KR102240076B1 - Release composition and release film comprising release layer comprising cured product of the same - Google Patents

Abstract

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

Description

A release film comprising a release layer including a release composition and a cured product thereof TECHNICAL FIELD [RELEASE COMPOSITION AND RELEASE FILM COMPRISING RELEASE LAYER COMPRISING CURED PRODUCT OF THE SAME}

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

Release films are in various fields such as liquid crystal displays, plasma displays, personal digital assistants and navigation, organic light emitting diodes, polymer light emitting diodes, display units such as polarizers, coatings, adhesives, and adhesives. It is being used in. Mainly, the release film may protect the surface of the target article, the surface of the pressure-sensitive adhesive, the surface of the adhesive, or the like, or may serve as a carrier of the target article. The release film is attached to the target article during the manufacturing process, transportation, and storage process of the target article, but may be removed during the manufacture of the final article.

The release film may require a variety of release peeling force required according to the application object, and there is a problem in that a release layer having a release peeling force suitable for each application object must be separately developed.

Therefore, there is a need for research on a release layer of a release film capable of controlling the release peeling force.

Korean Patent Publication No. 10-2009-0022722

The present invention is to provide a release film comprising a release layer including a release composition and a cured product thereof.

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

An exemplary embodiment of the present invention is a silicone compound; Hardener; And a photoinitiator comprising at least one photopolymerization functional group of a benzophenone-based functional group, a quinone-based functional group, and a thioxanthone-based functional group.

Another exemplary embodiment of the present invention provides a release film including a release layer including a cured product of the release composition.

The release film according to an exemplary embodiment of the present invention has the advantage of being able to adjust the release peeling force according to the attached substrate.

The release layer of the release film according to an exemplary embodiment of the present invention has an advantage that can be further cured.

The release film according to an exemplary embodiment of the present invention has an advantage that can be applied to various members since the release peeling force can be adjusted according to the above-described additional curing.

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

In the present specification, the term "monomer polymerization unit" may refer to a form in which the monomer undergoes a polymerization reaction to form a skeleton, for example, a main chain or a side chain of the polymer.

In the present specification, the term "(meth)acrylate" may mean acrylate or methacrylate.

In the present specification, the unit "part by weight" may mean a ratio of weight between each component.

In the present specification, the content of the unsaturated alkyl group included in the silicone compound may mean a molar fraction of the number of moles of the unsaturated alkyl group included in the silicone compound to the total number of moles of the unsaturated alkyl group, saturated alkyl group, and hydrogen included in the silicone compound.

In the present specification, the number of moles of unsaturated alkyl group, saturated alkyl group, and hydrogen contained in the silicone compound may be a value measured through a graph measured using NMR (Nuclear Magnetic Resonance, Oxford 300 NMR, VARIAN Corporation).

In the present specification, the term "functional group" may refer to a common atomic group or bonding pattern of a group of organic compounds having common chemical properties.

In the present specification, the term "saturated alkyl group" may include a functional group including a single bonded hydrocarbon in a chain and/or branched form, and specifically may mean a functional group including an alkyl group having 1 to 20 carbon atoms.

In the present specification, the term "unsaturated alkyl group" may refer to a functional group including a hydrocarbon having one or more double bonds or triple bonds, and is bonded in a chain and/or branched form, and specifically, an egg having 1 to 20 carbon atoms. It may mean a functional group including a kenyl group.

In the present specification, the term "solid content" may mean a solid nonvolatile material, and the solid content of the release composition may mean the content of the residue after drying the release composition.

In the present specification, the term "viscosity" means a value measured by a viscometer (DV-II+, PRO Viscometer, manufactured by Brookfield) at 25° C. temperature, 50 RH% relative humidity, and 30 Hz frequency conditions.

The present inventors found that the conventional release film had a problem that the release peeling force could not be adjusted naturally, and the result of repeated research on the composition for a release film that can be applied to various members by controlling the release peeling force acquired , Came to the present invention.

Specifically, the present inventors applied a photoinitiator containing at least one photopolymerization functional group among a benzophenone-based functional group, a quinone-based functional group, and a thioxanthone-based functional group to a silicone-based release composition for preparing a release film, further curing by light irradiation. It was possible, and it was confirmed that the release force was increased, and the present invention was completed.

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

An exemplary embodiment of the present invention is a silicone compound; Hardener; And a photoinitiator comprising at least one photopolymerization functional group of a benzophenone-based functional group, a quinone-based functional group, and a thioxanthone-based functional group.

According to an exemplary embodiment of the present invention, the silicone compound is a main material of the release composition, and may mean a compound capable of imparting release properties to a release layer prepared using the release composition.

According to an exemplary embodiment of the present invention, the silicone compound may be an unsaturated alkyl group, a saturated alkyl group, and hydrogen bonded to a silicone skeleton. Specifically, the silicon skeleton may be a linear or branched chain, and the silicon skeleton may include a silicon atom and an oxygen atom.

According to an exemplary embodiment of the present invention, the silicone compound may include an unsaturated alkyl group, a saturated alkyl group, and hydrogen bonded to the silicone skeleton. Specifically, the silicone compound may substantially consist of a silicone skeleton, an unsaturated alkyl group, a saturated alkyl group, and hydrogen.

The fact that the silicone compound is substantially composed of a silicone skeleton, an unsaturated alkyl group, a saturated alkyl group, and hydrogen means that other components other than silicone, unsaturated alkyl group, saturated alkyl group and hydrogen are not bonded to the silicone skeleton at all or are partially bonded to other components. Compared to that, the content is very insignificant, and thus it may mean a case including an amount that is negligible as a composition component of the silicone compound.

In addition, the unsaturated alkyl group, saturated alkyl group, and hydrogen may be chemically bonded to a silicon atom constituting the silicon skeleton.

According to an exemplary embodiment of the present invention, the unsaturated alkyl group may be a vinyl (vinyl) group or a hexenyl (hexenyl) group. Specifically, the silicone compound may include at least one of a vinyl group and a hexenyl group. In the case of including a silicone compound containing at least one of a vinyl group and a hexenyl group as an unsaturated alkyl group, a release composition capable of stably reacting with a curing agent and a photoinitiator can be provided.

According to an exemplary embodiment of the present invention, the hexenyl group 1-hexenyl (1-hexenyl), 2-hexenyl (2-hexenyl), 3-hexenyl (3-hexenyl), 4-hexenyl (4- hexenyl) and 5-hexenyl.

According to an embodiment of the present invention, the saturated alkyl group may be a linear or branched alkyl group having 1 to 6 carbon atoms. Specifically, the saturated alkyl group may be a methyl group.

According to an exemplary embodiment of the present invention, the content of the unsaturated alkyl group in the silicone compound is 2 mol% or more and 5 mol% or less, 2.5 mol% or more and 4.5 mol% or less with respect to the total number of moles of the unsaturated alkyl group, saturated alkyl group, and hydrogen, It may be 3 mol% or more and 4.5 mol% or less, 3.5 mol% or more and 4 mol% or less, 2 mol% or more and 3 mol% or less, 3 mol% or more and 4 mol% or less, or 3.5 mol% or more and 5 mol% or less.

When the content of the unsaturated alkyl group is within the above range, the silicone compound can stably react with the curing agent and/or the photoinitiator, and the release peel force of the release layer prepared using the release composition can be appropriately adjusted. have.

According to an exemplary embodiment of the present invention, the content of the saturated alkyl group in the silicone compound is 70 mol% or more and 90 mol% or less, 70 mol% or more and 86 mol% or less with respect to the total number of moles of the unsaturated alkyl group, saturated alkyl group and hydrogen, 70 mol% or more and 85 mol% or less, 70 mol% or more and 83 mol% or less, 75 mol% or more and 90 mol% or less, 75 mol% or more and 86 mol% or less, 75 mol mol% or more and 85 mol% or less, 75 mol% or more 83 mol% or less, 80 mol% or more and 90 mol% or less, 80 mol% or more and 86 mol% or less, 80 mol% or more and 85 mol% or less, 80 mol% or more and 83 mol% or less, 83 mol% or more and 90 mol% or less, It may be 83 mol% or more and 86 mol% or less, or 83 mol% or more and 85 mol% or less.

When the content of the saturated alkyl group is within the above range, the silicone compound can stably react with the curing agent and/or the photoinitiator, and the release peeling force of the release layer prepared using the release composition can be appropriately adjusted. have.

According to an exemplary embodiment of the present invention, the content of hydrogen in the silicone compound is 5 mol% or more and 25 mol% or less, 5 mol% or more and 20 mol%, 5 mol% with respect to the total number of moles of the unsaturated alkyl group, saturated alkyl group, and hydrogen. mol% or more 18 mol%, 5 mol% or more and 15 mol% or less, 8 mol% or more and 25 mol% or less, 8 mol% or more and 20 mol% or less, 8 mol% or more and 18 mol% or less, 8 mol% or more and 15 mol% Below, 10 mol% or more and 25 mol% or less, 10 mol% or more and 20 mol% or less, 10 mol% or more and 18 mol% or less, 10 mol% or more and 15 mol% or less, 15 mol% or more and 25 mol% or less, 15 mol% It may be greater than or equal to 20 mol%, or greater than or equal to 15 mol% and less than or equal to 18 mol%.

When the content of hydrogen is within the above range, the silicone compound may stably react with the curing agent and/or the photoinitiator, and the release peeling force of the release layer prepared using the release composition may be appropriately adjusted. .

According to an exemplary embodiment of the present invention, the viscosity of the silicone compound is 5,000 cPs or more and 8,000 cPs or less, 5,000 cPs or more and 7,500 cPs or less, 5,000 cPs or more and 7,000 cPs or less, at a temperature of 25° C., a humidity of 50 RH% and a frequency of 30 Hz, 5,000 cPs or more 6,800 cPs or less, 5,500 cPs or more 8,000 cPs or less, 5,5000 cPs or more 7,500 cPs or less, 5,500 cPs or more 7,000 cPs or less, 5,500 cPs or more 6,800 cPs or less, 6,000 cPs or more 8,000 cPs or less, 6,000 cPs or more 7,500 cPs or less , 6,000 cPs or more and 7,000 cPs or less, 6,000 cPs or more and 6,800 cPs or less, 6,500 cPs or more and 8,000 cPs or less, 6,500 cPs or more and 7,500 cPs or less, 6,500 cPs or more and 7,000 cPs or less, 6,500 cPs or more and 6,800 cPs or less.

When the viscosity of the silicone compound is within the above range, the release composition including the silicone compound can be easily handled when the release layer is formed, and the surface flatness of the prepared release layer can be very excellently controlled.

According to an exemplary embodiment of the present invention, the curing agent may control a contact angle and surface energy of a release film prepared using the release composition to enable proper release peeling force of the release layer.

According to an exemplary embodiment of the present invention, the curing agent may include at least one of a tin-based curing agent, a platinum-based curing agent, a cerium-based curing agent, and a titanium-based curing agent. However, the present invention is not limited thereto, and a known curing agent may be applied to achieve the required physical properties.

According to an exemplary embodiment of the present invention, the content of the curing agent is 1 part by weight or more and 10 parts by weight or less, 1 part by weight or more and 7 parts by weight or less, 1 part by weight or more and 6 parts by weight or less, 3 Parts by weight or more 10 parts by weight or less, 3 parts by weight or more and 7 parts by weight or less, 3 parts by weight or more and 6 parts by weight or less, 4 parts by weight or more and 10 parts by weight or less, 4 parts by weight or more and 7 parts by weight or less, or 4 parts by weight or more 6 It may be less than or equal to parts by weight.

When the content of the curing agent is within the above range, it is possible to sufficiently cure the release composition including the curing agent, while preventing the occurrence of problems such as overcuring, rapid curing, or change with time.

According to an exemplary embodiment of the present invention, the photoinitiator may include at least one photopolymerization functional group of a benzophenone-based functional group, a quinone-based functional group, and a thioxanthone-based functional group.

As a result of research by the present inventors, when a type 1 photoinitiator such as acetphenones, benzoin, acylfosypin oxides, etc. is included as a photoinitiator, it may be possible to further cure the release film by light irradiation. It was difficult to control the release peeling force of the release film accordingly.

Accordingly, the present inventors believe that when using a second type photoinitiator, preferably a photoinitiator including the above-described photopolymerization functional group, additional curing of the release film by light irradiation may be possible, and the release peeling force of the release film according to the additional curing Therefore, it was confirmed that the release peeling force could be adjusted according to the additional hardening, and the present invention was reached.

According to an exemplary embodiment of the present invention, the photopolymerization functional group may be a hydrogen-recycling type. Specifically, the photopolymerization functional group may include an ester bond (-CO-), and the ester bond may be decomposed into oxygen radicals and carbon radicals upon curing of the release composition.

More specifically, the oxygen radical may decompose the hydrogen radical of the silicon compound by decomposing a bond between silicon and hydrogen on one side of the silicon compound.

In addition, the oxygen radical of the photopolymerization functional group may be combined with the hydrogen radical desorbed from the silicon compound to form a hydroxy group. In addition, when the release composition is cured, the carbon radical of the photopolymerization functional group may form a single bond with the silicone of the silicone compound.

According to an exemplary embodiment of the present invention, the benzophenone-based functional group is benzophenone, benzoyl benzoic acid, benzoyl benzoic acid methyl ether, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldi It may be a functional group derived from at least one compound selected from the group consisting of phenyl sulfide and 3,3'-methyl-4-methoxybenzophenone.

According to an exemplary embodiment of the present invention, the quinone-based functional group is quinone, anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, and 2,6-dichloro-9,10-anthraquinone. It may be a functional group derived from at least one compound selected from the group consisting of.

According to an exemplary embodiment of the present invention, the thioxanthone-based functional group is a group consisting of thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, and isopropyl thioxanthone It may be a functional group derived from at least one compound selected from.

According to an exemplary embodiment of the present invention, the photoinitiator may be benzophenone (meth)acrylate.

According to an exemplary embodiment of the present invention, the photoinitiator may include at least one of the compounds represented by the following Chemical Formulas 1 and 2.

[Formula 1]

In Formula 1,

n is an integer from 2 to 12, preferably an integer from 2 to 8,

R ₁ to R ₂₀ are each independently hydrogen; Or a straight or branched alkyl group having 1 to 15 carbon atoms,

[Formula 2]

In Formula 2,

R ₂₁ to R ₂₃ are each independently hydrogen; Or a linear or branched alkyl group having 1 to 15 carbon atoms,

A ₁ to A ₃ are each independently a substituent represented by the following formula (3),

[Formula 3]

In Chemical Formula 3,

m is an integer of 2 to 12, preferably an integer of 2 to 8,

* Is a position bonded to any one of _{A 1} to A _{2 of Formula 2,}

R ₂₄ to R ₃₄ are each independently hydrogen; Or it is a C1-C15 linear or branched alkyl group.

According to an exemplary embodiment of the present invention, the compound represented by Formula 1 may be a compound represented by the following Formula 1-1:

[Formula 1-1]

According to an exemplary embodiment of the present invention, the compound represented by Formula 2 may be a compound represented by the following Formula 2-1:

[Formula 2-1]

A in Formula 2-1 is a substituent represented by Formula 3-1:

[Chemical Formula 3-1]

In the above formula 3-1

* Is a position bonded to the position of A in Formula 2-1.

According to an exemplary embodiment of the present invention, the content of the photoinitiator is 0.5 parts by weight or more and 50 parts by weight or less, 0.5 parts by weight or more and 30 parts by weight or less, 1 part by weight or more and 50 parts by weight or less, or It may be 1 part by weight or more and 30 parts by weight.

When the content of the photoinitiator is within the above range, the release peel force may be adjusted when the release layer prepared using the release composition is further cured.

Specifically, when the content of the photoinitiator exceeds the above range, the release layer may be overcured, resulting in a problem in that the peeling force is rather reduced, and when the content of the photoinitiator is less than the range, additional curing may not proceed sufficiently. Problems can arise.

According to an exemplary embodiment of the present invention, the release composition may further include an organic solvent.

According to an exemplary embodiment of the present invention, the organic solvent may include at least one of toluene, hexane, heptane methyl ethyl ketone (MEK), 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 content of the organic solvent is 250 parts by weight or more and 700 parts by weight or less, 400 parts by weight or more and 600 parts by weight or less, 200 parts by weight or more and 300 parts by weight or less, based on 100 parts by weight of the silicone compound. , 350 parts by weight or more and 500 parts by weight or less, or 550 parts by weight or more and 700 parts by weight or less. When the content of the organic solvent is within the above range, the solid content of the release composition may be controlled to 3% or more and 10% or less.

According to an exemplary embodiment of the present invention, the solid content of the release composition is 3% or more and 10% or less, 4.5% or more and 9% or less, 6% or more and 8% or less, 4% or more and 6% or less, 5% or more and 7.5% or less. , Or 8% or more and 10% or less.

When the solid content is within the above range, the release composition can be easily applied. In addition, it is possible to prevent the wettability of the release layer from deteriorating by preventing the viscosity from rapidly increasing during curing of the release composition.

Specifically, when the content of the solid content contained in the release composition is less than the above range, the flowability of the release composition may be excessive and handling may not be easy during application, and the durability of the release film due to insufficient amount of the silicone compound. This deterioration problem may occur.

In addition, when the content of the solid content contained in the release composition exceeds the above range, the viscosity rapidly increases during curing of the release composition for preparing the release layer, resulting in a problem of lowering the surface flatness of the release layer. .

According to an exemplary embodiment of the present invention, the release composition may further include a crosslinking agent. As the release composition further includes a crosslinking agent, durability of a release layer prepared using the release composition may be ensured.

The crosslinking agent may include at least one of an epoxy crosslinking agent, an epoxy crosslinking agent, a silicone crosslinking agent, a urethane crosslinking agent, an acrylic crosslinking agent, and an amide crosslinking agent, and preferably a silicone crosslinking agent.

According to an exemplary embodiment of the present invention, the content of the crosslinking agent is 0.1 parts by weight or more and 20 parts by weight or less, 0.1 parts by weight or more and 5 parts by weight or less, 1 part by weight or more and 20 parts by weight or less, or It may be 1 part by weight or more and 5 parts by weight or less.

When the content of the crosslinking agent is within the above range, durability of the release layer prepared using the release composition may be sufficiently secured. Specifically, if it is less than the above range, the crosslinking reaction between the constituents in the release composition may not be sufficiently induced, and thus the release layer may not be properly formed.

In addition, if it exceeds the above range, the crosslinking reaction between the components included in the release composition proceeds excessively, and thereafter, further curing of the release film may no longer proceed, and there may be a problem in that the release peeling force cannot be controlled. .

Another exemplary embodiment of the present invention provides a release film including a release layer including a cured product of the release composition.

According to an exemplary embodiment of the present invention, the release film may include a substrate and the release layer provided on the substrate.

The release film may be a release liner commonly referred to in the art.

In addition, the substrate may be freely applied as long as it is used as a substrate for a release liner, such as paper or plastic film.

According to an exemplary embodiment of the present invention, the release layer may be prepared using the release composition. Specifically, the release layer may be prepared by curing the release composition.

According to an exemplary embodiment of the present invention, the release layer is subjected to additional curing after the first curing of the release composition, and the release peeling is 1.5 to 10 times the release peeling force of the Tesa7475 standard adhesive tape at the time of the first curing. It may be that the force is regulated.

That is, the release layer can be further cured after the first curing, and through the additional curing, the release peeling force of the release film is 1.5 to 10 times the release peeling force of the Tesa 7475 standard adhesive tape at the time of the first curing. Can be adjusted.

In addition, the Tesa 7475 is only one example of a standard adhesive tape, and the release peel force may be measured using a standard adhesive tape used for measuring the release peel force.

According to an exemplary embodiment of the present invention, the first curing may be thermal curing of the release composition at a temperature of 130° C. or more and 170° C. or less, or 140° C. or more and 160° C. or less for a time of 0.5 to 5 minutes.

According to an exemplary embodiment of the present invention, the additional curing may be photocuring by irradiating ultraviolet rays having a light amount of ^{1 J/cm 2} to 5 J/cm ^{2 after the first curing of the release composition.}

According to an exemplary embodiment of the present invention, the light source of the ultraviolet light may use a metal halide, a high pressure mercury, or a UV LED, but if it is capable of irradiating the aforementioned amount of ultraviolet light, freely selectable from light sources generally known in the art. It can be.

According to an exemplary embodiment of the present invention, the release peel force of the release layer to the standard adhesive tape during the first curing may be 15 gf/in or more, specifically 15.8 gf/in or more at 25° C. and 50 RH%.

According to an exemplary embodiment of the present invention, the release peel force with respect to the standard adhesive tape when the release layer is further cured may be 40 gf/in, specifically 45.5 gf/in or more at 25°C and 50 RH%.

The release peeling force of the release layer may be a release peeling force of the release film to the exposed release layer.

According to an exemplary embodiment of the present invention, the release layer may be one that satisfies Equation 1 below:

[Equation 1]

15≤{(Y-X)/X}×100≤800

In Equation 1 above,

X may mean a release peeling force with respect to the Tesa7475 standard adhesive tape at the time of the first curing of the release layer,

Y may mean a release peeling force with respect to the Tesa7475 standard adhesive tape when the release layer is further cured.

In the present specification, the term "releasing peeling force against the Tesa7475 standard adhesive tape at the time of the first curing of the release layer" refers to the prepared release layer being aged at 50° C. for 24 hours, and then the Tesa 7475 standard adhesive tape is brought into contact with the release layer. And then stored at 25°C for 24 hours, using a measuring device (AR-1000, Chem Instruments) at 25°C, the peeling force measured at a peeling rate of 300 mm/min and a peeling angle of 180° is measured. It can mean.

In the present specification, the term "releasing peel force against the Tesa7475 standard adhesive tape upon further curing of the release layer" refers to the prepared release layer being aged at 50° C. for 24 hours, and then bringing the Tesa 7475 standard adhesive tape into contact with the release layer. Attached, stored for 24 hours at 25°C, cured by irradiation with ultraviolet rays, and then cured at 25°C using a measuring device (AR-1000, Chem Instruments) with a peeling rate of 300 mm/min and a peeling angle of 180° It may mean the peeling force measured in.

That is, the release composition may be further cured after the first curing, and the release layer prepared through the additional curing may have a higher release peeling force than the release layer prepared through the first curing. Therefore, the release layer may increase the release peeling force through additional curing, specifically, additional photocuring.

The release film according to an exemplary embodiment of the present invention can be applied to various members because the release force can be freely adjusted according to the properties of the adherend.

According to an exemplary embodiment of the present invention, the thickness of the release film is 10 µm or more and 250 µm or less, 10 µm or more and 200 µm or less, 10 µm or more and 150 µm or less, 20 µm or more and 250 µm or less, 20 µm or more and 200 µm or less, It may be 20 µm or more and 150 µm or less, 50 µm or more and 250 µm or less, 50 µm or more and 200 µm or less, or 50 µm or more and 150 µm or less. However, it is not limited thereto, and may be freely adjusted according to the type and thickness of the substrate to be attached.

Hereinafter, examples will be described in detail in order to describe the present invention in detail. However, the embodiments according to the present invention may be modified in various forms, and the scope of the present invention is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely describe the present invention to those of ordinary skill in the art.

[ Example One]

Silicone compounds having an unsaturated alkyl group, a saturated alkyl group, and a hydrogen content bonded to the silicone skeleton with respect to the total number of moles of the unsaturated alkyl group, saturated alkyl group, and hydrogen, respectively, were prepared in 3.5 mol%, 11 mol%, and 85.5 mol%. The unsaturated alkyl group bonded to the silicone skeleton was a vinyl group, and the saturated alkyl group was a methyl group.

Using a viscometer (DV-II ⁺ PRO Viscometer, Brookfield Co.), the viscosity of the silicone compound was 5,000 to 8,000 cPs measured under the conditions of a temperature of 25° C., a humidity of 50 RH%, and a frequency of 30 Hz.

With respect to 100 parts by weight of the prepared silicone compound, 500 parts by weight of toluene as an organic solvent, 5 parts by weight of a platinum-based curing agent (PL-50T, Shin-Etsu Silicone) as a curing agent, and 5 parts by weight of a crosslinking agent (X-92-122, Shin-Etsu Silicon) A release composition was prepared by adding parts and 1 part by weight of benzophenone methacrylate as a photoinitiator. The solid content of the release composition was 5%.

The prepared release composition was applied at ^{about 2.5 g/m 2} on a polyethylene terephthalate (PET) substrate having a thickness of 50 μm using Mayer Bar #8. Thereafter, the release composition applied on the substrate was cured at 150° C. for 1 minute to prepare a release film.

[ Example 2]

A release film was prepared in the same manner as in Example 1, except that 5 parts by weight of benzophenone methacrylate was added.

[ Example 3]

A release film was prepared in the same manner as in Example 1, except that 10 parts by weight of benzophenone methacrylate was added.

[ Example 4]

A release film was prepared in the same manner as in Example 1, except that 30 parts by weight of benzophenone methacrylate was added.

[ Example 5]

A release film was prepared in the same manner as in Example 1, except that 1 part by weight of the compound represented by Formula 2-1 was added instead of benzophenone methacrylate as a photoinitiator.

[ Example 6]

A release film was prepared in the same manner as in Example 5, except that 5 parts by weight of the compound represented by Formula 2-1 was added.

[ Example 7]

A release film was prepared in the same manner as in Example 5, except that 10 parts by weight of the compound represented by Formula 2-1 was added.

[ Example 8]

A release film was prepared in the same manner as in Example 5, except that 30 parts by weight of the compound represented by Formula 2-1 was added.

[ Comparative example One]

A release film was prepared in the same manner as in Example 1, except that a photoinitiator was not added.

[ Comparative example 2]

A release film was prepared in the same manner as in Example 1, except that 1 part by weight of anthracene (LG Chemical) was added as a photoinitiator.

[ Comparative example 3]

A release film was prepared in the same manner as in Comparative Example 2, except that 5 parts by weight of anthracene (LG Chemical) was added as a photoinitiator.

[ Comparative example 4]

A release film was prepared in the same manner as in Comparative Example 2, except that 10 parts by weight of anthracene (LG Chemical) was added as a photoinitiator.

[ Comparative example 5]

A release film was prepared in the same manner as in Comparative Example 2, except that 30 parts by weight of anthracene (LG Chemical) was added as a photoinitiator.

The release peel force of the Tesa 7475 standard adhesive tape at the time of primary curing of Examples 1 to 8 and Comparative Examples 1 to 5 measured according to the above-described method of measuring the release peel force is shown in Table 1 below. I got it.

division Release peel force (gf/in) Example 1 28.5 Example 2 29.6 Example 3 22.5 Example 4 24.9 Example 5 19.5 Example 6 15.8 Example 7 24.3 Example 8 22.9 Comparative Example 1 28.6 Comparative Example 2 25.1 Comparative Example 3 26.6 Comparative Example 4 24.1 Comparative Example 5 22.9

In addition, the release films prepared according to Examples 1 to 8 and Comparative Examples 1 to 5 were further cured by irradiation with ultraviolet rays (light source: metal halide) having a light amount ^{of 5 J/cm 2.}

The release peeling force of the release layer at the time of the additional curing and the change rate of the release force that can be represented by Equation 1 were measured and shown in Table 2 below.

division Release peel force (gf/in) Release force change rate (%) Example 1 46.4 63 Example 2 42.7 44 Example 3 56.6 151 Example 4 61.1 146 Example 5 54.3 179 Example 6 45.5 188 Example 7 81.0 234 Example 8 204.5 792 Comparative Example 1 29.0 1.39 Comparative Example 2 28.8 15 Comparative Example 3 31.4 18 Comparative Example 4 32.3 34 Comparative Example 5 26.9 17

According to Table 1, it was confirmed that the release compositions according to Examples and Comparative Examples did not show a significant difference in release peeling force during the first curing.

However, according to Table 2, it was confirmed that the rate of change of the release force of the release films additionally cured according to Examples 1 to 8 was much greater than the rate of change of the release force of the release films additionally cured according to Comparative Examples 1 to 5 .

Specifically, it was confirmed that in the case of Comparative Example 1 in which the photoinitiator was not added, the release peeling force hardly increased even by light irradiation. That is, in the case of Comparative Example 1, it was confirmed that hardly any additional hardening occurred. Through this, it can be seen that in order to enable additional curing, a photoinitiator should be further added to the release composition.

In addition, in the case of Comparative Examples 2 to 5 containing anthracene, a photoinitiator containing a photoinitiator that does not correspond to a photopolymerization functional group according to an exemplary embodiment of the present invention, the release force change rate is not greater than that of Examples 1 to 8. It was confirmed that the release force did not increase significantly even when the anthracene content was increased.

The release peeling force of the release film of Examples 1 to 8 to the standard adhesive tape of the release film is increased through additional curing, so that the release peeling force must be included in the form of a photoinitiator according to an exemplary embodiment of the present invention. I could see that I could.

In summary, in order to manufacture a release film in which release peeling force can be adjusted and the type of member that can be applied is not limited, the release composition must contain a photoinitiator of the kind according to an exemplary embodiment of the present invention. I could confirm that.

Claims (13)

Silicone compounds;
Hardener; And
Including; a photoinitiator containing at least one photopolymerization functional group of a benzophenone-based functional group, a quinone-based functional group, and a thioxanthone-based functional group,
The content of the photoinitiator is 1 part by weight or more and 30 parts by weight or less based on 100 parts by weight of the silicone compound. delete The method according to claim 1,
The photoinitiator is a release composition comprising at least one of the compounds represented by the following formulas 1 and 2:
[Formula 1]

In Formula 1,
n is an integer from 2 to 12,
R ₁ to R ₂₀ are each independently hydrogen; Or a straight or branched alkyl group having 1 to 15 carbon atoms,
[Formula 2]

In Formula 2,
R ₂₁ to R ₂₃ are each independently hydrogen; Or a linear or branched alkyl group having 1 to 15 carbon atoms,
A ₁ to A ₃ are each independently a substituent represented by the following formula (3),
[Formula 3]

In Chemical Formula 3,
m is an integer of any one of 2 to 12,
* Is a position bonded to any one of _{A 1} to A _{3 of Formula 2,}
R ₂₄ to R ₃₄ are each independently hydrogen; Or it is a C1-C15 linear or branched alkyl group. The method according to claim 1,
The release composition of the curing agent comprises at least one of a tin-based curing agent, a platinum-based curing agent, a cerium-based curing agent, and a titanium-based curing agent. The method according to claim 1,
The content of the curing agent is 1 part by weight or more and 10 parts by weight or less based on 100 parts by weight of the silicone compound. The method according to claim 1,
The silicone compound has a viscosity of 5,000 cPs or more and 8,000 cPs or less at a temperature of 25° C., a humidity of 50 RH%, and a frequency of 30 Hz. The method according to claim 1,
The silicone compound is a release composition in which an unsaturated alkyl group, a saturated alkyl group, and hydrogen are bonded to the silicone skeleton. The method of claim 7,
The content of the unsaturated alkyl group in the silicone compound is 2 mol% or more and 5 mol% or less with respect to the total number of moles of the unsaturated alkyl group, saturated alkyl group, and hydrogen. The method of claim 7,
The content of the saturated alkyl group in the silicone compound is 70 mol% or more and 90 mol% or less with respect to the total number of moles of the unsaturated alkyl group, saturated alkyl group, and hydrogen. The method of claim 7,
The content of the hydrogen in the silicone compound is 5 mol% or more and 25 mol% or less with respect to the total number of moles of the unsaturated alkyl group, saturated alkyl group, and hydrogen. A release film comprising a release layer comprising a cured product of the release composition according to claim 1. The method of claim 11,
The release layer is a release film in which the release peeling force is adjusted 1.5 to 10 times with respect to the release peeling force of the Tesa7475 standard adhesive tape at the time of the first curing through additional curing after the first curing of the release composition. The method of claim 11,
The release film of the release layer at the time of the first curing of the Tesa7475 standard adhesive tape is 15 gf/in or more at 25° C. and 50 RH%.