed through a bond between a radical of the silicon atom and a radical of the phenyl group. As described above, at least one of the unsaturated alkyl group, saturated alkyl group, and hydrogen may be bonded to the radical of the silicon skeleton. Further, the silicone skeleton may be linear or branched chain.

According to an exemplary embodiment of the present invention, the silicone-based resin containing the phenyl group may have a molar ratio of phenyl bonded to silicon and hydrogen bonded to silicon at 1: 1 to 1: 1.5. Specifically, in the silicone-based resin containing the phenyl group, the molar ratio of the phenyl group bonded to silicon and hydrogen bonded to silicon is 1: 1 to 1: 1.4, 1: 1 to 1: 1.3, or 1: 1.1 to 1: 1.3 Can be A composition for a release layer comprising a silicone-based resin containing the phenyl group in which the molar ratio of phenyl groups bonded to silicon and hydrogen bonded to silicon satisfies the above-described range is a release film comprising a release layer having appropriate surface energy and release peel force You can implement In the case of a release film formed from a release agent composition using a silicone-based resin containing only a conventional vinyl group, a tunneling phenomenon in which the film formed on the release film is easily peeled off from the release film occurs, or the film is not easily peeled from the release film. There was a problem in that it was not easy to control the release peel force of the release film.

On the other hand, according to an exemplary embodiment of the present invention, by using a silicone-based resin containing the phenyl group having a molar ratio of the phenyl group bonded to silicon and hydrogen bonded to silicon satisfying the above-described range, it has the appropriate release peel force and has been described above. The tunneling phenomenon and the phenomenon that the film is not peeled off from the release film can be effectively suppressed. That is, the composition for the release layer has an advantage of providing a release film having excellent performance as a release film. In particular, the release film containing the cured product of the composition for the release layer may be specialized in the production of paint protection films.

According to an exemplary embodiment of the present invention, the viscosity of the silicone-based resin containing the phenyl group may be 5,000 cps or more and 10,000 cps or less. Specifically, the viscosity measured at a temperature of 25 ° C, a humidity of 50 RH% and a frequency of 30 Hz of the silicone-based resin containing the phenyl group is 5,000 cps or more and 10,000 cps or less, 6,000 cps or more, 9,000 cps or less, or 7,000 cps or more and 8,500 cps or less. You can. The silicone-based resin containing the phenyl group having a viscosity in the aforementioned range is easy to mix with the silicone-based crosslinking agent, silane coupling agent, metal catalyst, and solvent, thereby providing a release film with homogeneous quality.

According to an exemplary embodiment of the present invention, the weight average molecular weight of the silicone-based resin containing the phenyl group may be 50,000 g / mol or more and 150,000 g / mol or less. Specifically, the weight average molecular weight of the silicone-based resin containing the phenyl group may be 70,000 g / mol or more and 140,000 g / mol or less, 85,000 g / mol or more, 135,000 g / mol or less, or 100,000 g / mol or more and 130,000 g / mol or less have. By adjusting the weight average molecular weight of the silicone-based resin containing the phenyl group to the aforementioned range, it is possible to effectively prevent the surface energy of the release layer containing the cured product of the release layer composition from being excessively high or low. Furthermore, when the weight average molecular weight of the silicone-based resin containing the phenyl group is within the above-described range, the release peel force of the release layer containing the cured product of the release layer composition can be implemented at an appropriate level.

According to an exemplary embodiment of the present invention, the content of the silicone-based resin containing the phenyl group may be 2.5 parts by weight or more and 15 parts by weight or less with respect to 100 parts by weight of the solvent. Specifically, the content of the silicone-based resin containing the phenyl group may be 5 parts by weight or more and 12.5 parts by weight or less, 7.5 parts by weight or more, 10 parts by weight or less, 8 parts by weight or more and 12 parts by weight or less based on 100 parts by weight of the solvent. By adjusting the content of the silicone-based resin containing the phenyl group to the above-described range, the composition for the release layer can be more easily cured. In addition, when the content of the silicone-based resin containing the phenyl group is within the above-described range, the release layer containing the cured product of the composition for the release layer may have appropriate surface energy and release peel force.

According to an exemplary embodiment of the present invention, the content of the silicone-based crosslinking agent is 1.5 parts by weight or more and 4.5 parts by weight or less, 2 parts by weight or more, 4 parts by weight or less, 1.5 parts by weight or more and 3.5 parts by weight or more based on 100 parts by weight of the silicone-based resin containing the phenyl group. It may be less than or equal to 2 parts by weight, less than or equal to 3.5 parts by weight, or greater than or equal to 2 parts by weight and less than or equal to 2.5 parts by weight. By adjusting the content of the silicone-based crosslinking agent to the above-described range, it is possible to effectively prevent the release peel force of the release layer from being excessively increased. Specifically, when the content of the silicone-based crosslinking agent is within the above-described range, even when the release film is stored for a long time under high temperature conditions, it can be suppressed that the release peel force of the release layer is significantly increased. In addition, it is possible to improve the durability of the release film containing a cured product of the composition for the release layer. Furthermore, when the content of the silicone-based crosslinking agent is within the above-described range, it is possible to prevent the curability of the release layer composition from being lowered. Therefore, the composition for release layer can suppress that the release performance of the release layer, that is, the peeling performance, is lowered.

According to an exemplary embodiment of the present invention, the silicone-based crosslinking agent may be used without limitation to be used in preparing a release agent composition in the art. For example, the silicone-based crosslinking agent is a polyorganohydrogen siloxane having at least two silicon atom-bonded hydrogen atoms in one molecule, specifically dimethylhydrogensiloxy group terminal blockage dimethylsiloxane-methylhydrogensiloxane copolymer, trimethyl Siloxy group terminal block dimethylsiloxane-methylhydrogensiloxane copolymer, trimethylsiloxy group terminal block poly (methylhydrogensiloxane), poly (hydrogensilsesquioxane), and methylhydrogen siloxane. However, the type of the silicone-based crosslinking agent is not limited. In the present invention, methylhydrogen siloxane can be used as a silicone-based crosslinking agent.

According to an exemplary embodiment of the present invention, the content of the silane coupling agent may be 1.5 parts by weight or more and 4.5 parts by weight or less with respect to 100 parts by weight of the silicone-based resin containing the phenyl group. Specifically, the content of the silane coupling agent may be 2 parts by weight or more and 4 parts by weight or less, 2 parts by weight or more and 3 parts by weight or less, or 1.5 parts by weight or more and 3 parts by weight or less based on 100 parts by weight of the silicone-based resin containing the phenyl group have. By adjusting the content of the silane coupling agent to the above-described range, the durability of the release layer can be improved, and the phenomenon that the film provided in the release layer is not peeled off can be effectively prevented.

According to an exemplary embodiment of the present invention, the silane coupling agent used in the art to prepare a release agent composition can be employed without limitation. For example, the silane coupling agent may include at least one of an amino-based silane coupling agent, an epoxy-based silane coupling agent, and a mercapto-based silane coupling agent. In addition, the silane coupling agent, vinyl trimethoxysilane, vinylphenyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, γ-methacryloxypropyl trimethoxysilane, γ-glycidoxypropyl tree Methoxysilane, 4-glycidylbutyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3- Aminopropoxy) phthaloxy) propyl-3-aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, γ-mercaptopropyltrimethoxysilane, and vinyl trimethoxy silane. However, the type of the silane coupling agent is not limited to those described above. In the present invention, vinyl trimethoxy silane can be used as the silane coupling agent. Moreover, as said silane coupling agent, 2 or more types of silane coupling agents can be mixed and used.

According to an exemplary embodiment of the present invention, the content of the metal catalyst may be 3 parts by weight or more and 9.5 parts by weight or less with respect to 100 parts by weight of the silicone-based resin containing the phenyl group. Specifically, the content of the metal catalyst is 3 parts by weight or more and 9.5 parts by weight or less, 3.5 parts by weight or more, 9 parts by weight or less, 4 parts by weight or more, 8 parts by weight or less, or 5 parts by weight based on 100 parts by weight of the silicone resin containing the phenyl group It may be greater than or equal to 6.5 parts by weight. Specifically, the metal catalyst serves to promote the curing reaction of the silicone-based resin containing the phenyl group and the silicone-based crosslinking agent, and by adjusting the content of the metal catalyst to the above-described range, the composition for the release layer is uncured Alternatively, over-curing can be effectively suppressed.

According to an exemplary embodiment of the present invention, as the metal catalyst, those used in preparing a release agent composition in the art can be used without limitation. Specifically, the metal catalyst may include at least a platinum-based catalyst. Further, the platinum-based catalyst may include at least one of particulate platinum, particulate platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, and olefin complexes of chloroplatinic acid, but the type of the platinum-based catalyst It is not limited. In the present invention, PL-50T of Shin-Etsu Silicone Co., Ltd. may be used as the platinum-based catalyst.

According to an exemplary embodiment of the present invention, the solvent may be at least one of toluene, xylene, hexane, heptane, methyl ethyl ketone and ethyl acetate. However, the present invention is not limited thereto, and may be freely selected from organic solvents generally known in the art.

According to an exemplary embodiment of the present invention, the solid content of the composition for the release layer may be 0.5% or more and 30% or less. Specifically, the solid content of the composition for the release layer is 1% or more, 25% or less, 5% or more, 20% or less, 10% or more, 15% or less, 1% or more, 5% or less, 8% or more, 15% or less, or 20% or more 28% or less.

According to an exemplary embodiment of the present invention, by controlling the solid content of the composition for the release layer to the above-described range, the composition for the release layer can be easily applied. In addition, it is possible to prevent the viscosity from rapidly increasing upon curing of the composition for a release layer, thereby preventing the wettability during application from deteriorating. Specifically, when the solid content of the composition for the release layer is within the above-mentioned range, the content of the phenyl group-containing silicone-based resin contained in the composition for the release layer is relatively small, thereby preventing the durability of the cured product of the composition for the release layer from deteriorating. . In addition, when the composition for a release layer is cured, the viscosity rapidly increases, and the surface flatness of the cured product can be effectively suppressed.

According to an exemplary embodiment of the present invention, the composition for a release layer may further include other additives including at least one of a release agent, silica particles, and a photoinitiator. However, the type of other additives is not limited, and a known configuration used in the art may be used.

According to an exemplary embodiment of the present invention, the composition for the release layer may be cured through photocuring or thermal curing. Specifically, the composition for the release layer may be thermally cured, and the heat curing of the composition for the release layer may be performed at a temperature of 100 ° C. or higher and 180 ° C. or lower, for a period of 30 seconds to 180 seconds. By controlling the curing temperature and curing time of the composition for the release layer to the above-described range, the composition for the release layer can be stably cured to improve the durability of the cured product.

One embodiment of the present invention, the description; And it is provided on one surface of the substrate, and provides a release film comprising a release layer containing a cured product of the composition for the release layer.

The release film according to an exemplary embodiment of the present invention has an advantage that is suitable for the production of a film used in various fields, as it possesses an appropriate release peel force.

According to an exemplary embodiment of the present invention, the release film includes a release layer and a substrate, and the release layer may include a cured product of the composition for the release layer.

According to one embodiment of the present invention, by applying and curing the composition for a release layer on one surface of the substrate, it is possible to provide a release film comprising a release layer provided on one surface of the substrate. As a method of applying the composition for the release layer on one surface of the substrate, a known process can be used. Specifically, an inkjet printing process, a dispensing process, a silk screen process, a spray coating process, a spin coating process, a knife coating process, a dip coater coating process, a Meyer bar coating process, a gravure coating process, a micro gravure coating process, etc. may be used. .

According to an exemplary embodiment of the present invention, the substrate includes at least one of polyethylene resin, polyethylene terephthalate resin, polyether ether ketone resin, polyimide resin, polypropylene resin, stretched polypropylene resin, cellulose and polyvinyl chloride resin However, the type of the substrate is not limited.

According to an exemplary embodiment of the present invention, the thickness of the substrate may be 5 μm or more and 200 μm or less. The release film including a substrate having a thickness in the aforementioned range may have excellent durability.

According to an exemplary embodiment of the present invention, the release layer may have a thickness of 0.01 μm or more and 10 μm or less. The release film including a release layer having a thickness in the above-described range may have a suitable release peel force.

According to an exemplary embodiment of the present invention, the release layer may satisfy Equation 1 below.

[Equation 1]

20% ≤ {(X-Y) / Y} x 100 ≤ 35%

In Equation 1, X is the release layer attached to the Tesa7475 standard adhesive tape, the release force of the release layer after storage at 25 ℃ for 1 day, Y is the release layer attached to the Tesa7475 standard adhesive tape, 60 It means the release peel force of the release layer after storage at 7 ° C for 7 days.

That is, the release layer of the release layer (initial release force) stored at 25 ° C. for 7 days at 60 ° C. after the heat release treatment (after heat treatment) Release release force) may be 20% or more and 35% or less. Specifically, the amount of change of the release peel force after heat treatment for the initial release peel force may be 22% or more and 34% or less, 20% or more and 25% or less, or 30% or more and 35% or less. The release peel force including the release layer satisfying the above-described range of the amount of change of the release peel force after heat treatment for the initial release peel force has an advantage of maintaining the release performance at an appropriate level even under high temperature conditions. That is, the release film may be exposed to various conditions after being provided in the actual product, and particularly, even when exposed to high temperature conditions, the release film can realize an appropriate level of release performance.

In addition, when the amount of change of the release peel force after heat treatment for the initial release peel force satisfies the above-mentioned range, it can be confirmed that the unreacted compound remaining in the release layer is small, and the quality of the release layer is uniformly implemented. have.

According to an exemplary embodiment of the present invention, the release peel force of the release layer is 0.3 m under a humidity condition of 50 RH% after attaching the release layer to a Tesa7475 standard adhesive tape and storing the release film for a set temperature and time. / min peel rate and 180 ° peel angle may be measured.

According to an exemplary embodiment of the present invention, the release layer of the release layer after attaching the release layer to the Tesa7475 standard adhesive tape and storing at 25 ° C. for 1 day may be 500 gf / in or more and 1,250 gf / in or less. Since the release film containing the release layer having a release release force after storage at 25 ° C. for one day satisfies the above-described range has an appropriate level of release release force, the film formed on the release layer has a tunneling phenomenon and no Peeling phenomenon can be suppressed.

According to one embodiment of the present invention, the release layer of the release layer after attaching the release layer to the Tesa7475 standard adhesive tape and storing at 60 ° C. for 7 days may be 1,200 gf / in or more and 1,650 gf / in or less. The release film comprising the release layer that satisfies the above-described release release force after storage at 60 ° C. for 7 days has an advantage of realizing excellent release performance even under high temperature conditions. That is, even in a high temperature condition, the film formed on the release layer can be suppressed from tunneling and unpeeling.

According to an exemplary embodiment of the present invention, the surface energy of the release layer may be 25 mN / m or more and 35 mN / m or less. The release film in which the surface energy of the release layer satisfies the above-described range may have an appropriate level of release peel force.

According to an exemplary embodiment of the present invention, the release film may be applied to a paint protection film. Specifically, the release film may be applied to the manufacturing process of the paint protection film and the process of transporting the paint protection film. More specifically, a polyurethane resin composition capable of forming a base film of a paint protection film on a release layer of the release film is applied, and the polyurethane resin composition is cured to form a polyurethane resin layer (paint on the release layer). Protection film). Thereafter, since the release layer has an appropriate release peel force, the substrate of the paint protection film is suppressed from being generated from the release layer and the tunneling phenomenon, and the substrate of the paint protection film can be easily removed. It can be peeled from the release layer.

Hereinafter, examples will be described in detail to specifically describe the present invention. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present invention to those skilled in the art.

Preparation of release film

Example  One

Using a Brookfield viscometer (DV-II ⁺ PRO Viscometer, Brookfield Co.) as a viscosity meter, the viscosity measured at a temperature of 25 ° C, a humidity of 50 RH% and a frequency of 30 Hz is 7,000 cps, and the weight average measured by the aforementioned method. Molecular weight of 100,000 g / mol, silicone-based resin (Shin-Etsu Silicone Co., Ltd.) containing a phenyl group having a molar ratio of phenyl group (Si-Ph) bound to silicon and hydrogen (Si-H) bonded to silicon 1: 1.1, silicone-based crosslinking agent ( X-92-122, Shin-Etsu Silicon Co.), a silane coupling agent (X-92-158, Shin-Etsu Silicon Co.), a platinum-based catalyst (PL-50T, Shin-Etsu Silicon Co.), and toluene as a solvent were prepared.

Thereafter, the content of the silicone-based resin containing a phenyl group with respect to 100 parts by weight of toluene is 10 parts by weight, the content of the silicone-based crosslinking agent is 2 parts by weight, 2 parts by weight of the silane coupling agent, based on 100 parts by weight of the silicone-based resin containing the phenyl group, A composition for a release layer containing 5 parts by weight of a platinum-based catalyst was prepared.

Thereafter, the prepared release layer composition was applied to a polyethylene terephthalate substrate having a thickness of 50 μm using a Meyer Bar No. 8 to a thickness of 2.5 g / m ² . Thereafter, the composition for the release layer applied on the substrate was cured at 150 ° C for 1 minute, and then aged at 50 ° C for 24 hours to prepare a release film.

Example  2 to Example  3

A silicone-based resin containing a phenyl group as shown in Table 1 was prepared, and a composition for a release layer containing a silicone-based resin containing a phenyl group, a silicone-based crosslinking agent, a silane coupling agent, and a platinum-based catalyst was prepared as shown in Table 2 above. A release film was prepared in the same manner as in Example 1.

At this time, in Example 3, the silicone-based resin containing the phenyl group prepared in Example 1 was used. In addition, in Example 2, the content of the silicone-based resin containing a phenyl group with respect to 100 parts by weight of toluene was 10 parts by weight, and in Example 3, the content of a silicone-based resin containing a phenyl group with respect to 100 parts by weight of toluene was 5 parts by weight.

Silicone-based resin containing phenyl group Viscosity
(cps) Molecular Weight
(g / mol) Si-Ph: Si-H Example 1 7,000 100,000 1: 1.1 Example 2 8,500 130,000 1: 1.3 Example 3 7,000 100,000 1: 1.1

Phenyl containing
Silicone resin
(Parts by weight) Silicone-based crosslinking agent
(Parts by weight) Silane coupling agent
(Parts by weight) Platinum catalyst
(Parts by weight) Solids
(%) Example 1 100 2 2 5 2.8 Example 2 100 2 2 5 2.9 Example 3 100 2 2 5 3.1

In Table 2, the content of the silicone-based crosslinking agent, silane coupling agent, and platinum-based catalyst is based on 100 parts by weight of the silicone-based resin containing a phenyl group.

Comparative example  1 to Comparative example  6

Prepare a silicone-based resin containing a vinyl group without containing a phenyl group as shown in Table 3, and containing a silicone-based resin containing a vinyl group without containing a phenyl group, a silicone-based crosslinking agent, a silane coupling agent, a platinum-based catalyst as shown in Table 4 below. A release film was prepared in the same manner as in Example 1, except that the composition for a release layer was prepared.

At this time, in Comparative Examples 1 to 6, the content of the silicone-based resin containing no phenyl group and containing a vinyl group with respect to 100 parts by weight of toluene was 10 parts by weight.

Silicone-based resin containing no phenyl group and vinyl group Viscosity
(cps) Molecular Weight
(g / mol) Si-Vi: Si-H Comparative Example 1 15,000 400,000 1: 1 Comparative Example 2 12,000 300,000 1: 2 Comparative Example 3 15,000 300,000 1: 0.7 Comparative Example 4 2,000 100,000 1: 0.5 Comparative Example 5 4,000 200,000 1: 1 Comparative Example 6 500 200,000 1: 2

Silicone-based resin containing no phenyl group and vinyl group
(Parts by weight) Silicone-based crosslinking agent
(Parts by weight) Silane coupling agent
(Parts by weight) Platinum catalyst
(Parts by weight) Solids
(%) Comparative Example 1 100 2 2 5 2.9 Comparative Example 2 100 2 2 5 3.1 Comparative Example 3 100 2 2 5 3.2 Comparative Example 4 100 2 2 5 2.9 Comparative Example 5 100 2 2 5 2.8 Comparative Example 6 100 2 2 5 3.0

In Table 4, the content of the silicone-based crosslinking agent, silane coupling agent, and platinum-based catalyst is based on 100 parts by weight of the silicone-based resin containing a phenyl group.

Comparative example  7 to Comparative example  16

In Comparative Examples 7 to 16, silicone-based resins containing phenyl groups prepared in Example 1 were used. A release film was prepared in the same manner as in Example 1, except that a composition for a release layer containing a silicone-based resin containing a phenyl group, a silicone-based crosslinking agent, a silane coupling agent, and a platinum-based catalyst was prepared as shown in Table 5 below.

At this time, the content of the silicone-based resin containing a phenyl group with respect to 100 parts by weight of toluene in Comparative Examples 7 to 16 was 10 parts by weight.

Phenyl containing
Silicone resin
(Parts by weight) Silicone-based crosslinking agent
(Parts by weight) Silane coupling agent
(Parts by weight) Platinum catalyst
(Parts by weight) Solids
(%) Comparative Example 7 100 One 2 5 2.9 Comparative Example 8 100 5 2 5 3.0 Comparative Example 9 100 2 One 5 3.1 Comparative Example 10 100 2 5 5 2.9 Comparative Example 11 100 2 2 2.5 2.8 Comparative Example 12 100 2 2 10 3.0 Comparative Example 13 100 One One 5 3.1 Comparative Example 14 100 One 5 5 3.0 Comparative Example 15 100 5 One 5 3.1 Comparative Example 16 100 5 5 5 2.9

Evaluation of release film properties

Surface energy measurement

The surface energies of the release films prepared in Examples 1 to 3 and Comparative Examples 1 to 16 were measured as follows. 1 mL of deionized water, a solvent for measuring surface energy, is dropped onto a release film at a rate of 1 uL / s, and the contact angle of the measurement solvent is measured using a measuring device (OCA20, Dataphysics), and the release film is used. The surface energy was calculated. Table 6 shows the surface energy values measured by the above method.

Release Peeling force  Measure

The release peel forces of the release films prepared in Examples 1 to 3 and Comparative Examples 1 to 16 were measured as follows.

The release layer of the release film is attached to the Tesa7475 standard adhesive tape by reciprocating three times with a load of 2Kg, stored for 1 day at 25 ° C and 50 RH% atmosphere, and then measured at 25 ° C and 50 RH% atmosphere (AR-1000 , Chem Instruments, to measure the release peel force. With respect to the sample size of 50 × 1,500 mm and the peeling force measurement size of 250 × 1,500 mm, it was performed under a 180 ° peeling angle, and the average value of 5 repeated measurements was obtained to obtain a release force (gf / in).

In addition, the release layer of the release film was attached to the Tesa7475 standard adhesive tape by reciprocating three times with a load of 2Kg, stored for 7 days at 60 ° C and 50 RH% atmosphere, and then measured at 25 ° C and 50 RH% atmosphere (AR -1000, Chem Instruments) was used to measure the release force. With respect to the sample size of 50 × 1,500 mm and the peeling force measurement size of 250 × 1,500 mm, it was performed under a 180 ° peeling angle, and the average value of 5 repeated measurements was obtained to obtain the release peel force (gf / in).

Release force of the release layer after storage at 25 ° C for 1 day measured through the method described above (initial release force) and release force of the release layer after storage at 60 ° C for 7 days (release force after heat treatment) , And the amount of change in the release peel force after heat treatment for the initial release peel force is shown in Table 6 below.

Release layer  Measurement of adhesion of substrate (Rub-off test)

The adhesion between the release layer of the release film prepared in Examples 1 to 3 and Comparative Examples 1 to 16 and the substrate was measured as follows.

After releasing the release layer of the release film with your finger removed, rub it over 1, 3, 5, 10, 10 times or more, and then paint the release layer with an oil-based pen. At this time, when the ink of the oil-based pen is applied to the release layer, it means that the adhesion between the release layer and the substrate is inferior. Specifically, if the ink of the oil pen is smeared in 1 time, X, the ink of the oil pen is smeared in 3 times, △ ~ X, if the ink of the oil pen is smeared in 5 times, △, the ink of the oil pen is smeared in 10 times After ○ ~ △, even if it exceeds 10 times, it is judged as ○ if the ink of the oil-based pen does not come out, it is shown in Table 6 below.

Tunneling  Measure

The tunneling phenomenon of the release layer of the release films prepared in Examples 1 to 3 and Comparative Examples 1 to 16 was measured as follows.

After cutting the release films prepared in Examples 1 to 3 and Comparative Examples 1 to 16 to 50 mm in width and 1,500 mm in length, the release layer of the release film was Tesa7475 3 times with 2Kg load on a standard adhesive tape. Samples were prepared by attaching by reciprocating pressing, and stored at 25 ° C. and 50 RH% atmosphere for 1 day. Thereafter, after the sample was deformed so that the sample had a radius of curvature of about 5 R, it was confirmed whether the release layer of the release film was lifted.

At this time, the case where the release layer is lifted immediately, X when the release layer is not lifted within 10 seconds, △ ~ X, when the release layer is not lifted within 60 minutes, △, when the release layer is not lifted within 3 days ○ ~ (Triangle | delta), when the release layer exceeds 7 days, it is judged as (circle) and it is shown in Table 6 below.

Unexploited  Measure

The unpeeling phenomenon of the release layer of the release films prepared in Examples 1 to 3 and Comparative Examples 1 to 16 was measured as follows.

After cutting the release films prepared in Examples 1 to 3 and Comparative Examples 1 to 16 to 50 mm in width and 1,500 mm in length, the release layer of the release film was Tesa7475 3 times with 2Kg load on a standard adhesive tape. Samples were prepared by attaching by reciprocating pressing, and stored at 25 ° C. and 50 RH% atmosphere for 1 day. Subsequently, using a measuring device (AR-1000, Chem Instruments Co., Ltd.), for the peel force measurement size of 250 × 1,500 mm, an experiment was performed in which the release layer was peeled from the Tesa7475 standard adhesive tape under a 180 ° peel angle.

At this time, through the process of peeling the release layer of the release film from the produced sample, it was possible to confirm the peeling properties of the release layer. Δ, the case where the release layer was not peeled even through the above method was judged as X, and is shown in Table 6 below.

surface
energy
(mN / M) Release peel force Rub-off Tunneling Unreleased Early release
Peeling force
(gf / in) After heat treatment
Release peel force
(gf / in) Amount of change
(%) Example 1 29.5 1001.6 1221.1 22 ○ ○ ○ Example 2 26.3 531.2 678.1 28 ○ ~ △ ○ ~ △ ○ Example 3 32.3 1211.5 1626.6 34 ○ ○ △ Comparative Example 1 20.1 10.3 12.1 17 ○ X ○ Comparative Example 2 21.3 17.7 21.1 19 ○ X ○ Comparative Example 3 22.1 23.1 31.3 35 ○ X ○ Comparative Example 4 18.7 15.6 16.1 3 ○ ~ △ X ○ Comparative Example 5 21.1 56.1 77.7 38.5 ○ ~ △ X ○ Comparative Example 6 20.5 103 121.1 18 ○ ~ △ X ○ Comparative Example 7 26.4 678.1 1735.5 156 ○ ~ △ ○ ~ △ △ Comparative Example 8 31.1 1189.3 1823.3 53 ○ ○ △ Comparative Example 9 28.8 1056.6 1195.5 13 △ ○ △ Comparative Example 10 28.9 1087.4 1200.0 10 ○ ○ △ Comparative Example 11 26.1 881.3 1562.2 77 △ ~ X ○ ~ △ X Comparative Example 12 31.5 1211.2 1278.3 6 ○ ~ △ ○ △ Comparative Example 13 27.1 653.0 1564.4 140 △ ~ X ○ ~ △ X Comparative Example 14 26.9 678.3 1773.1 161 △ ○ ~ △ X Comparative Example 15 30.0 1211.3 1671.3 38 △ ~ X ○ △ Comparative Example 16 30.7 1278.8 1900.3 49 ○ ○ △

Referring to Table 1, Table 2, and Table 6, Example 1 in which a silicone-based resin containing a phenyl group was used, and the content of the silicone-based crosslinking agent was 1.5 parts by weight or more and 4.5 parts by weight or less with respect to 100 parts by weight of a silicone-based resin containing a phenyl group. The release layer formed from the composition for a release layer according to Example 6 has a suitable surface energy, satisfies 20% to 35% of the change in release release force after heat treatment compared to the initial release release force, rub-off test, tunneling, and beauty As a result of the peeling test, it was confirmed to have excellent quality. On the other hand, in the case of the release layers of Comparative Examples 1 to 6 using a silicone-based resin containing no phenyl group and containing a vinyl group, the release strength after the heat treatment compared to the initial release strength The amount of change did not satisfy 20% to 35%, and the tunneling test confirmed that it had very inferior quality.

In addition, in the case of the release layers of Comparative Examples 7 and 8 that did not satisfy the range of 1.5 parts by weight or more and 4.5 parts by weight or less with respect to 100 parts by weight of the silicone-based resin containing the phenyl group, compared with the initial release peel force It was confirmed that the amount of change of the release peel force after heat treatment did not satisfy 20% to 35%, and the unreleased test result showed that the quality was inferior to the release layers of Examples 1 to 3 of the present invention.

In addition, in the case of the release layer of Comparative Example 9 and Comparative Example 10 in which the content of the silane coupling agent does not satisfy the range of 1.5 parts by weight or more and 4.5 parts by weight or less with respect to 100 parts by weight of the silicone resin containing a phenyl group, initial release peel force It was confirmed that the change amount of the release peel force after the contrast heat treatment did not satisfy 20% to 35%, and the quality of the release layer of Examples 1 to 3 of the present invention was inferior to that of the Rub-off test and unreleased test.

In addition, in the case of the release layers of Comparative Examples 11 and 12 that do not satisfy the range of 3 parts by weight or more and 9.5 parts by weight or less with respect to 100 parts by weight of the silicone-based resin containing a phenyl group, the initial release peel force The amount of change in the release peel force after the contrast heat treatment did not satisfy 20% to 35%, and the quality of the inferior quality of the release layers of Examples 1 to 3 of the present invention was inferior to the Rub-off test, tunneling test, and unreleased test result. Confirmed.

In addition, in the case of the release layers of Comparative Examples 13 to 16, wherein the content of the silicone-based crosslinking agent and the silane coupling agent does not satisfy the range of 1.5 parts by weight or more and 4.5 parts by weight or less with respect to 100 parts by weight of the silicone-based resin each containing a phenyl group, Compared to the initial release peel force, the amount of change of the release peel force after heat treatment does not satisfy 20% to 35%, and the rub-off test, tunneling test, and unreleased test result show that the release layer of Examples 1 to 3 of the present invention is less than the release layer. It was confirmed that the quality was inferior.

Therefore, it can be seen that the composition for a release layer according to an exemplary embodiment of the present invention has an appropriate release peel force and can provide a release film suitable for the production of films used in various fields.

Claims (12)

Silicone-based resins containing phenyl groups; Silicone-based crosslinking agents; Silane coupling agents; Metal catalysts; And a solvent;
The content of the silicone-based crosslinking agent is 1.5 parts by weight or more and 4.5 parts by weight or less based on 100 parts by weight of the silicone-based resin containing the phenyl group.
The method according to claim 1,
The content of the silane coupling agent is a composition for a release layer that is 1.5 parts by weight or more and 4.5 parts by weight or less with respect to 100 parts by weight of the silicone-based resin containing the phenyl group.
The method according to claim 1,
The content of the metal catalyst is 3 parts by weight or more and 9.5 parts by weight or less based on 100 parts by weight of the silicone resin containing the phenyl group.
The method according to claim 1,
The content of the silicone-based resin containing the phenyl group is 1 part by weight or more and 15 parts by weight or less based on 100 parts by weight of the solvent.
The method according to claim 1,
The silicone-based resin containing the phenyl group, a composition for a release layer having a molar ratio of phenyl group bonded to silicon and hydrogen bonded to silicon is 1: 1 to 1: 1.5.
The method according to claim 1,
The viscosity of the silicone-based resin containing the phenyl group is 5,000 cps or more and 10,000 cps or less.
The method according to claim 1,
The weight average molecular weight of the silicone-based resin containing the phenyl group, the release layer composition of 50,000 g / mol or more and 150,000 g / mol or less.
materials; And
A release film comprising; provided on one side of the substrate, and a release layer comprising a cured product of the release layer composition according to claim 1.
The method according to claim 8,
The release layer is a release film that satisfies Equation 1 below:
[Equation 1]
20% ≤ {(X-Y) / Y} x 100 ≤ 35%
In Equation 1,
X is the release peel force of the release layer after attaching the release layer to the Tesa7475 standard adhesive tape and storing at 25 ° C for 1 day,
Y means the release force of the release layer after the release layer is attached to the Tesa7475 standard adhesive tape and stored at 60 ° C for 7 days.
The method according to claim 8,
A release film having a release force of 500 gf / in or more and 1,250 gf / in or less after the release layer is attached to a Tesa7475 standard adhesive tape and stored at 25 ° C for 1 day.
The method according to claim 8,
A release film having a release force of 1,200 gf / in or more and 1,650 gf / in or less after the release layer is attached to a Tesa7475 standard adhesive tape and stored at 60 ° C for 7 days.
The method according to claim 8,
The release layer has a surface energy of 25 mN / m or more and 35 mN / m or less.