Recycling release film and device comprising same

Abstract

Disclosed are a recycling release film and a device comprising same. The recycling release film comprises a substrate and a release layer positioned on at least one surface of the substrate, wherein the release layer can be peeled off by light source irradiation for 400 μs to 30 ms at a wavelength of 900 nm to 1100 nm.

Description

Recycled release film and device including the same

[0001] The present disclosure relates to a recycled release film and a device including the same.

[0002] Release films are typically used as protective films, with an adhesive film attached to protect the adhesive from foreign substances or unwanted adhesives in the air. Release films typically have a structure in which a release layer is formed on a polyester base film.

[0003] Release films are also used as carrier films for thinly and uniformly applying ceramic slurry to the green sheets that make up multi-layer ceramic capacitors (MLCCs). The green sheets used here are formed by uniformly applying ceramic slurry onto a carrier film, which serves as a support, and then firing it. The carrier film for forming the green sheets uses a biaxially oriented polyester film as a substrate, which has excellent mechanical strength, dimensional stability, heat resistance, and price competitiveness, and a release film with a high-molecular silicone release layer applied to one side thereof is used. The release film is discarded after use, and the coating of the silicone release layer makes recycling the substrate difficult.

[0004] Therefore, there is still a need for a recyclable release film and a device including the same that can easily peel off a silicone-based release layer, a non-silicon-based release layer, or both a silicone-based release layer and a non-silicon-based release layer.

[0005] One aspect is to provide a recyclable release film that can easily peel off a silicone-based release layer, a non-silicon-based release layer, or both a silicone-based release layer and a non-silicon-based release layer.

[0006] Another aspect is to provide a device comprising the above-described recycled heteromorphic film.

[0007] According to one aspect,

[0008] Description; and

[0009] A heterogeneous layer located on at least one side of the above-described substrate;

[0010] A recyclable release film is provided, wherein the above-mentioned release layer can be peeled off by light source irradiation at a wavelength of 900 nm to 1100 nm for 400 μs to 30 ms.

[0011] The above heterogeneous layer can satisfy the peeling force change rate (%) expressed by the following equation 1:

[0012] [Formula 1]

[0013] [(P i -P r ) / P i ] x 100(%) ≥ 50%

[0014] During the meal,

[0015] P i It may be the peeling force (gf / in) when an acrylic tape is attached to the surface of a release layer and the acrylic tape is peeled from the release layer at a temperature of 180 ℃ and a speed of 0.3 m / min after 5 minutes at room temperature.

[0016] P r It may be the peeling force (gf / in) when an acrylic tape is attached to the surface of a release layer after irradiation with a light source for 1000 μs under a xenon flash lamp having a wavelength of 900 nm to 1100 nm and the acrylic tape is peeled from the release layer at a temperature of 180°C and a speed of 0.3 m / min.

[0017] The above release layer may be a cured layer of a composition containing a release agent and an additive,

[0018] The above additive may include at least one of an infrared absorber and a surfactant.

[0019] The above release agent may include a silicone-based compound, a non-silicon-based compound, or a mixture of a silicone-based compound and a non-silicon-based compound.

[0020] The above infrared absorber may include at least one selected from a dithiol-based metal complex compound, a cyanine-based compound, a benzothiazole-based compound, a squarylium-based compound, a chroconium-based compound, a diimmonium-based compound, and a phthalocyanine-based compound.

[0021] The content of the infrared absorbent may be 0.01 part by weight to less than 1 part by weight based on 100 parts by weight of the composition.

[0022] The above composition may further comprise a catalyst.

[0023] The above catalyst may include at least one of a silicon-based catalyst and a non-silicon-based catalyst.

[0024] When the density of silicon elements present in the above heterogeneous layer is measured by XRF (X-Ray Fluorescence), the above heterogeneous layer can satisfy the silicon density change rate (%) expressed by the following equation 2:

[0025] [Formula 2]

[0026] [(D i -D r ) / D i ] x 100(%) ≥ 80%

[0027] During the meal,

[0028] D i is D i The density of silicon elements present in the heterogeneous layer (g / m) was measured by attaching and removing the tape once before irradiating the light source. 3 ) can be,

[0029] D r After irradiating the film with a xenon flash lamp of wavelength 900 nm to 1100 nm for 1000 ㎲, the tape was attached and removed once, and the density of silicon elements present in the release layer (g / m) was measured. 3 ) may be.

[0030] The thickness of the above heterogeneous layer may be 0.01 ㎛ to 2 ㎛.

[0031] The above description may not include an infrared absorber and an adhesive.

[0032] The change in residual adhesion ratio (ΔR) expressed by Equation 4 below before and after the above light source irradiation p ) can satisfy:

[0033] [Formula 4]

[0034] ΔR p = [(R p1 -R p2 )] ≥ 80%

[0035] During the meal,

[0036] R p1 It may be the residual adhesion rate of the surface of the release layer after the tape is attached and removed once before the light source irradiation.

[0037] R p2 It can be the residual adhesion rate of the surface of the release layer after the tape is attached once and then removed after irradiation for 1000 ㎲ under a xenon flash lamp with a wavelength of 900 nm to 1100 nm.

[0038] Depending on other aspects,

[0039] A device comprising the aforementioned recycled heteromorphic film is provided.

[0040] A recycling release film according to one aspect comprises a substrate and a release layer located on at least one side of the substrate, wherein the release layer is peelable by light irradiation at a wavelength of 900 nm to 1100 nm for 400 μs to 30 ms.

[0041] Figure 1 is a cross-sectional schematic diagram of a recycling heteromorphic film according to one embodiment.

[0042] Hereinafter, a recycling release film and a device including the same will be described in detail with reference to embodiments and drawings of the present invention. These embodiments are provided solely as examples to more specifically illustrate the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these embodiments.

[0043] The term "including" in this specification means that other components may be included rather than excluding other components unless specifically stated to the contrary.

[0044] As used herein, the term "and / or" is meant to include any and all combinations of one or more of the items described herein. As used herein, the term "or" means "and / or." The expressions "at least one" or "one or more" preceding elements herein may supplement the entire list of elements and do not imply that they supplement individual elements described above.

[0045] The term "combination of these" in this specification means a mixture or combination of one or more of the described components.

[0046] When a component is referred to herein as being "on" or "over" another component, the component may be directly on the other component, or there may be intervening components between the components. Conversely, when a component is referred to as being "directly on" or "directly over" another component, there may not be intervening components.

[0047] In this specification, “~-based resin”, “~-based polymer”, or / and “~-based copolymer” are broad concepts that include all of “~ resin”, “~ polymer”, “~ copolymer”, or / and “derivatives of ~ resin, polymer, or copolymer”.

[0048] In this specification, each component is a concept that includes both singular and plural.

[0049] Unless stated otherwise herein, all percentages, parts, ratios, etc. are by weight. Furthermore, whenever an amount, concentration, or other value or parameter is given as a range, a preferred range, or a list of upper preferred values ​​and lower preferred values, this should be understood to specifically disclose all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Whenever a range of numerical values ​​is recited herein, unless stated otherwise, the range is intended to include the endpoints thereof and all integers and fractions therein. The scope of the present invention is not intended to be limited to the specific values ​​recited when defining a range.

[0050] Unless otherwise specified, the units “parts by weight” and “weight %” refer to the weight ratio between each component, and the units “parts by mass” and “mass %” refer to the weight ratio between each component converted to solid content.

[0051] As used herein, "about" means within an acceptable range of deviation from a stated value, as determined by one of ordinary skill in the art, taking into account the errors associated with the measurement and measurement of a particular quantity (i.e., the limits of the measurement system). For example, "about" may mean within one or more standard deviations, or within ± 30%, 20%, 10%, or 5% of the stated value.

[0052] Throughout this specification, the terms "one embodiment," "an embodiment," and the like mean that a particular element described in connection with an embodiment is included in at least one embodiment described herein and may or may not be present in other embodiments. It should also be understood that the elements described may be combined in any suitable manner across various embodiments.

[0053] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by those skilled in the art to which this disclosure pertains. Furthermore, it will be understood that terms defined in commonly used dictionaries should be interpreted to have a meaning consistent with their meaning in the relevant art and the context of this disclosure, and should not be interpreted as idealized or overly formal.

[0054] In the prior art, to facilitate the separation of a release layer from a substrate, a soluble layer containing a soluble resin was formed between the substrate and the release layer, and the release layer was separated by treating it with a soluble solvent. However, when using a typical soluble resin, the soluble layer can easily deform, which can adversely affect the physical properties of the release film, such as the residual adhesion rate and adhesive strength. Furthermore, the solubility of the soluble layer decreases, making it difficult to completely separate the substrate from the release layer.

[0055] Taking this into consideration, the present inventors propose the following recycling heteromorphic film and a device including the same.

[0056] Figure 1 is a cross-sectional schematic diagram of a recycling heteromorphic film according to one embodiment.

[0057] Referring to FIG. 1, a recycling release film (120) according to one embodiment has a substrate (100) and a release layer (110) arranged in sequence.

[0058] The substrate (100), release layer (110), and elements constituting the recycling release film (120) are described in detail as follows.

[0059]

[0060] [Description (100)]

[0061] The substrate (100) used in the present invention may be a known film or sheet known as a substrate for a heteromorphic film.

[0062] For example, a polyester resin film can be used as the substrate (100). A known polyester base film commonly used in the field of release films can be used as the polyester resin film.

[0063] For example, the polyester-based base film may be a polyester-based base film disclosed in Korean Patent Registration No. 10-1268584, Korean Patent Publication No. 2012-45213, and Korean Patent Publication No. 2012-99546.

[0064] However, in one embodiment of the present invention, in order to explain only the features of the present invention, a polyester-based base film is described without limitation, but it should be understood that it includes technical features related to a known polyester-based base film.

[0065] The polyester-based substrate film may include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, polypropylene, polycarbonate, polyolefin, polyetheretherketone, polyphthalamide, polyimide, polysulfone, polyethersulfone, polyetherimide, or a combination thereof.

[0066] For example, the polyester-based substrate film may be a polyethylene terephthalate (PET) substrate film. The polyethylene terephthalate (PET) substrate film has excellent physical stability over a wide temperature range from low to high temperatures, and has excellent chemical resistance, mechanical strength, and surface properties. In addition, the polyethylene terephthalate (PET) substrate film has good thickness uniformity and excellent adaptability to process conditions for various purposes. In addition, it has a high recyclability rate in terms of environmental pollution issues, and is therefore widely used in recycled release films (120).

[0067] The polyester resin forming the base film of the present invention may be a polyester obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic glycol.

[0068] Examples of aromatic dicarboxylic acids include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, and oxycarboxylic acids (e.g., ρ-oxybenzoic acid). Examples of aliphatic glycols include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanol, and neopentyl glycol. These polyester resins may use two or more types of dicarboxylic acid components and glycol components in combination, and copolymers containing a third component are also possible.

[0069] Polyester-based substrate films can be used as uniaxially or biaxially oriented films, which offer high transparency and superior productivity and processability. For example, the polyester-based substrate film can be used as a biaxially oriented film.

[0070] Optionally, the polyester-based substrate film may contain particles to impart excellent roll-to-roll running properties, and any added particles that exhibit excellent sliding properties may be used without limitation.

[0071] Examples of such particles may include particles of silica, silicon oxide, calcium carbonate, calcium sulfate, calcium phosphate, magnesium carbonate, magnesium phosphate, barium carbonate, kaolin, aluminum oxide, titanium oxide, etc., and the shape of the particles used is not limited, but for example, any of spherical, block-shaped, rod-shaped, and plate-shaped particles may be used.

[0072] There are no restrictions on the hardness, specific gravity and color of the particles, but two or more types may be used in parallel as needed, and the average particle diameter of the particles used may be 0.1 to 5 ㎛, for example, those in the range of 0.1 to 2 ㎛ may be used. At this time, if the average particle diameter of the particles is less than 0.1 ㎛, agglomeration between particles may occur, resulting in poor dispersion, and if the average particle diameter of the particles exceeds 5 ㎛, the surface roughness characteristics of the film may deteriorate, resulting in poor coating during post-processing.

[0073] When particles are included in the polyester-based substrate film, the particle content may be 0.01 to 5 wt%, for example, 0.01 to 3 wt%, based on the total weight of the polyester-based substrate film. If the particle content is less than 0.01 wt%, the slip properties of the polyester film may deteriorate, resulting in poor running properties between rolls. If the particle content exceeds 5 wt%, the surface smoothness of the film may deteriorate.

[0074] The polyester-based substrate film has no thickness restrictions, but may be 10 to 200 ㎛.

[0075] If the polyester-based base film is too thin, less than 10 ㎛, there is a risk of deformation due to heat treatment during processing, and if it is too thick, more than 200 ㎛, there may be a problem with curing because heat may not be sufficiently transmitted.

[0076] The substrate (100) may not include an infrared absorber and an adhesive.

[0077] [Lee Hyeong-cheong (110)]

[0078] According to one embodiment, the heterogeneous layer (110) can be peeled off by light source irradiation for 400 μs to 30 ms at a wavelength of 900 nm to 1100 nm.

[0079] Any light source capable of irradiating within the above-mentioned wavelength range can be used as a light source, but examples include laser light sources or flash lamps. These light sources can have instantaneous intensity and transmit energy in very short pulses for irradiation.

[0080] The heterogeneous layer (110) according to one embodiment can satisfy the peeling force change rate (%) expressed by the following equation 1:

[0081] [Formula 1]

[0082] [(P i -P r ) / P i ] x 100(%) ≥ 50%

[0083] During the meal,

[0084] P i It may be the peeling force (gf / in) when an acrylic tape is attached to the surface of a release layer and the acrylic tape is peeled from the release layer at a temperature of 180 ℃ and a speed of 0.3 m / min after 5 minutes at room temperature.

[0085] P r It may be the peeling force (gf / in) when an acrylic tape is attached to the surface of a release layer after irradiation with a light source for 1000 μs under a xenon flash lamp with a wavelength of 900 nm to 1100 nm and the acrylic tape is peeled from the release layer at a temperature of 180°C and a speed of 0.3 m / min.

[0086] When the density of silicon elements present in the heterogeneous layer (110) is measured by XRF (X-Ray Fluorescence), the heterogeneous layer (110) can satisfy the silicon density change rate (%) expressed by the following equation 2:

[0087] [Formula 2]

[0088] [(D i -D r ) / D i ] x 100(%) ≥ 80%

[0089] During the meal,

[0090] D i The density of silicon elements present in the heterogeneous layer (g / m) was measured by attaching and removing the tape once before irradiating the light source. 3 ) can be,

[0091] D r After irradiating the film with a xenon flash lamp of wavelength 900 nm to 1100 nm for 1000 ㎲, the tape was attached and removed once, and the density of silicon elements present in the release layer (g / m) was measured. 3 ) may be.

[0092] According to one embodiment, the heterogeneous layer (110) can be easily peeled off by irradiating with a light source for a short period of time, satisfying Equations 1 and 2.

[0093] According to one embodiment, the release layer (110) is a cured layer of a composition including a release agent and an additive, and the additive may include at least one of an infrared absorber and a surfactant.

[0094] The above-mentioned release agent may include a silicone-based compound, a non-silicon-based compound, or a silicone-based compound and a non-silicon-based compound.

[0095] The silicone compound may include a reactive silicone compound and a cross-linkable silicone compound. The silicone compound may include a hydrogen-containing polysiloxane, an alkoxy-containing polysiloxane, a hydroxy-containing polysiloxane, and a vinyl-containing polysiloxane. Such a silicone compound may generally be a low-viscosity, easily flowable liquid resin. Generally, in an inline coating method, the silicone compound may be used in the form of an aqueous emulsion. The silicone compound in the form of an aqueous emulsion does not pose a risk of fire or environmental pollution when applying a composition for forming a release layer to at least one surface of a substrate (100). Therefore, the composition for forming a release layer is easy to handle during concentration adjustment, application process, and hot air drying process.

[0096] The non-silicon compound may be a melamine compound. Examples of the melamine compound include methylolated melamine, methyl etherified melamine, butyl etherified melamine, methylated melamine, butylated melamine, or methylurea melamine. For example, the melamine compound is produced by the reaction of melamine and formaldehyde. The methylolated melamine thus produced is reacted with an alcohol having an appropriate carbon number under acid catalyst conditions to produce an alkyl etherified melamine resin. Here, the carbon number of the alkyl group is not limited, and can be selected within a range that satisfies the surface energy properties of the release layer (110).

[0097] The infrared absorber may include at least one selected from dithiol-based metal complex compounds, cyanine-based compounds, benzothiazole-based compounds, squarylium-based compounds, chroconium-based compounds, diimmonium-based compounds, and phthalocyanine-based compounds.

[0098] The content of the infrared absorber may be 0.01 part by weight to less than 1 part by weight based on 100 parts by weight of the composition. If the content of the infrared absorber is less than 0.01 part by weight, the photoreaction by light source irradiation is insufficient, and if the content of the infrared absorber is 1 part by weight or more, the curing of the release agent is hindered or the coating is poor due to insufficient solubility.

[0099] The above composition may further comprise a catalyst.

[0100] The catalyst may include at least one of a silicon-based catalyst and a non-silicon-based catalyst.

[0101] The silicon-based catalyst may use silicon and one or more metals or amphoteric elements selected from groups 4 to 14 of the periodic table, for example, silicon and one or more selected from Rh, Pt, Sn, Ti, Pd, Ir, W, and Co. For example, the catalyst may include a silicon and platinum chelate catalyst.

[0102] The non-silicon catalyst may be a melamine catalyst.

[0103] The content of the catalyst may be 0.01 parts by weight to less than 5 parts by weight based on 100 parts by weight of the composition. If the content of the catalyst is less than 0.01 parts by weight, the release layer (110) may not be cured, and if the content of the catalyst is 5 parts by weight or more, the properties of the release layer (110) may be poor due to the residual catalyst.

[0104] The heterogeneous layer (110) may further include a peeling control agent to control peelability.

[0105] A silicone polymer component such as polydimethylsiloxane can be added and used as a peeling control agent. The content of the silicone polymer component can be used in an amount of 50 parts by weight or less based on 100 parts by weight of the entire composition to ensure the stability of the release layer (110) over time.

[0106] In some cases, the heterogeneous layer (110) may further include one or more of organic and inorganic particles, an antistatic agent, a conductivity enhancer, a pH regulator, and an antifouling agent.

[0107] The organic or inorganic particles may be inorganic particles selected from natural minerals; oxides, hydroxides, sulfides, nitrides, or halides of elements of groups 1 to 4, 11 to 12, 14, and 16 to 18; carbonates, sulfates, acetates, phosphates, phosphites, carboxylates, silicates, titanates, borates, or hydrates thereof; and complex compounds thereof.

[0108] The organic particles may be organic particles selected from fluorine-based resins, melamine-based resins, styrene-based resins, acrylic-based resins, silicone-based resins, styrene-divinylbenzene-based copolymer resins, and polymers or copolymers crosslinked with these resins.

[0109] The shape of the organic and inorganic particles is not particularly limited, and may be spherical, blocky, rod-shaped, or flat. In addition, the hardness, specific gravity, color, etc. of the organic and inorganic particles are not limited, and, if necessary, these organic and inorganic particles may be used singly or in combination of two or more.

[0110] The average particle diameter (D50) of the organic and inorganic particles may be 1 μm to 5 μm. For example, the average particle diameter (D50) of the organic and inorganic particles may be 3 μm to 5 μm or 1 μm to 2 μm. As used herein, the term "average particle diameter (D50)" refers to the particle diameter value corresponding to 50% of the smallest particle when the total number of particles is 100% in a cumulative distribution curve from the smallest particle size to the largest particle size. The D50 value can be measured by a method well known to those skilled in the art, for example, by measuring with a particle size analyzer, or by measuring from a TEM photograph or an SEM photograph. Alternatively, a measuring device using dynamic light-scattering can be used for measurement, data analysis can be performed to count the number of particles for each particle size range, and then the D50 value can be easily obtained through calculation.

[0111] If the average particle diameter (D50) of the organic and inorganic particles is less than 1 ㎛, sufficient surface roughness cannot be obtained, and thus blocking cannot be prevented. If the average particle diameter (D50) of the organic and inorganic particles exceeds 5 ㎛, it may act as a defect in the film.

[0112] The antistatic agent may be a known antistatic agent widely used in the field of the release film, but may be selected from, for example, PEDOT (Poly(3,4-ethylenedioxythiophene)), PEDOT:PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate), polyaniline, polypyrrole, quaternary ammonium salts, sulfonates, phosphates, and combinations thereof. The content of the antistatic agent may be 1 to 20 parts by weight based on 100 parts by weight of the entire composition.

[0113] The conductivity improver may be a known conductivity improver widely used in the field of the release film, but may be selected from, for example, ethylene glycol, dimethyl sulfoxide, N-methyl-2-pyrrolidone, propylene glycol, butyl glycol, dipropylene glycol dimethyl ether, gamma-butyrolactone, sulfolane, dimethyl carbonate, sorbitol, and combinations thereof. The content of the conductivity improver may be 1 part by weight to 20 parts by weight based on 100 parts by weight of the entire composition.

[0114] The pH regulator may be a known pH regulator widely used in the field of the release film, but may be selected from, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia water, and combinations thereof. The content of the conductivity improver may be 0.05 to 0.3 parts by weight based on 100 parts by weight of the entire composition.

[0115] The antifouling agent may be a known antifouling agent widely used in the field of the release film, but may be selected from, for example, fluorine, fluorine-containing silane compounds, fluorine-containing organic compounds, self-emulsifying silicone, and combinations thereof. The content of the antifouling agent may be 0.1 to 0.3 parts by weight based on 100 parts by weight of the entire composition.

[0116] The composition for forming a release layer is prepared by containing a solvent with a solid content of 0.5 to 10 wt%. The solvent may be used without limitation as long as it can disperse the solid content and apply it to a substrate, and examples thereof include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methyl cyclohexane, and isoparaffin; hydrocarbon solvents such as industrial gasoline (rubber gasoline, etc.), petroleum benzene, and solvent naphtha; ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, acetonylacetone, and cyclohexanone; Ester solvents such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and isobutyl acetate; ether solvents such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1,2-dimethoxy ethane, and 1,4-dioxane; solvents having ester and ether moieties such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, and 2-butoxyethyl acetate; siloxane solvents such as hexamethyldisiloxane, octamethyltrisiloxane, octamethyl cyclotetrasiloxane, decanemethyl cyclopentasiloxane, tris(trimethylsiloxy)methylsilane, and tetrakis(trimethylsiloxy)silane; Fluorinated solvents such as trifluorotoluene, hexafluoroxylene, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, or a mixed solvent thereof may be used. For example, toluene may be used as a solvent used in a composition for forming a release layer.

[0117] If the solid content of the composition for forming a release layer is less than 0.5 wt%, sufficient coating thickness may not be formed, and thus release properties may not be developed. If the solid content of the composition for forming a release layer exceeds 10 wt%, the viscosity of the composition for forming a release layer may be high, which may cause leveling unevenness, resulting in poor thickness uniformity of the release layer, and the coating thickness may become thick and not be cured.

[0118] The thickness of the release layer (110) may be 0.01 ㎛ to 2 ㎛. If the thickness of the release layer (110) is less than 0.01 ㎛, the release layer (110) may not peel off when bonded with an acrylic adhesive due to poor coverage. If the thickness of the release layer (110) exceeds 2 ㎛, a large amount of heat is required during curing, which may cause thermal deformation of the substrate (100), and the peelability may not be improved, which may increase the cost.

[0119] [Recycling release film (120)]

[0120] According to an embodiment, the recycling release film (120) has a residual adhesion rate change (ΔR) expressed by the following equation 4 before and after the light source irradiation. p ) can satisfy:

[0121] [Formula 4]

[0122] ΔR p = [(R p1 -R p2 )] ≥ 80%

[0123] During the meal,

[0124] R p1 It may be the residual adhesion rate of the surface of the release layer after the tape is attached and removed once before the light source irradiation.

[0125] R p2 It can be the residual adhesion rate of the surface of the release layer after the tape is attached once and then removed after irradiation for 1000 ㎲ under a xenon flash lamp with a wavelength of 900 nm to 1100 nm.

[0126] The recycling release film (120) can easily peel off a silicone-based release layer, a non-silicon-based release layer, or both a silicone-based release layer and a non-silicon-based release layer.

[0127] [Element]

[0128] A device according to another embodiment may include the aforementioned recycled film (120). Examples of the device include semiconductor devices, next-generation electronic devices, or MLCC devices.

[0129]

[0130] Hereinafter, the composition and resulting effects of the present invention will be described in more detail through examples and comparative examples. However, it should be understood that these examples are intended to illustrate the present invention more specifically, and that the scope of the present invention is not limited to these examples.

[0131]

[0132] [Example]

[0133]

[0134] Example 1: Recycled release film

[0135] (Composition for forming a heteromorphic layer)

[0136] A composition for forming a heteromorphic layer was prepared by mixing the following components.

[0137] ·Melamine compound release agent (CYMEL) ® 303 LF Resin, Allnex) 0.5 parts by weight

[0138] ·1.0 parts by weight of silicone emulsion release agent (SLY-OFF 7920, Dow Chemical)

[0139] ·0.1 part by weight of silicone catalyst (SLY-OFF 7924, Dow Chemical)

[0140] ·Melamine-based catalyst (Cycat) ® 4040 catalyst, Allnex) 0.06 parts by weight

[0141] ·0.01 parts by weight of silicone surfactant (BYK348, BYK)

[0142] · 0.25 parts by weight of diimonium compound infrared absorber (FND100, Wooksung Chemical)

[0143] ·5:5 mixture of isopropyl alcohol (IPA) and distilled water

[0144] (Lee Hyung Film)

[0145] The prepared composition for forming a release layer was applied to one side of a 50 ㎛ thick polyethylene terephthalate base film (XD500, Toray Advanced Materials Korea) using a bar coater. The applied composition for forming a release layer was dried and cured using a hot air dryer at a temperature of 140° C. for 30 seconds to form a release layer, thereby producing a recycled release film.

[0146] Example 2: Recycled release film

[0147] A recycled release film was manufactured by forming a release layer in the same manner as in Example 1, except that a composition for forming a release layer excluding a melamine compound release agent and a melamine-based catalyst was used.

[0148] Example 3: Recycled release film

[0149] A recycled release film was manufactured by forming a release layer in the same manner as in Example 1, except that a composition for forming a release layer other than a silicone emulsion release agent and a silicone-based catalyst was used.

[0150] Example 4: Recycled release film

[0151] A recycled release film was manufactured by forming a release layer in the same manner as in Example 1, except that 0.25 parts by weight of a phthalocyanine-based infrared absorber (GREEN 7, Union Chem) was used instead of a dimonium-based infrared absorber.

[0152] Example 5: Recycled release film

[0153] A recycling release film was manufactured by forming a release layer in the same manner as in Example 1, except that 0.25 parts by weight of a dithiol-based metal complex infrared absorber (2,5-Dimercapto-1,3,4-thiadiazole dipotassium salt, 97%, Thermo Scientific Chemicals) was used instead of the dimonium-based compound infrared absorber.

[0154] Example 6: Recycled release film

[0155] A recycled release film was manufactured by forming a release layer in the same manner as in Example 1, except that 0.25 parts by weight of a benzothiazole compound infrared absorber (benzothiazole, 97%, Thermo Scientific Chemicals) was used instead of the dimonium compound infrared absorber.

[0156] Comparative Example 1: Recycled release film

[0157] A recycled release film was manufactured by forming a release layer in the same manner as in Example 1, except that a composition for forming a release layer other than a dimonium compound infrared absorber was used.

[0158] Comparative Example 2: Recycled release film

[0159] A recycled release film was manufactured by forming a release layer in the same manner as in Example 1, except that a composition for forming a release layer excluding a melamine compound release agent, a melamine-based catalyst, and a dimonium-based compound infrared absorber was used.

[0160] Comparative Example 3: Recycled release film

[0161] A recycled release film was manufactured by forming a release layer in the same manner as in Example 1, except that a composition for forming a release layer other than a silicone emulsion release agent, a silicone-based catalyst, and a dimonium-based compound infrared absorber was used.

[0162] Comparative Example 4: Recycled release film

[0163] A recycling release film was manufactured by forming a release layer in the same manner as in Example 1, except that 0.56 parts by weight of a co-polyethylene terephthalate compound (Co-PET, EW-210S, Base Korea) was used instead of a melamine compound release agent and a melamine-based catalyst, and a composition for forming a release layer excluding a silicone emulsion release agent, a silicone-based catalyst, and a dimonium-based compound infrared absorber was used.

[0164] Comparative Example 5: Recycled release film

[0165] A recycling release film was manufactured by forming a release layer in the same manner as in Example 1, except that 0.56 parts by weight of an acrylate compound (NEOPOL 8470, Biwon International) was used instead of a melamine compound release agent and a melamine catalyst, and a composition for forming a release layer excluding a silicone emulsion release agent, a silicone catalyst, and a dimonium compound infrared absorber was used.

[0166] Comparative Example 6: Recycled release film

[0167] A recycled release film was manufactured by forming a release layer in the same manner as in Example 1, except that a composition for forming a release layer using 0.005 parts by weight of a dimonium compound infrared absorber was used.

[0168] Comparative Example 7: Recycled release film

[0169] A recycled release film was manufactured by forming a release layer in the same manner as in Example 1, except that a composition for forming a release layer using 1 part by weight of a dimonium compound infrared absorber was used.

[0170]

[0171] Evaluation Example 1: Physical Property Evaluation

[0172] The physical properties of the recycled release films manufactured in Examples 1 to 6 and Comparative Examples 1 to 7 were evaluated using the following method, and the results are shown in Table 1.

[0173] (1) Peeling force (gf / in) and peeling force change rate (%) before and after light source irradiation

[0174] Each recycled release film was cut to a size of 10 cm x 2.54 cm to prepare a sample. TESA7475 acrylic adhesive tape was attached to the prepared sample with a 2 kg roller before and after light irradiation. The peeling force (gf / in) when peeling the TESA7475 acrylic adhesive tape was measured after 5 minutes at room temperature.

[0175] ·Measuring instrument: TESA 7475_HEIDON

[0176] ·Measurement method: 180° peeling angle, 0.3 m / min peeling speed

[0177] The light source used in the investigation was a xenon flash lamp (XF750, Unilam Co., Ltd.) with a wavelength of 900 nm to 1100 nm, and the irradiation was performed for 1000 μs.

[0178] The peeling force before and after the measured light source irradiation was substituted into Equation 1 below to obtain the peeling force change rate (%).

[0179] [Formula 1]

[0180] [(P i -P r ) / P i ] x 100(%) ≥ 50%

[0181] During the meal,

[0182] P i is the peeling force (gf / in) when an acrylic tape is attached to the surface of a release layer and the acrylic tape is peeled from the release layer at a temperature of 180 ℃ and a speed of 0.3 m / min after 5 minutes at room temperature.

[0183] P ris the peeling force (gf / in) when an acrylic tape is attached to the surface of a release layer after irradiation with a light source for 1000 μs under a xenon flash lamp with a wavelength of 900 nm to 1100 nm and the acrylic tape is peeled from the release layer at a temperature of 180°C and a speed of 0.3 m / min.

[0184]

[0185] (2) Density of silicon element before and after light source irradiation (g / m) 3 ) and density change rate (%)

[0186] Each recycled release film was cut to a size of 2.54 cm x 2.54 cm to prepare a sample. Tape (3M adhesive tape) was attached once to the surface of the release layer of the prepared sample before and after light source irradiation, and then removed. The density of silicon elements present in the release layer of each sample was measured using XRF (LAB X-3500, manufactured by OXFORD).

[0187] The light source used in the investigation was a xenon flash lamp (XF750, Unilam Co., Ltd.) with a wavelength of 900 nm to 1100 nm, and the irradiation was performed for 1000 μs.

[0188] The density of silicon elements in the heterogeneous layer before and after the measured light source irradiation was substituted into Equation 2-1 below to obtain the silicon density change rate (%).

[0189] [Formula 2-1]

[0190] [(D i -D r ) / D i ] x 100(%)

[0191] During the meal,

[0192] D i The density of silicon elements present in the heterogeneous layer (g / m) was measured by attaching the tape once before irradiating the light source and then removing it. 3 ) and,

[0193] D rAfter irradiating the film with a xenon flash lamp of wavelength 900 nm to 1100 nm for 1000 ㎲, the film was attached with tape once and then removed, and the density of silicon elements present in the release layer (g / m) was measured. 3 )am.

[0194]

[0195] (3) Residual adhesion rate (%) and change in residual adhesion rate (ΔR p )

[0196] Each recycled release film was cut to a size of 10 cm x 2.54 cm to prepare a sample. TESA7475 acrylic adhesive tape was attached to the surface of the release layer and exposed to 20 g / cm2 at room temperature. 2 It was pressed for 24 hours under a load. The TESA7475 acrylic adhesive tape attached to the surface of the release layer was collected without contamination. The collected TESA7475 acrylic adhesive tape was attached to the surface of a polyethylene terephthalate (PET) substrate film with a flat and clean surface and pressed once with a 2 kg tape roller (ASTMD-1000-55T) in a reciprocating motion. The TESA7475 acrylic adhesive tape was peeled from the PET substrate film and the peeling force was measured.

[0197] Separately, unused TESA7475 acrylic adhesive tape was attached to the surface of a polyethylene terephthalate (PET) substrate film with a flat and clean surface, and the peeling force was measured after pressing it back and forth once with a 2 kg tape roller (ASTMD-1000-55T). Each measured peeling force was substituted into Equation 3-1 below to obtain the residual adhesion rate (%). In addition, the change in the residual adhesion rate on the surface of the release layer after attaching and removing the tape once before and after light irradiation (ΔR p ) was obtained by substituting it into Equation 4-1.

[0198] ·Measuring instrument: TESA 7475_HEIDON

[0199] ·Measurement method: 180° peeling angle, 0.3 m / min peeling speed

[0200] [Formula 3-1]

[0201] Residual adhesion rate (%) = [(Peel force measured when peeling off after adhering acrylic adhesive tape to the surface of the release layer) / (Peel force measured when peeling off after adhering unused acrylic adhesive tape to the surface of the base film) x 100]

[0202] [Formula 4-1]

[0203] Change in residual adhesion rate (ΔR p ) = R p1 -R p2

[0204] During the meal,

[0205] R p1 is the residual adhesion rate on the surface of the release layer after the tape is attached and removed once before the light source irradiation.

[0206] R p2 This is the residual adhesion rate of the surface of the release layer after the tape is attached and removed once after being irradiated for 1000 μs under a xenon flash lamp with a wavelength of 900 nm to 1100 nm.

[0207]

[0208] (4) Rub-off

[0209] The release layer of each recycled release film was rubbed back and forth 10 times with force applied with the thumb, and the degree of change in the surface of the release layer was observed visually. The rub-off properties were evaluated using the following criteria.

[0210] ◎: If there is no change

[0211] ○: If there is slight wear and tear but there is no problem in use

[0212] △: When the surface of the heteromorphic layer becomes cloudy

[0213] X: If the heteromorphic layer is peeled off

[0214] (5) Appearance observation

[0215] The appearance of the substrate film surface was observed visually. The appearance was evaluated using the following criteria.

[0216] ○: If the surface of the substrate film is clean

[0217] △: When the surface of the substrate film becomes cloudy

[0218] ⅹ: If residue remains on the surface of the base film and appears blotchy

[0219]

[0220]

[0221] Referring to Table 1, the release layer of the recycled release film manufactured by Examples 1 to 6 had a peel strength change rate of 97.5% or more before and after 1000 μs of light irradiation at a wavelength of 900 nm to 1100 nm. The release layer of the recycled release film manufactured by Examples 1 to 6 had a Si density change rate of 80% or more measured after attaching and removing the tape before and after irradiation at a wavelength of 900 nm to 1100 nm. The residual adhesion change rate of the recycled release film manufactured by Examples 1 to 6 before and after 1000 μs of light irradiation at a wavelength of 900 nm to 1100 nm was 83.3% or more, and was excellent in rub-off and appearance observation.

[0222] In comparison, the release layer of the recycled release film manufactured by Comparative Examples 1 to 6 had a peel strength change rate of 5% or less before and after irradiation with a light source for 1000 μs at a wavelength of 900 nm to 1100 nm. The Si density change rate measured after attaching and removing the tape before and after irradiation with a light source on the release layer of the recycled release film manufactured by Comparative Examples 1, 2, and 6 was 2.8% or less. After rub-off of the recycled release film manufactured by Comparative Example 7, the surface of the release layer appeared cloudy and the appearance appeared mottled with residue remaining.

[0223] From this, the recyclable release film of the present invention can easily peel off a silicone-based release layer, a non-silicon-based release layer, or both a silicone-based release layer and a non-silicon-based release layer, so that the substrate can be recycled.

Claims

1. Description; and A heterogeneous layer located on at least one side of the above-described substrate; A recyclable release film, wherein the above-mentioned release layer can be peeled off by light source irradiation at a wavelength of 900 nm to 1100 nm for 400 μs to 30 ms.

2. In paragraph 1, A recyclable release film in which the above release layer satisfies the peeling force change rate (%) expressed by the following equation 1: [Formula 1] [(P i -P r ) / P i ] x 100(%) ≥ 50% During the meal, P i is the peeling force (gf / in) when an acrylic tape is attached to the surface of a release layer and the acrylic tape is peeled from the release layer at a temperature of 180 ℃ and a speed of 0.3 m / min after 5 minutes at room temperature. P r is the peeling force (gf / in) when an acrylic tape is attached to the surface of a release layer after irradiation with a light source for 1000 μs under a xenon flash lamp with a wavelength of 900 nm to 1100 nm and the acrylic tape is peeled from the release layer at a temperature of 180°C and a speed of 0.3 m / min.

3. In paragraph 1, The above-mentioned release layer is a cured layer of a composition containing a release agent and an additive, A recycled release film, wherein the additive comprises at least one of an infrared absorber and a surfactant.

4. In paragraph 3, A recycled release film, wherein the release agent comprises a silicone-based compound, a non-silicon-based compound, or a mixture of a silicone-based compound and a non-silicon-based compound.

5. In paragraph 3, A recycled release film, wherein the infrared absorbent comprises at least one selected from a dithiol-based metal complex compound, a cyanine-based compound, a benzothiazole-based compound, a squarylium-based compound, a chroconium-based compound, a diimmonium-based compound, and a phthalocyanine-based compound.

6. In paragraph 3, A recycled release film, wherein the content of the infrared absorbent is 0.01 part by weight to less than 1 part by weight based on 100 parts by weight of the composition.

7. In paragraph 3, A recyclable release film, wherein the composition further comprises a catalyst.

8. In paragraph 7, A recyclable heteromorphic film, wherein the catalyst comprises at least one of a silicon-based catalyst and a non-silicon-based catalyst.

9. In paragraph 1, A recycled release film in which the release layer satisfies the silicon density change rate (%) expressed by the following equation 2 when measuring the density of silicon elements present in the release layer using XRF (X-Ray Fluorescence): [Formula 2] [(D i -D r ) / D i ] x 100(%) ≥ 80% During the meal, D i The density of silicon elements present in the heterogeneous layer (g / m) was measured by attaching the tape once before irradiating the light source and then removing it. 3 ) and, D r After irradiating the film with a xenon flash lamp of wavelength 900 nm to 1100 nm for 1000 ㎲, the film was attached with tape once and then removed, and the density of silicon elements present in the release layer (g / m) was measured. 3 )am.

10. In paragraph 1, A recycled release film having a thickness of the release layer of 0.01 ㎛ to 2 ㎛.

11. In paragraph 1, A recycled release film, wherein the above description does not contain an infrared absorber and an adhesive.

12. In paragraph 1, Change in residual adhesion ratio (ΔR) expressed by Equation 4 before and after the above light source irradiation p ) that satisfies the following requirements: [Formula 4] ΔR p = [(R p1 -R p2 )] ≥ 80% During the meal, R p1 is the residual adhesion rate of the surface of the release layer after the tape is attached and removed once before the light source irradiation. R p2 This is the residual adhesion rate of the surface of the release layer after the tape is attached and removed once after irradiation for 1000 μs under a xenon flash lamp with a wavelength of 900 nm to 1100 nm.

13. A device comprising a recycled release film according to any one of claims 1 to 12.

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