Release film and method for manufacturing laminated electronic components using the same

Abstract

This invention provides a release film that enables the molding of ceramic green sheets with fewer defects. [Solution] One embodiment of the present invention provides a release film comprising a base layer and a release layer disposed on one surface of the base layer and containing a cured product of a release composition, wherein the release layer has a silicon content (at%) ratio (Si / C) of 0.15 or more to 0.20 or less when surface analysis is performed using X-ray photoelectron spectroscopy (XPS), a surface hardness of 200 MPa or more to 300 MPa when measured by nanoindentation, and the other surface of the base layer facing the one surface has a centerline mean roughness (Ra) of 15 nm or less.

Description

[Technical Field]

[0001] This invention relates to a release film and a method for manufacturing a laminated electronic component using the same. [Background technology]

[0002] Generally, release films, which use a polyester film as a base material and have a release layer formed on it, are used to mold ceramic green sheets used in the manufacture of multilayer electronic components, such as multilayer ceramic capacitors (MLCCs).

[0003] Recently, in order to miniaturize MLCCs, the thickness of the ceramic green sheet has decreased, which has led to problems such as wrinkles and breakage defects occurring in the ceramic green sheet when it is separated from the release film.

[0004] Furthermore, while release films are generally produced using a roll-to-roll method, this method results in strong contact between the ceramic green sheet and the opposite side of the release film (the side opposite to the side where the release layer is placed), leading to the problem of damage to the ceramic green sheet.

[0005] Manufacturing MLCCs with damaged ceramic green sheets can induce short-circuit defects in the MLCCs, highlighting the need for research into release films that can mold ceramic green sheets with fewer defects. [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] One of the various objectives of the present invention is to provide a release film that can form ceramic green sheets with fewer defects.

[0007] However, the object of the present invention is not limited to the above-described content and can be more easily understood in the process of describing specific embodiments of the present invention. [Means for solving the problem]

[0008] One embodiment of the present invention provides a release film comprising a base layer and a release layer disposed on one surface of the base layer and containing a cured product of a release composition, wherein the release layer has a silicon content (at%) ratio (Si / C) of 0.15 or more and 0.20 or less when surface analysis is performed using X-ray photoelectron spectroscopy (XPS), a surface hardness of 200 MPa or more and 300 MPa or less measured by nanoindentation, and the other surface of the base layer facing the one surface has a centerline mean roughness (Ra) of 15 nm or less. [Effects of the Invention]

[0009] One of the various effects of the present invention is the provision of a release film that can be used to mold ceramic green sheets with fewer defects.

[0010] However, the diverse and beneficial advantages and effects of the present invention are not limited to those described above and can be more easily understood in the process of describing specific embodiments of the present invention. [Brief explanation of the drawing]

[0011] [Figure 1] This is a schematic cross-sectional view showing a release film according to one embodiment of the present invention. [Figure 2] This is a schematic cross-sectional view showing the state in which a ceramic green sheet is formed on the release film shown in Figure 1. [Figure 3] This is a schematic cross-sectional view of a laminated electronic component manufactured using a release film according to one embodiment of the present invention. [Modes for carrying out the invention]

[0012] Hereinafter, embodiments of the present invention will be described with reference to specific embodiments and the accompanying drawings. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. Also, the embodiments of the present invention are provided to more fully explain the present invention to ordinary technicians. Therefore, the shape and size of elements in the drawings may be enlarged or reduced (or emphasized or simplified) for a clearer explanation, and elements indicated by the same reference numerals in the drawings are the same elements.

[0013] And, in order to clearly explain the present invention in the drawings, parts not related to the explanation are omitted, and the sizes and thicknesses of each configuration shown in the drawings are arbitrarily shown for the convenience of explanation. Therefore, the present invention is not necessarily limited to what is shown in the drawings. Also, for components with the same function within the scope of the same concept, they will be described using the same reference numerals. Furthermore, throughout the specification, when a certain part "includes" a certain component, this means that, unless otherwise stated to the contrary, it does not exclude other components, but can further include other components.

[0014] And throughout the specification, "~ - based compound", "~ - based resin", "~ - based polymer", "~ - based polymer", "~ - based copolymer" are broad concepts that include all of "~ compound", "~ resin", "~ polymer", "~ polymer", "~ copolymer", and / or their derivatives. Also, the "compound" in this specification is a broad concept that includes all of "monoatomic molecule", "oligomer", and "polymer compound including homopolymer and copolymer". Also, unless otherwise specified in this specification, the unit "parts by weight" means the weight ratio between each component, and the unit "parts by mass" means the value obtained by converting the weight ratio between each component into solid content.

[0015] Release film FIG. 1 is a cross-sectional view schematically showing a release film according to an embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing a state in which a ceramic green sheet is formed on the release film of FIG. 1. The release film 100 according to an embodiment of the present invention may include a base material layer 110 and a release layer 120 disposed on one surface of the base material layer 110.

[0016] (Base material layer) The base material layer be a base material film or a base material sheet can . The base material layer 110 can be, for example, a polyester-based base material film. The polyester-based base material film can include, for example, one or more of polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. The polyester-based base material film can be obtained, for example, by polycondensing an aromatic dicarboxylic acid and an aliphatic glycol. Examples of the aromatic dicarboxylic acid include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, or oxycarboxylic acid. Examples of the aliphatic glycol include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1,4-cyclohexanedimethanol, or neopentyl glycol. The polyester-based base material film can also use two or three or more of the above dicarboxylic acid components and glycol components in combination. Further, the polyester-based base material film can be a uniaxially or biaxially stretched oriented film.

[0017] In consideration of heat resistance, chemical resistance, strength, and economic efficiency, etc., the base material layer 110 can be a polyethylene terephthalate (PET) film. The PET film can be formed, for example, by polycondensing terephthalic acid and ethylene glycol, and can be formed, for example, using a direct method using terephthalic acid, but the present invention is not limited thereto.

[0018] The other surface of the substrate layer 110 facing the surface on which the release layer 120 is placed can have a center-line average roughness (Ra, hereinafter referred to as Ra1) of 15 nm or less. If the center-line average roughness (Ra1) of the other surface of the substrate layer 110 is within the above range, the other surface of the substrate layer 110 can be remarkably smooth.

[0019] When the release film 100 is produced using a roll-to-roll method, the ceramic green sheet GS and the opposite side of the substrate layer 110 where the release layer 120 is placed (hereinafter referred to as the other side of the substrate layer) may come into strong contact. In this case, if the centerline average roughness (Ra1) of the other side of the substrate layer 110 is too high, it may damage the ceramic green sheet GS, and the quality of the laminated electronic component may deteriorate due to the damaged ceramic green sheet GS. According to one embodiment of the present invention, by ensuring that the centerline average roughness (Ra1) of the other side of the substrate layer 110 is 15 nm or less, damage to the ceramic green sheet GS can be prevented and the quality of the laminated electronic component can be improved. The lower limit of the centerline average roughness (Ra1) of the other side of the substrate layer 110 is not particularly limited, but for example it can be greater than 0 nm. Alternatively, in order to improve the windability of the release film 100, the centerline average roughness (Ra1) of the other side of the substrate layer 110 can be 5 nm or more.

[0020] The maximum height roughness (Rmax, hereinafter referred to as Rmax1) of the other surface of the substrate layer 110 can be, for example, 300 nm or less. If the maximum height roughness (Rmax1) of the other surface of the substrate layer 110 is within the above range, the other surface of the substrate layer 110 can be remarkably smooth. By satisfying the maximum height roughness (Rmax1) of the other surface of the substrate layer 110 being 300 nm or less, damage to the ceramic green sheet GS can be prevented and the quality of the laminated electronic component can be improved. The lower limit of the maximum height roughness (Rmax1) of the other surface of the substrate layer 110 is not particularly limited and can be, for example, greater than 0 nm. Alternatively, in order to improve the windability of the release film 100, the maximum height roughness (Rmax1) of the other surface of the substrate layer 110 can be 50 nm or more.

[0021] If the average centerline roughness (Ra1) of the other surface of the substrate layer 110 is 15 nm or less, and the maximum height roughness (Rmax1) of the other surface of the substrate layer 110 is 300 nm or less, the damage prevention effect of the ceramic green sheet GS of the present invention can be further enhanced.

[0022] In one embodiment, the centerline mean roughness (Ra, hereinafter referred to as Ra2) of the surface on which the release layer 120 of the base layer 110 is placed can be greater than 0 nm and less than or equal to 15 nm. If the centerline mean roughness (Ra2) of the surface on which the release layer 120 of the base layer 110 is placed is greater than 15 nm, the release layer 120 may be damaged by protrusions of the base layer 110 during the winding process, which may induce dent damage to the ceramic green sheet GS after the molding is completed.

[0023] In one embodiment, when the centerline average roughness (Ra) of the surface of the release layer that comes into contact with the ceramic green sheet GS during molding is Ra3, the ratio of the centerline average roughness (Ra3) of the surface of the release layer to the centerline average roughness (Ra1) of the other surface of the base layer 110 (Ra3 / Ra1) can be 0.05 or more and 0.95 or less. When Ra3 / Ra1 satisfies the above range, defects such as dents in the ceramic green sheet GS can be suppressed.

[0024] On the other hand, in this specification, the centerline mean roughness (Ra) and the maximum height roughness (Rmax) can be measured based on the ISO 25178 (Geometric Product Specifications (GPS) - Surface texture: area) standard. The centerline mean roughness (Ra) and the maximum height roughness (Rmax) can be measured, for example, using a three-dimensional contact surface roughness measuring instrument.

[0025] To adjust the slipperiness and surface roughness of the release film 100, the base layer 110 may contain one or more particles from, for example, silica, silicon oxide, calcium carbonate, calcium sulfate, calcium phosphate, magnesium carbonate, magnesium phosphate, barium carbonate, kaolin, aluminum oxide, and titanium oxide. The shape of the particles can be, for example, spherical, lumpy, rod-shaped, or plate-shaped, but there are no limitations on the shape of the particles used.

[0026] If necessary, two or more of the above particles may be used in parallel, and the average particle size of the particles used can be approximately 30 nm to 1 μm. If the average particle size is less than 30 nm, dispersion failure may occur, and if the average particle size exceeds 1 μm, the surface roughness of the substrate layer 110 may increase, potentially inducing damage to the ceramic green sheet GS.

[0027] The thickness ts of the base layer 110 is not particularly limited, but for example, it can be between 10 μm and 200 μm. By having a thickness ts of 10 μm or more, thermal deformation of the base layer 110 can be suppressed. Furthermore, by having a thickness ts of 200 μm or less, the amount of base layer 110 to be discarded after use can be reduced, thereby reducing the environmental burden.

[0028] (Release layer) The release layer 120 may include a cured product of the release composition. The release composition may include, for example, polydimethylsiloxane and a cyclic compound.

[0029] 1. Polydimethylsiloxane Polydimethylsiloxane can be an additive to impart release properties to the release layer 120. Polydimethylsiloxane can bond with the cyclic compound to improve the durability of the release layer 120. The polydimethylsiloxane contained in the release composition may have polar functional groups.

[0030] The above polar functional groups can be introduced to one or both ends of the polydimethylsiloxane, and the number of positions in which the polar functional groups are introduced can be one or more. The polydimethylsiloxane may have one or more of the following polar functional groups: hydroxyl group, carboxyl group, amino group, amine group, carbonyl group, acrylic group, acryloyl group, nitrile group, vinyl group, halogen group, urethane group, and ester group. The polydimethylsiloxane contained in the above release composition may have, for example, a hydroxyl group for bonding with a cyclic compound.

[0031] The content of the polydimethylsiloxane contained in the above release composition may be, for example, 1 part by weight or more and 15 parts by weight or less, based on 100 parts by weight of the total of the polydimethylsiloxane and the cyclic compound. The weight-average molecular weight of the polydimethylsiloxane contained in the above release composition does not need to be particularly limited, but may be 1,000 or more and 500,000 or less.

[0032] 2. Cyclic compounds The cyclic compound can be the main component of the release layer 120. The cyclic compound included in the release composition may include one or more aromatic compounds and heteroaromatic compounds. The cyclic compound can give the release layer 120 a high elastic modulus, thereby preventing defects such as bending of the ceramic green sheet GS (so-called wrinkle defects) when the ceramic green sheet GS molded on the release layer 120 is peeled off.

[0033] The cyclic compound may include, for example, one or more melamine compounds, pyridine compounds, naphthalene compounds, and benzene compounds. More preferably, the cyclic compound may include one or more melamine compounds, pyridine compounds, and naphthalene compounds. The melamine compound may include the compound represented by the following chemical formula 1, its polymer, its copolymer, and / or derivative thereof. [C1] [ka] (Here, X represents a hydrogen atom or -CH2-O-R , , and they can be the same or different from each other. R 1 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and they can be the same or different from each other.)

[0034] The pyridine-based compound can include a compound represented by the following Chemical Formula 2, its polymer, its copolymer, and / or its derivative. [Chemical Formula 2] [Chemical Structure] (Here, Y represents -NH2, -OH, -COOH, -CH2-O-R 2 , -CONR 3 2 or a phenyl group substituted with a carboxy group, and they can be the same or different from each other. R 2 and R 3 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and they can be the same or different from each other.)

[0035] The naphthalene-based compound can include a compound represented by the following Chemical Formula 3, its polymer, its copolymer, and / or its derivative. [Chemical Formula 3] [Chemical Structure] (Here, Z1 represents -NH2, -OH, -COOH, -CH2-O-R<00​​​​​​​​​​​​​ [ka] (Here, Z2 is -NH2, -OH, -COOH, -CH2-OR 6 ,-CONR 7 R represents a phenyl group substituted with 2 or a carboxyl group, which can be the same or different. 6 and R 7 (This represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and these can be the same or different.)

[0037] 3. Acid catalysts and solvents The above-mentioned release composition may further contain an acid catalyst and a solvent in addition to the above-mentioned components. The acid catalyst can play a role in promoting the crosslinking reaction with the cyclic compound contained in the above-mentioned release composition.

[0038] The above acid catalyst may contain, for example, one or more of methanesulfonic acid, trifluoromethanesulfonic acid, isoprenesulfonic acid, camphorsulfonic acid, hexanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, decanesulfonic acid, hexadecanesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, p-toluenesulfonic acid, melaminetrisulfonic acid, cumenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and nonylnaphthalenesulfonic acid, but the present invention is not limited thereto.

[0039] The amount of acid catalyst added can be, for example, 0.1 to 10 parts by weight per 100 parts by weight of the cyclic compound. If the acid catalyst content is less than 0.1 parts by weight, the curing reaction may be slowed, and if it exceeds 10 parts by weight, the storage stability of the release composition may decrease.

[0040] The solvent can be any solvent that is compatible with the cyclic compound. The solvent may include, for example, one or more of the following: acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, methanol, ethanol, butanol, isopropyl alcohol, isobutyl alcohol, ethyl acetate, butyl acetate, propyl acetate, isopropyl acetate, hexane, heptane, octane, and isooctane.

[0041] In addition, the above release composition may further contain a binder, a conductivity enhancer, a pH adjuster, and / or a surfactant, to the extent that it does not alter the properties of the release layer.

[0042] 4. Characteristics of the release layer When surface analysis of the release layer 120 is performed using X-ray photoelectron spectroscopy (XPS), the ratio of silicon content (at%) to carbon content (at%) (Si / C) can be between 0.15 and 0.20. In the XPS analysis of the surface of the release layer 120, the silicon (Si) content can be attributed mostly to polydimethylsiloxane.

[0043] In this case, if the ratio of silicon content to carbon content is less than 0.15, the release properties will be insufficient, resulting in a problem of high peeling force, which may cause defects in which the ceramic green sheet GS does not peel off the release film 100 (so-called non-peeling defects). If the ratio of silicon content to carbon content is greater than 0.20, wrinkle defects may occur in which the ceramic green sheet GS folds when peeled off.

[0044] The release layer 120 may contain silicon (Si), carbon (C), nitrogen (N), and oxygen (O). In one embodiment, the release layer 120 does not need to contain substantially fluorine (F). This makes it possible to provide an environmentally friendly halogen-free release film 100. In this specification, "substantially fluorine-free" may mean that fluorine (F) components are not intentionally added to the release composition that forms the release layer. For example, in the manufacturing process of the release layer 120, it is possible that very small amounts of fluorine components may be unexpectedly present. Taking this into consideration, the ratio of fluorine (F) content (at%) to silicon (Si) content (at%) (F / Si) of the release layer 120 can be 0.01 or less when surface analysis is performed using XPS.

[0045] The release layer 120 can have a surface hardness of 200 MPa or more and 300 MPa or less, as measured by nanoindentation. If the surface hardness of the release layer 120 as measured by nanoindentation is less than 200 MPa, a problem may arise in which the hardness of the surface of the release layer 120 is low, and when the ceramic green sheet GS is peeled off from the release film 100, wrinkle defects such as folding of the ceramic green sheet GS may occur. If the surface hardness of the release layer 120 as measured by nanoindentation is greater than 300 MPa, the hardness of the surface of the release layer 120 will be high, or fracture defects of the ceramic green sheet GS may occur.

[0046] In one embodiment, the surface energy of the release layer 120 can be 28 mN / m or more and 30 mN / m or less. The surface energy of the release layer 120 is related to the applicability and peeling force of the release layer 120. Specifically, the higher the surface energy of the release layer 120, the better the applicability of the ceramic slurry applied on the release layer 120, and the lower the surface energy of the release layer 120, the better the peeling force of the release film 100.

[0047] If the surface energy of the release layer 120 is less than 28 mN / m, the wettability and smoothness may decrease when applying the ceramic slurry onto the release layer 120. Furthermore, if the surface energy of the release layer 120 exceeds 30 mN / m, the peeling force of the release film 100 may increase excessively, potentially resulting in unpeeled defects.

[0048] The thickness (tr) of the release layer 120 does not need to be particularly limited. The thickness (tr) of the release layer 120 can be between 75 nm and 250 nm, taking into consideration the release performance and the smoothness of the release layer surface. Here, the thickness (tr) of the release layer 120 can mean the average thickness of the release layer 120. For example, the average thickness of the release layer 120 can be determined by measuring the thickness of the release layer 120 five times while moving the observation position using a scanning electron microscope (SEM) or transmission electron microscope (TEM), and then calculating the average value.

[0049] Manufacturing method for multilayer electronic components Figure 3 is a schematic cross-sectional view showing a laminated electronic component 200 manufactured using a release film according to one embodiment of the present invention.

[0050] The multilayer electronic component 200 may include a body 210 containing a dielectric layer 211 and internal electrodes 221 and 222, and external electrodes 231 and 232 disposed outside the body 210 and connected to the internal electrodes 221 and 222. More specifically, the multilayer electronic component 200 may include a first external electrode 231 connected to a first internal electrode 221 and a second external electrode 232 connected to a second internal electrode 222.

[0051] Furthermore, the main body 210 may include a capacitance forming section in which capacitance is formed by first internal electrodes 221 and second internal electrodes 222 that are alternately arranged with a dielectric layer 211 in between, and cover sections 212 and 213 arranged on both sides of the capacitance forming section facing the first direction.

[0052] The following describes an example of a method for manufacturing a laminated electronic component 200 using a release film 100 according to one embodiment of the present invention. The release film 100 according to the aforementioned embodiment of the present invention can be used as a carrier film for forming a ceramic green sheet GS.

[0053] (Dielectric layer) First, ceramic powder is prepared to form the dielectric layer 211. The ceramic powder is not particularly limited as long as sufficient capacitance can be obtained, but for example, barium titanate-based materials, lead-composite perovskite-based materials, or strontium titanate-based materials can be used, and examples of the above ceramic powders include BaTiO3, (Ba 1-x Ca x )TiO3(0 <x<1)、Ba(Ti 1-y Ca y )O3(0 <y<1)、(Ba 1-x Ca x )(Ti 1-y Zr y )O3(0 <x<1、0<y<1)、Ba(Ti 1-y Zr y )O3(0 <y<1)、CaZrO3、または(Ca 1-x Sr x )(Zr 1-y Ti y Examples include )O3 (0≦x≦0.5, 0≦y≦0.5). Among the above ceramic powders, BaTiO3 can be synthesized, for example, by reacting a titanium raw material such as titanium dioxide with a barium raw material such as barium carbonate. The above ceramic powders can be synthesized by methods such as the solid-phase method, the sol-gel method, and the hydrothermal synthesis method, but the present invention is not limited to these.

[0054] Next, a ceramic slurry can be produced by mixing ceramic powder, an organic solvent such as ethanol, and a binder such as polyvinyl butyral. Thereafter, the ceramic slurry can be applied to and dried on a release film 100 according to one embodiment of the present invention to form a ceramic green sheet GS. The average thickness (tg) of the ceramic green sheet GS is not particularly limited, but can be, for example, 0.5 μm to 5.0 μm.

[0055] (Internal electrode) Next, an internal electrode pattern can be formed on the ceramic green sheet GS. The internal electrode pattern can be formed by firing to create internal electrodes 221 and 222. The internal electrode pattern can be formed by printing a conductive paste for internal electrodes, containing metal powder, a binder, etc., to a predetermined thickness on the ceramic green sheet GS using a screen printing method or gravure printing method. The metal powder may include, for example, one or more of Ni, Cu, Pd, Ag, Au, Pt, Sn, W, Ti, and alloys thereof, but the present invention is not limited thereto.

[0056] (Lamination and cutting) Next, after peeling the ceramic green sheet GS on which the internal electrode pattern is formed from the release film 100, multiple ceramic green sheets GS can be laminated and pressed together to form a ceramic laminate. Furthermore, in order to form the cover portions 212 and 213 after firing, a predetermined number of ceramic green sheets GS without the internal electrode pattern printed on them can be laminated on the upper and lower parts of the ceramic laminate.

[0057] On the other hand, the ceramic laminate can be cut to a predetermined chip size as needed. Furthermore, binders and other materials contained in the ceramic laminate or the cut chips can preferably be removed through a de-bindering process. The conditions for the de-bindering process can vary depending on the type of binder used and are not particularly limited.

[0058] Thereafter, the ceramic laminate or cut chip can be fired. The firing temperature is not particularly limited, but for example, it can be between 1000°C and 1300°C. The ceramic laminate or cut chip can become a body 210 including a dielectric layer 211 and internal electrodes 221 and 222 by firing.

[0059] (external electrode) Finally, external electrodes 231 and 232 can be formed. First, the main body 210 can be dipped in a conductive paste containing metal powder and glass, and then fired to form electrode layers 231a and 232a. At this time, the firing temperature can be, for example, 700°C to 900°C. On the other hand, the electrode layers 231a and 232a can consist only of fired electrode layers containing metal and glass, but the present invention is not limited thereto, and the electrode layers 231a and 232a can have a multilayer structure. For example, the electrode layers 231a and 232a can include a fired electrode layer containing metal and glass, and a resin electrode layer disposed on the fired electrode layer containing metal particles and resin.

[0060] Next, plating layers 231b and 232b can be formed using electrolytic plating and / or electroless plating. Plating layers 231b and 232b can be plating layers containing Ni, Sn, Pd and / or alloys containing these, and can be formed in multiple layers. For example, plating layers 231b and 232b can be in a form in which a Ni plating layer and a Sn plating layer are formed sequentially.

[0061] However, the manufacturing method described above is just one example, and the manufacturing method of the stacked electronic component 200 is not limited to the method described above.

[0062] The configuration of the present invention and its effects will be described in more detail below through examples and comparative examples. However, it is obvious that the following examples are provided to illustrate the present invention more specifically, and the scope of the present invention is not limited to the following examples.

[0063] Examples (Example 1-1) A release composition was prepared by adding 11 parts by weight of polydimethylsiloxane (PDMS), 89 parts by weight of melamine, and 0.5 parts by weight of p-toluenesulfonic acid catalyst to an isopropyl alcohol solvent, based on a total of 100 parts by weight of polydimethylsiloxane (PDMS) and melamine. The above release composition was applied to a polyester substrate film and cured by heat treatment in a hot air dryer at 120°C for 1 minute. This produced a release film by forming a release layer with an average thickness of 250 nm after curing.

[0064] (Examples 1-2) The release film was manufactured in the same manner as in Example 1-1, except that 3 parts by weight of polydimethylsiloxane and 97 parts by weight of melamine were used, based on a total of 100 parts by weight of polydimethylsiloxane and melamine, and the average thickness of the release layer after curing was 130 nm.

[0065] (Examples 1-3) The release film was manufactured in the same manner as in Example 1-1, except that 9 parts by weight of polydimethylsiloxane and 91 parts by weight of melamine were used, based on a total of 100 parts by weight of polydimethylsiloxane and melamine, and the average thickness of the release layer after curing was 155 nm.

[0066] (Examples 1-4) The release film was manufactured in the same manner as in Example 1-1, except that 1 part by weight of polydimethylsiloxane and 99 parts by weight of melamine were used, based on a total of 100 parts by weight of polydimethylsiloxane and melamine, and the average thickness of the release layer after curing was 170 nm.

[0067] (Example 2-1) Ammeline was used as the cyclic compound instead of melamine. The release film was manufactured in the same manner as in Example 1-1, except that 15 parts by weight of polydimethylsiloxane and 85 parts by weight of ammeline were used based on a total of 100 parts by weight of polydimethylsiloxane and ammeline, and the average thickness of the release layer after curing was 150 nm.

[0068] (Example 2-2) The release film was manufactured in the same manner as in Example 2-1, except that 5 parts by weight of polydimethylsiloxane and 95 parts by weight of amerin were used, based on a total of 100 parts by weight of polydimethylsiloxane and amerin, and the average thickness of the release layer after curing was 90 nm.

[0069] (Example 3-1) Naphthalene-2,7-diamine was used as the cyclic compound instead of melamine. The release film was manufactured in the same manner as in Example 1-1, except that 2 parts by weight of polydimethylsiloxane and 98 parts by weight of naphthalene were used, based on a total of 100 parts by weight of polydimethylsiloxane and naphthalene, and the average thickness of the release layer after curing was 75 nm.

[0070] (Example 3-2) The release film was manufactured in the same manner as in Example 3-1, except that 14 parts by weight of polydimethylsiloxane and 86 parts by weight of naphthalenediamine were used, based on a total of 100 parts by weight of polydimethylsiloxane and naphthalenediamine, and the average thickness of the release layer after curing was 130 nm.

[0071] (Example 4-1) Dicarboxyphenylpyridine (3,5-di(3-carboxyphenyl)pyridine) was used as the cyclic compound instead of melamine. The release film was manufactured in the same manner as in Example 1-1, except that 1.5 parts by weight of polydimethylsiloxane and 98.5 parts by weight of dicarboxyphenylpyridine were used based on a total of 100 parts by weight of polydimethylsiloxane and dicarboxyphenylpyridine, and the average thickness of the release layer after curing was 120 nm.

[0072] (Example 4-2) The release film was manufactured in the same manner as in Example 4-1, except that 13 parts by weight of polydimethylsiloxane and 87 parts by weight of dicarboxyphenylpyridine were used, based on a total of 100 parts by weight of polydimethylsiloxane and dicarboxyphenylpyridine, and the average thickness of the release layer after curing was 230 nm.

[0073] The composition, content, and average thickness of the release layers for Examples 1-1 to 4-2 are summarized in Table 1 below.

[0074] [Table 1]

[0075] (Comparative Example 1-1) The release film was manufactured using the same method as in Example 1-1, except that 17 parts by weight of polydimethylsiloxane and 83 parts by weight of melamine were used, based on a total of 100 parts by weight of polydimethylsiloxane and melamine, and the average thickness of the release layer after curing was 100 nm.

[0076] (Comparative Example 1-2) The release film was manufactured in the same manner as in Comparative Example 1-1, except that polydimethylsiloxane was not used and only 100 parts by weight of melamine was used.

[0077] (Comparative Examples 1-3) A release film was manufactured in the same manner as in Comparative Example 1-1, except that a release composition consisting of 100 parts by weight of polydimethylsiloxane and melamine was used, with 1.5 parts by weight of polydimethylsiloxane, 98.5 parts by weight of melamine, and 1 part by weight of p-toluenesulfonic acid catalyst being used, and the release composition was subjected to a curing heat treatment in a hot air dryer at 120°C for 2 minutes.

[0078] (Comparative Examples 1-4) The release film was manufactured using the same method as in Comparative Example 1-1, except that 7 parts by weight of polydimethylsiloxane and 93 parts by weight of melamine were used, based on a total of 100 parts by weight of polydimethylsiloxane and melamine, and the average thickness of the release layer after curing was 140 nm.

[0079] (Comparative Example 2-1) Amelin was used as the cyclic compound instead of melamine. The release film was manufactured in the same manner as in Example 1-1, except that 21 parts by weight of polydimethylsiloxane and 79 parts by weight of amelin were used, based on a total of 100 parts by weight of polydimethylsiloxane and amelin, and the average thickness of the release layer after curing was 130 nm.

[0080] (Comparative Example 2-2) The release film was manufactured using the same method as in Comparative Example 2-1, except that 0.5 parts by weight of polydimethylsiloxane and 99.5 parts by weight of amerin were used, based on a total of 100 parts by weight of polydimethylsiloxane and amerin, and the average thickness of the release layer after curing was 375 nm.

[0081] (Comparative Example 2-3) A release film was manufactured using the same method as in Comparative Example 2-1, except that 3 parts by weight of polydimethylsiloxane, 97 parts by weight of amerin, and 1 part by weight of p-toluenesulfonic acid catalyst were used, based on a total of 100 parts by weight of polydimethylsiloxane and amerin; the release composition was subjected to a curing heat treatment in a hot air dryer at 120°C for 2 minutes; and the average thickness of the cured release layer was 180 nm.

[0082] (Comparative Example 3-1) Naphthalenediamine was used as the cyclic compound instead of melamine. The release film was manufactured in the same manner as in Example 1-1, except that 16 parts by weight of polydimethylsiloxane and 84 parts by weight of naphthalenediamine were used based on a total of 100 parts by weight of polydimethylsiloxane and naphthalenediamine, and the average thickness of the release layer after curing was 380 nm.

[0083] (Comparative Example 3-2) The release film was manufactured using the same method as in Comparative Example 3-1, except that polydimethylsiloxane was not used and only 100 parts by weight of naphthalenediamine was used, and the average thickness of the release layer after curing was 200 nm.

[0084] (Comparative Example 3-3) The release film was manufactured using the same method as in Comparative Example 3-1, except that 18 parts by weight of polydimethylsiloxane and 82 parts by weight of naphthalenediamine were used, based on a total of 100 parts by weight of polydimethylsiloxane and naphthalenediamine, and the average thickness of the release layer after curing was 240 nm.

[0085] (Comparative Example 4-1) Dicarboxyphenylpyridine was used as the cyclic compound instead of melamine. The release film was manufactured in the same manner as in Example 1-1, except that 50 parts by weight of polydimethylsiloxane and 50 parts by weight of dicarboxyphenylpyridine were used based on a total of 100 parts by weight of polydimethylsiloxane and dicarboxyphenylpyridine, and the average thickness of the release layer after curing was 150 nm.

[0086] (Comparative Example 4-2) A release film was manufactured in the same manner as in Comparative Example 4-1, except that 5 parts by weight of polydimethylsiloxane, 95 parts by weight of dicarboxyphenylpyridine, and 1 part by weight of p-toluenesulfonic acid catalyst were used, based on a total of 100 parts by weight of polydimethylsiloxane and dicarboxyphenylpyridine; the release composition was subjected to a curing heat treatment in a hot air dryer at 120°C for 2 minutes; and the average thickness of the cured release layer was 130 nm.

[0087] (Comparative Example 4-3) A release film was manufactured in the same manner as in Comparative Example 4-1, except that 9 parts by weight of polydimethylsiloxane and 91 parts by weight of dicarboxyphenylpyridine were used, based on a total of 100 parts by weight of polydimethylsiloxane and dicarboxyphenylpyridine.

[0088] (Comparative Example 5-1 and Comparative Example 5-2) The release film was manufactured in the same manner as in Example 1-1, except that only 100 parts by weight of polydimethylsiloxane was used instead of cyclic compounds, and the average thickness of the release layer after curing was 50 nm.

[0089] The composition, content, and average thickness of the release layer for Comparative Examples 1-1 to 5-2 are summarized in Table 2 below.

[0090] [Table 2]

[0091] Physical property evaluation (XPS analysis) The surface of the release layer was analyzed using X-ray photoelectron spectroscopy (XPS). The XPS analysis was performed using a PHI Quantera SXM instrument in a vacuum environment. In the obtained XPS spectrum, the silicon content (at%) calculated in the 95 eV to 105 eV region and the carbon content (at%) calculated in the 275 eV to 295 eV region were measured. Subsequently, the ratio of silicon content to carbon content (Si / C) was calculated.

[0092] (Surface hardness measurement) After cutting the release film into 1cm x 1cm pieces, the release layer is analyzed using a nanoindenter analyzer (Anton Paar's UNHT). 3 The surface hardness was measured using a 3D printer under conditions of 25°C, 50% humidity, and an intrusion rate of 0.1 nm / sec.

[0093] (Surface energy measurement) After dropping distilled water and methylene iodide onto the surface of the release layer, the contact angle of the droplets formed on the surface of the release layer was measured using a Phoenix300Touch instrument. The measured contact angle values ​​were substituted into the Owens-Wendt model to calculate the surface energy.

[0094] (Measurement of surface roughness) The release film was cut to a size of 3 cm x 3 cm and then fixed to a glass plate. Subsequently, the centerline mean roughness (Ra1) and maximum height roughness (Rmax1) of the polyester substrate film on the side opposite to the side where the release layer was placed were measured using a Bruker 3D microscope, the Contour GTX instrument (measurement mode: PSI mode, measurement magnification: objective lens 20x, eyepiece: 2x) under conditions of 25°C and 50% humidity.

[0095] (Measurement of defect rate in lamination / delamination process) A ceramic slurry was applied to a release film and dried to form a ceramic green sheet. Subsequently, after peeling the ceramic green sheet from the release film, multiple ceramic green sheets were laminated and fired to produce sample chips. The total number of laminated ceramic green sheets was 300, and 10 sample chips each were produced for the example and comparative example, each consisting of 300 laminated ceramic green sheets.

[0096] Subsequently, the percentage of cases where the ceramic green sheet failed to peel off the release film (non-peeling defects) was measured for each example and comparative example. In addition, the percentage of cases where the ceramic green sheet peeled off the release film but was folded (wrinkled defects) and the percentage of cases where the ceramic green sheet broke were measured by observing the cross-section of the sample chips.

[0097] (Measurement of dent defect rate) After producing ceramic green sheets on the release films of the examples and comparative examples using a roll-to-roll method, the presence or absence of dents in the ceramic green sheets was checked using Bruker's Countour GTX 3D microscope. If even one dent with a depth of 100 nm or more occurred, it was judged as defective (NG), and if no dents with a depth of 100 nm or more occurred, it was judged as normal (OK).

[0098] (Measurement of short-circuit ratio) MLCCs were fabricated by laminating ceramic green sheets produced using the release films of the examples and comparative examples. After fabricating a total of 100 MLCCs for each example and comparative example, the capacitance of the MLCCs was measured under conditions of a frequency of 1 kHz and a voltage of 1 Vrms to check for the occurrence of short circuits.

[0099] The results of the physical property evaluation for Examples 1-1 to 4-2 are summarized in Table 3 below.

[0100] [Table 3]

[0101] Referring to Examples 1-1 to 4-2, it can be confirmed that when the release layer satisfies the requirement that the ratio of silicon content to carbon content (Si / C) is 0.15 or more and 0.20 or less during surface analysis using XPS, and the surface hardness measured by nanoindentation satisfies the requirement that it is 200 MPa or more and 300 MPa or less, virtually no defects in peeling, wrinkling, or fracture occur.

[0102] Furthermore, in Examples 1-1 to 4-2, it can be confirmed that dent defects do not occur if the average centerline roughness (Ra1) of the other surface of the substrate layer is 15 nm or less, or if the maximum height roughness (Rmax1) of the other surface of the substrate layer is 300 nm or less. This confirms that if MLCCs are manufactured using the release films of Examples 1-1 to 4-2, short-circuit defects in the MLCCs will hardly occur.

[0103] The results of the physical property evaluation for Comparative Examples 1-1 to 5-2 are summarized in Table 4 below.

[0104] [Table 4]

[0105] Referring to Comparative Examples 1-2, 2-2, and 3-2, it can be confirmed that when the ratio of silicon content to carbon content (Si / C) is less than 0.15 during surface analysis of the release layer using XPS, the release properties of the release layer are insufficient, resulting in defects where the mold does not peel off. Furthermore, referring to Comparative Examples 1-1, 2-1, 3-1, 3-3, 4-1, 5-1, and 5-2, it can be confirmed that when the ratio of silicon content to carbon content (Si / C) is greater than 0.2 during surface analysis of the release layer using XPS, the surface hardness and peeling force of the release layer are reduced, resulting in defects where the mold does not peel off. When MLCCs are manufactured using ceramic green sheets where defects where the mold does peel off occur, it can be confirmed that the shorting rate of the MLCCs increases excessively.

[0106] On the other hand, in Comparative Examples 1-3, 2-3, and 4-2, where the curing temperature was increased to increase the surface hardness of the release layer, it was confirmed that failures in the fracture of the ceramic green sheet occurred when the surface hardness of the release layer exceeded 300 MPa. On the other hand, in Comparative Examples 1-2, 1-3, 2-2, 2-3, 3-2, and 4-2, the MLCC manufacturing process could not be completed due to the large number of non-peelable and fractured defects, and therefore the shorting rate could not be measured.

[0107] Furthermore, referring to Comparative Examples 1-4, 2-3, 3-3, 4-3, and 5-2, it can be confirmed that if the centerline average roughness (Ra1) of the other side of the substrate layer exceeds 15 nm, or if the maximum height roughness (Rmax1) of the other side of the substrate layer exceeds 300 nm, indentation defects in the ceramic green sheet can be confirmed, and it can be confirmed that when MLCCs are manufactured using ceramic green sheets with indentation defects, the short-circuit rate of the MLCCs increases excessively.

[0108] In particular, comparing Comparative Example 5-1 and Comparative Example 5-2, it can be confirmed that even if the physical properties of the release layer are similar, if the centerline mean roughness (Ra) of the substrate layer exceeds 15 nm, dent defects occur in the ceramic green sheet and the short-circuit rate of the MLCC increases.

[0109] As a result, referring to Tables 3 and 4 above, it can be seen that the release films manufactured in Examples 1-1 to 4-2 are more suitable for the manufacturing process of laminated electronic components, particularly MLCCs.

[0110] The present invention is not limited by the embodiments described above and the accompanying drawings, but is limited by the claims provided. Therefore, various forms of substitution, modification, and alteration are possible by persons with ordinary skill in the art, without departing from the technical idea of ​​the present invention as described in the claims, and these also fall within the scope of the present invention.

[0111] Furthermore, the expression "one embodiment" used in this invention does not mean that each embodiment is identical to the others, but is provided to emphasize and describe the unique and distinct features of each embodiment. However, the above-presented embodiments do not preclude their realization in combination with the features of other embodiments. For example, even if a matter described in a particular embodiment is not described in another embodiment, it can be understood as a description related to the other embodiment, as long as there is no contradictory or contrary explanation of that matter in the other embodiment. [Explanation of symbols]

[0112] 100: Release film 110: Base material layer 120: Release layer 200: Stacked Electronic Components 210: Main unit 211: Dielectric layer 212, 213: Cover section 221, 222: Internal electrode 231, 232: External electrode

Claims

1. A base layer and The substrate layer is disposed on one surface of the substrate layer and includes a release layer containing a cured product of the release composition, The aforementioned release layer, when surface analysis is performed using X-ray photoelectron spectroscopy (XPS), has a silicon content (at%) ratio (Si / C) of 0.15 or more and 0.20 or less to carbon content (at%), and its surface hardness, measured by nanoindentation, is 200 MPa or more and 300 MPa or less. The other surface of the substrate layer facing the aforementioned surface has a center-line average roughness (Ra) of 15 nm or less. Release film.

2. The other surface of the aforementioned substrate layer has a maximum height roughness (Rmax) of 300 nm or less. The release film according to claim 1.

3. The surface energy of the release layer is 28 mN / m or more and 30 mN / m or less. The release film according to claim 1.

4. The average thickness of the release layer is 70 nm or more and 250 nm or less. The release film according to claim 1.

5. The aforementioned release composition comprises polydimethylsiloxane and a cyclic compound. The release film according to claim 1.

6. The cyclic compound comprises one or more aromatic compounds and heteroaromatic compounds. The release film according to claim 5.

7. The cyclic compound comprises one or more of the following: melamine compounds, pyridine compounds, and naphthalene compounds. The release film according to claim 5.

8. The content of the polydimethylsiloxane contained in the release composition is 1 part by weight or more and 15 parts by weight or less, based on 100 parts by weight of the total of the polydimethylsiloxane and the cyclic compound. The release film according to claim 5.

9. The release composition further comprises an acid catalyst and a solvent. The release film according to claim 5.

10. The release layer is substantially free of fluorine (F). The release film according to claim 1.

11. A step of forming a ceramic green sheet on a release film according to any one of claims 1 to 10, The steps include forming an internal electrode pattern on the ceramic green sheet, The steps include peeling the ceramic green sheet from the release film and stacking multiple ceramic green sheets to form a ceramic laminate, The step of firing the ceramic laminate is included. Manufacturing method for multilayer electronic components.

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