JP2015134476A - Mold release film, method for producing green sheet and method for producing multilayer ceramic electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a mold release film capable of producing a thin green sheet and preventing winding displacement during winding and the occurrence of blocking during storage, and to provide a method for producing a green sheet and a method for producing a multilayer ceramic electronic component.SOLUTION: There is provided a mold release film 1 which can be stored by winding in a roll shape on a core material, wherein the mold release film comprises: a base material film 11 having a first surface 11a and a second surface 11b; a release layer 12 provided on the first surface 11a of the base material film 11; and an application film (protective film) 20 releasably fixed on the second surface 11b of the base material film 11, and an outer surface 20a of the application film (protective film) 20 is a rough surface.

Description

  The present invention relates to a release film, a method for producing a green sheet, and a method for producing a multilayer ceramic electronic component, and more specifically, a release film capable of preventing the occurrence of blocking during winding and blocking during storage, The present invention relates to a green sheet manufacturing method and a multilayer ceramic electronic component manufacturing method.

  Conventionally, a release film used for manufacturing a multilayer ceramic capacitor has been proposed (see, for example, Patent Document 1). This release film has a base film and a release agent layer provided on the base film, and is wound up in a roll shape and transported and stored.

International Publication No. 2013/146295

  Incidentally, in recent years, there has been a demand for further miniaturization and thinning of electronic components such as multilayer ceramic capacitors, and there is an increasing demand for further thinning of green sheets. In a conventional green sheet manufacturing process, a release film having a green sheet formed on the surface is wound and transported and stored. For this reason, in order to further reduce the thickness of the green sheet, it is effective to increase the smoothness of the front and back surfaces of the release film in contact with the surface of the green sheet.

  However, when the smoothness of the front and back surfaces of the release film is increased, winding deviation occurs when the release film is wound into a roll shape, and the front and back surfaces of the release film wound into a roll shape are in close contact during storage. Blocking may occur.

  The present invention has been made in view of such a situation, and it is possible to produce a thin film green sheet, and further, release that can prevent winding deviation during winding and blocking during storage. It aims at providing the manufacturing method of a film, a green sheet, and the manufacturing method of a multilayer ceramic electronic component.

  The release film of the present invention is a release film that can be wound and stored on a core material in a roll shape, and has a base material having a first surface and a second surface, and the first surface of the base material. A release layer provided, and a protective layer fixed to the second surface of the base material in a peelable manner, and at least a portion of the outer surface of the protective layer is a rough surface. It is characterized by.

  According to this release film, since one surface of the release film is a rough surface, an appropriate gap is formed between the rough surface of the protective layer and the outer surface of the release layer when the release film is wound. It becomes possible to prevent air from being involved when winding the release film. As a result, it is possible to prevent the occurrence of winding deviation when the release film is wound around the core material in a roll shape and blocking during storage.

  In the release film of the present invention, the protective layer preferably has an arithmetic average roughness Ra of the outer surface of 10 nm or more and 200 nm or less, and a maximum protrusion height Rp of 60 nm or more and 2000 nm or less. With this configuration, since one surface of the release film becomes an appropriate rough surface, it is possible to prevent winding deviation when winding the release film and blocking during storage.

  In the release film of the present invention, the release layer preferably has an arithmetic average roughness Ra of the outer surface of less than 15 nm and a maximum protrusion height Rp of less than 100 nm. With this configuration, the smoothness of the outer surface of the release layer can be sufficiently obtained. Therefore, for example, when used in the manufacture of a green sheet, it is easy to reduce the thickness of the green sheet formed on the release layer.

  In the release film of the present invention, it is preferable that the base material has an arithmetic average roughness Ra of the second surface of less than 20 nm and a maximum protrusion height Rp of less than 150 nm. With this configuration, the smoothness of the second surface of the base material is sufficiently obtained. For example, when used in the manufacture of a green sheet, the base material on which the green sheet is formed and the release layer are wound up, Even when storing in a state where the two surfaces and the green sheet are in contact with each other, the green sheet can be prevented from being damaged by the uneven protrusions present on the second surface of the substrate.

  In the release film of the present invention, the protective layer preferably includes a support and a release layer provided on the support and releasably fixed on the second surface of the substrate. . With this configuration, the support is fixed on the second surface of the base material via the release layer, so that the peelability of the protective layer from the base material is improved.

  The green sheet manufacturing method of the present invention includes a first step of obtaining a first laminate by providing a green sheet on the release layer of the release film, and peeling the protective layer from the first laminate. It includes a second step of obtaining a second laminate, and a third step of winding the second laminate in a roll shape.

  According to this method for producing a green sheet, since a release film having one rough surface is used, even when a release film wound up in a roll shape is used for producing a green sheet, The trouble by blocking can be prevented. And since a protective layer is peeled after forming a green sheet on a mold release layer, even if it is a case where the 2nd layered product is rolled up, the 2nd surface of the protective layer at the time of winding and a green sheet It is possible to prevent the green sheet from being damaged due to contact with the.

  The method for producing a multilayer ceramic electronic component of the present invention is a lamination in which an internal electrode is provided on a green sheet produced by the green sheet production method, and the green sheet provided with the internal electrode is laminated to obtain an intermediate laminate. The method includes a step, a forming step of forming the intermediate laminate into a desired shape, and an external electrode forming step of forming an external electrode on the intermediate laminate.

  According to the method for manufacturing a multilayer ceramic electronic component, since the green sheet manufactured by the green sheet manufacturing method is used, the multilayer ceramic electronic component can be reduced in size and thickness by reducing the thickness of the green sheet. And since malfunctions, such as breakage of a green sheet, can be prevented, the reliability of a multilayer ceramic electronic component can be improved.

  According to the present invention, a thin film green sheet can be produced, and a release film that can prevent winding deviation during winding and blocking during storage, a method for producing a green sheet, and a multilayer ceramic An electronic component manufacturing method can be realized.

FIG. 1 is a schematic cross-sectional view of a release film according to an embodiment of the present invention. FIG. 2A is an explanatory diagram of the green sheet manufacturing method according to the embodiment of the present invention. FIG. 2B is an explanatory diagram of the green sheet manufacturing method according to the embodiment of the present invention. FIG. 3 is a schematic cross-sectional view of the multilayer ceramic capacitor according to the embodiment of the present invention. FIG. 4A is a process diagram of a method for manufacturing a multilayer ceramic capacitor according to an embodiment of the present invention. FIG. 4B is a process diagram of the method for manufacturing the multilayer ceramic capacitor according to the embodiment of the present invention. FIG. 4C is a process diagram of the method for manufacturing the multilayer ceramic capacitor according to the embodiment of the present invention. FIG. 4D is a process diagram of the method for manufacturing the multilayer ceramic capacitor according to the embodiment of the present invention.

  In order to produce a thin green sheet, the inventor needs to improve the smoothness of the front and back surfaces of the release film, while sufficiently improving the smoothness of the front and back surfaces of the release film. It was noticed that defects due to winding deviation when winding the film and blocking during storage may occur. And this inventor provides the smoothness of the front and back of a release film by providing in a state which can peel the protective layer which has a moderate rough surface in the surface on the opposite side to the release layer of a release film. Even in such a case, it was found that problems due to winding deviation when winding the release film and blocking during storage can be eliminated, and the present invention has been completed.

  Hereinafter, an embodiment of the present invention will be described in detail with reference to the accompanying drawings. In addition, it is not limited to each following embodiment, It can implement by changing suitably. Further, in the following, common constituent elements are denoted by the same reference numerals to avoid duplication of explanation.

  FIG. 1 is a schematic cross-sectional view of a release film 1 according to this embodiment. As shown in FIG. 1, the release film 1 according to the present embodiment can be transported and stored in a state of being wound in a roll shape, for example, and is unwound from a film roll and ceramic slurry on one surface. Is a release film that can be transported and stored in a state of being wound together with the manufactured green sheet after the green sheet is coated and dried. The release film 1 includes a carrier film 10 and an application film (protective layer) 20 provided on one main surface of the carrier film 10.

  The carrier film 10 includes a base film (base material) 11 having a first surface 11 a and a second surface 11 b, and a release layer 12 provided on the first surface 11 a of the base film 11. On the outer surface 12a of the release layer 12, for example, when used for manufacturing a green sheet, a green sheet is provided by applying and drying a ceramic slurry. By providing this release layer 12, it becomes easy to peel the carrier film 10 from the green sheet.

  On the second surface 11b of the base film 11, an application film 20 is provided. The application film 20 includes a support 21 and a release layer 22 provided on the support 21. The application film 20 is fixed to the second surface 11 b of the base film 11 by the release layer 22 so as to be peelable. Has been. The application film 20 has a rough surface such that an appropriate gap is formed between the outer surface 20a and the surface of the release layer 12 when the release film 1 is wound. For example, when used for manufacturing a green sheet, a ceramic slurry is applied and dried on the release layer 12 and then peeled off from the base film 11. The peeling layer 22 contains a material that can be peeled from the base film 11 such as a re-peelable pressure-sensitive adhesive and a pseudo-adhesive. Note that the release layer 22 is not necessarily provided as long as the support 21 of the application film 20 can be fixed to the second surface 11b of the base film 11 in a peelable manner.

  In the release film 1 according to the present embodiment, the arithmetic average roughness Ra of the outer surface 20a of the application film 20 is preferably 10 nm to 200 nm, and the maximum protrusion height Rp is preferably 60 nm to 2000 nm. . When the arithmetic average roughness Ra of the outer surface 20a of the application film 20 is 10 nm or more and 200 nm or less, the outer surface 20a of the application film 20 is appropriately roughened. Thus, when the release film 1 is wound around a core material made of paper, plastic, or metal in a roll shape, the outer surface 20a of the application film 20 and the outer surface 12a of the release layer 12 come into contact with each other. Even in this case, an appropriate gap is formed between the outer surface 20a of the application film 20 and the outer surface 12a of the release layer 12, so that air release during winding is improved and the release film 1 is wound. Misalignment can be prevented. Moreover, generation | occurrence | production of blocking in the front and back of the release film 1 wound by roll shape can be prevented by the moderate clearance gap between the outer surface 20a of the application film 20, and the outer surface 12a of the release layer 12. FIG.

  From the viewpoint of further improving the above-described effects, the arithmetic average roughness Ra of the outer surface 20a of the application film 20 is more preferably 11 nm or more, further preferably 12 nm or more, still more preferably 13 nm or more, and 150 nm or less. More preferably, it is more preferably 100 nm or less, and still more preferably 50 nm or less. Considering the above, the arithmetic average roughness Ra of the outer surface 20a of the application film 20 is more preferably 11 nm or more and 150 nm or less, further preferably 12 nm or more and 100 nm or less, and further preferably 13 nm or more and 50 nm or less.

  Moreover, if the maximum protrusion height Rp of the outer surface 20a of the application film 20 is 60 nm or more and 2000 nm or less, the outer surface 20a of the application film 20 becomes a moderately rough surface. Thus, when the release film 1 is wound around a core material made of paper, plastic, or metal in a roll shape, the outer surface 20a of the application film 20 and the outer surface 12a of the release layer 12 come into contact with each other. Even in this case, an appropriate gap is formed between the outer surface 20a of the application film 20 and the outer surface 12a of the release layer 12, so that air release during winding is improved and the release film 1 is wound. Misalignment can be prevented. Moreover, generation | occurrence | production of blocking in the front and back of the release film 1 wound by roll shape can be prevented by the moderate clearance gap between the outer surface 20a of the application film 20, and the outer surface 12a of the release layer 12. FIG.

  From the viewpoint of further improving the above-described effects, the maximum protrusion height Rp of the outer surface 20a of the application film 20 is more preferably 70 nm or more, further preferably 80 nm or more, still more preferably 85 nm or more, and 1500 nm or less. More preferably, 1000 nm or less is further preferable, and 750 nm or less is still more preferable. Considering the above, the maximum protrusion height Rp of the outer surface 20a of the application film 20 is more preferably 70 nm to 1500 nm, further preferably 75 nm to 1000 nm, and further preferably 80 nm to 750 nm.

  In the release film 1 according to the present embodiment, the release layer 12 preferably has an arithmetic average roughness Ra of the outer surface 12a of less than 15 nm and a maximum protrusion height Rp of less than 100 nm. . Since the smoothness of the outer surface 12a of the release layer 12 is sufficiently obtained if the arithmetic average roughness Ra of the outer surface 12a of the release layer 12 is less than 15 nm, the green sheet formed on the release layer 12 It is possible to prevent the occurrence of partial thickness variations, and it is easy to reduce the thickness of the green sheet.

  From the viewpoint of further improving the above-described effects, the arithmetic average roughness Ra of the outer surface 12a of the release layer 12 is more preferably 10 nm or less, still more preferably 7.5 nm or less, and even more preferably 5 nm or less. In addition, there is no restriction | limiting in particular about the lower limit of arithmetic mean roughness Ra of the outer surface 12a of the mold release layer 12, and it should just exceed 0 nm.

  Further, if the maximum protrusion height Rp of the outer surface 12a of the release layer 12 is less than 100 nm, the smoothness of the outer surface 12a of the release layer 12 can be sufficiently obtained and the protrusions of the outer surface 12a can be reduced. For example, when used in the production of a green sheet, it becomes possible to suppress variations in the thickness of the green sheet formed on the release layer 12 and the occurrence of pinholes, thereby improving the reliability of the green sheet.

  From the viewpoint of further improving the operational effects described above, the maximum protrusion height Rp of the outer surface 12a of the release layer 12 is more preferably 75 nm or less, still more preferably 50 nm or less, and even more preferably 25 nm or less. In addition, there is no restriction | limiting in particular about the lower limit of the maximum protrusion height Rp of the outer surface 12a of the mold release layer 12, and it should just exceed 0 nm.

  In the release film 1 of the present embodiment, the base film 11 preferably has an arithmetic average roughness Ra of the second surface 11b of less than 20 nm and a maximum protrusion height Rp of less than 150 nm. With this configuration, the smoothness of the second surface 11b of the base film 11 is sufficiently obtained. For example, when the base film 11 is used for manufacturing a green sheet, the base film 11 on which the green sheet is formed and the release layer 12 are rolled. Even when the second surface 11b of the base film 11 and the green sheet are kept in contact with each other, the green due to the uneven protrusions on the second surface 11b of the base film 11 is stored. Sheet damage can be prevented.

  From the viewpoint of further improving the above-described effects, the arithmetic average roughness Ra of the second surface 11b of the base film 11 is more preferably 18 nm or less, and further preferably 15 nm or less. In addition, there is no restriction | limiting in particular about the lower limit of arithmetic mean roughness Ra of the 2nd surface 11b of the base film 11, What is necessary is just to exceed 0 nm.

  Moreover, if the maximum protrusion height Rp of the second surface 11b of the base film 11 is less than 150 nm, sufficient smoothness of the second surface 11b of the base film 11 is obtained and the protrusions of the second surface 11b are reduced. Therefore, for example, when used in the manufacture of a green sheet, the base film 11 and the release layer 12 on which the green sheet is formed are rolled up so that the second surface 11b of the base film 11 and the green sheet are in contact with each other. Even when stored in contact with each other, the green sheet can be prevented from being damaged by the uneven protrusions present on the second surface 11b of the base film 11.

  From the viewpoint of further improving the above-described effects, the maximum protrusion height Rp of the second surface 11b of the base film 11 is more preferably 125 nm or less, and even more preferably 100 nm or less. In addition, there is no restriction | limiting in particular about the lower limit of the largest protrusion height Rp of the outer surface 12a of the mold release layer 12, What is necessary is just to exceed 0 nm. Hereinafter, various components of the release film 1 according to the present embodiment will be described in detail.

(Base film 11)
The base film 11 is not particularly limited as long as the effect of the present invention is achieved. As the base film 11, for example, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polypropylene and polymethylpentene, polycarbonate, polyvinyl acetate, and the like can be used. The base film 11 may be a single layer, or may be a multilayer of two or more layers of the same type or different types. Among these, the base film 11 is preferably a polyester film, more preferably a polyethylene terephthalate film, and still more preferably a biaxially stretched polyethylene terephthalate film. The polyethylene terephthalate film is less likely to generate dust during processing and use, and can effectively prevent, for example, defective coating of ceramic slurry due to dust or the like.

  The base film 11 may contain a filler in addition to the materials described above. Examples of the filler include silica, titanium oxide, calcium carbonate, kaolin, and aluminum oxide. These fillers may be used individually by 1 type, and may use 2 or more types together. By including such a filler, the mechanical strength of the base film 11 can be imparted, the slipperiness of the front and back surfaces can be improved, and blocking can be suppressed.

  As thickness of the base film 11, 10 micrometers or more and 300 micrometers or less are preferable, 15 micrometers or more and 200 micrometers or less are more preferable, and 20 micrometers or more and 125 micrometers or less are still more preferable.

(Release layer 12)
The release layer 12 is not particularly limited as long as the effects of the present invention are achieved. The release layer forming material used for forming the release layer 12 includes a silicone compound, a fluorine compound, an acrylic compound, an alkyd compound, and a long-chain alkyl group-containing compound having an alkyl group having 12 to 40 carbon atoms. Alternatively, thermoplastic resin materials such as olefin resin and diene resin can be used. These release layer forming materials are preferably thermosetting and active energy ray curable materials. Examples of the active energy rays include electromagnetic waves such as infrared rays, visible rays, ultraviolet rays, and X-rays, electron beams, ion beams, neutron rays, and particle rays such as α rays. Among these, as the active energy ray, ultraviolet rays are preferable from the viewpoint that the release layer 12 can be easily and reliably formed.

  Examples of the silicone compound described above include silicone compounds having organopolysiloxane as a basic skeleton. Examples of the silicone compound include thermosetting silicone compounds such as addition reaction type and condensation reaction type, and active energy ray curable silicone compounds such as ultraviolet ray curable type and electron beam curable type.

  Specific examples of the addition reaction type silicone compound described above include two alkenyl groups having 2 to 10 carbon atoms such as vinyl group, allyl group, propenyl group, and hexenyl group at the end and / or side chain of the molecule. The organopolysiloxane provided above is mentioned. When such an addition reaction type silicone compound is used, it is preferable to use a crosslinking agent and a catalyst in combination.

  Examples of the crosslinking agent described above include, for example, an organopolysiloxane having hydrogen atoms bonded to at least two silicon atoms in one molecule, specifically, a dimethylhydrogensiloxy group end-capped dimethylsiloxane-methylhydrogensiloxane copolymer. Examples thereof include a polymer, a trimethylsiloxy group end-capped dimethylsiloxane-methylhydrogensiloxane copolymer, a trimethylsiloxy group end-capped methylhydrogenpolysiloxane, and poly (hydrogensilsesquioxane).

  Further, the above-mentioned catalyst includes fine platinum, fine platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, palladium, rhodium and other white metal metals System compounds and the like. By using such a catalyst, the curing reaction of the composition for forming a release agent layer can be advanced more efficiently.

  Examples of the fluorine compound include a fluorine silicone compound, a fluorine boron compound, and a poly (perfluoroalkylene ether) chain-containing compound.

  As the acrylic compound, an acrylic compound having a crosslinked structure is generally used. The acrylic compound may be a modified product such as a long-chain alkyl-modified acrylic compound or a silicone-modified acrylic compound having an alkyl group having 12 to 40 carbon atoms.

  As the alkyd compound, an alkyd compound having a crosslinked structure is generally used. For the formation of the alkyd compound layer having a crosslinked structure, for example, a method of heat-curing a composition containing an alkyd compound, a crosslinking agent, and optionally a curing catalyst can be used. The alkyd compound may be a modified product such as a long-chain alkyl-modified alkyd compound or a silicone-modified alkyd compound having an alkyl group having 12 to 40 carbon atoms.

  As the long chain alkyl group-containing compound, for example, polyvinyl carbamate obtained by reacting a polyvinyl alcohol polymer with a long chain alkyl isocyanate having 12 to 40 carbon atoms in the alkyl group, polyethyleneimine, An alkylurea derivative obtained by reacting a long-chain alkyl isocyanate whose alkyl group has 12 to 40 carbon atoms is used.

  Examples of the active energy ray-curable release layer forming material include an active energy ray-curable compound (A) having a reactive functional group selected from a (meth) acryloyl group, an alkenyl group and a maleimide group, Those containing organosiloxane (B) are preferred. In the release layer 12 formed of this release layer forming material, the active energy ray-curable compound (A) and the polyorganosiloxane (B) having different molecular structures, polarities, and molecular weights are used. The polyorganosiloxane (B) is pushed up to the vicinity of the outer surface 12a of the release layer 12 before the release layer forming material is cured after application, and the components derived from the polyorganosiloxane (B) are segregated. Thereby, the mold release property of the mold release layer 12 can be improved.

<Active energy ray-curable compound (A)>
The active energy ray-curable compound (A) is a component that imparts curability to the release layer 12.
The active energy ray-curable compound (A) preferably has a reactive functional group selected from a (meth) acryloyl group, an alkenyl group and a maleimide group. Examples of the alkenyl group include alkenyl groups having 2 to 10 carbon atoms such as vinyl group, allyl group, propenyl group, and hexenyl group.

  The active energy ray-curable compound (A) preferably has three or more reactive functional groups in the molecule from the viewpoint of curability. By using the active energy ray-curable compound (A) having three or more reactive functional groups in the molecule, even with the release layer 12 having a thickness that is difficult to cure due to oxygen inhibition, excellent curability, Solvent and peelability can be obtained

  The reactive functional group content in the active energy ray-curable compound (A) is preferably 10 equivalents or more per kg of the active energy ray-curable compound (A). Thereby, even if it is a case where the mold release layer forming material is apply | coated with the thin film on the 1st surface 11a of the base film 11, the sclerosis | hardenability of an active energy ray hardening compound (A) becomes favorable.

  Examples of the active energy ray-curable compound (A) include dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and pentaerythritol. Polyfunctional (meth) acrylates such as tri (meth) acrylate and pentaerythritol tetra (meth) acrylate are exemplified. Among these, the active energy ray-curable compound (A) includes dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth). It is preferable to use at least one selected from the group consisting of acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate. Thereby, even if it is a case where the mold release layer forming material is apply | coated with the thin film on the 1st surface 11a of the base film 11, the sclerosis | hardenability of an active energy ray hardening compound (A) becomes favorable.

  The solid content of the active energy ray-curable compound (A) in the release layer forming material (content in the total solid content excluding the solvent) is preferably 65% by mass or more and 98.5% by mass or less. 71 mass% or more and 94 mass% or less are more preferable.

<Polyorganosiloxane (B)>
The polyorganosiloxane (B) is a component that imparts releasability to the release layer 12. Examples of the polyorganosiloxane (B) include those having a linear or branched molecular chain. In addition, the polyorganosiloxane (B) has a reactivity selected from a (meth) acryloyl group, an alkenyl group, and a maleimide group, directly or via a divalent linking group, on at least one of the molecular chain terminal and side chain. It is preferable to use a modified polyorganosiloxane having a functional group bonded to a silicon atom of the molecular chain. Examples of the alkenyl group include alkenyl groups having 2 to 10 carbon atoms such as vinyl group, allyl group, propenyl group, and hexenyl group. Examples of the divalent linking group include an alkylene group, an alkyleneoxy group, an oxy group, an imino group, a carbonyl group, and a divalent linking group obtained by combining these. The number of carbon atoms of the divalent linking group is preferably 1 or more and 30 or less, and more preferably 1 or more and 10 or less. Polyorganosiloxane (B) may be used independently and may use 2 or more types together.

  According to the modified organopolysiloxane, when the active energy ray-curable compound (A) is cured by irradiation with active energy rays, the modified organopolysiloxane has a crosslinked structure of the cured product of the active energy ray-curable compound (A). Built-in and fixed. Thereby, when using for manufacture of a green sheet, for example, it can control that polyorganosiloxane contained in mold release layer 12 moves to a green sheet provided on outer surface 12a of mold release layer 12.

  Examples of the organic group other than the reactive functional group of the polyorganosiloxane (B) include a monovalent hydrocarbon group having no aliphatic unsaturated bond. As this organic group, you may have two or more same type or different types. As a hydrocarbon group, a C1-C12 thing is preferable and a C1-C10 thing is more preferable. Examples of the hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, and a propyl group, and aryl groups such as a phenyl group and a tolyl group.

  As the polyorganosiloxane (B), 80 mol% or more of organic groups other than reactive functional groups in the molecule of the polyorganosiloxane (B) is a methyl group from the viewpoint of improving the releasability of the release layer 12. Some are preferred.

  The solid content of the polyorganosiloxane (B) in the release layer forming material is preferably 0.5% by mass or more and 5% by mass or less, and more preferably 0.7% by mass or more and 4% by mass or less. Thereby, for example, when used for the production of a green sheet, it becomes easy to apply on the base film 11 without repelling the ceramic slurry, and the releasability of the release film 1 is improved.

  Further, the blending amount of the active energy ray-curable compound (A) and the polyorganosiloxane (B) is (B) component / (A) component = 0.7 / 99.3 or more and 5/95 or less. It is preferable that (B) component / (A) component = 1/99 or more and 4.5 / 95.5 or less. Thereby, for example, when used for the production of a green sheet, it becomes easy to apply on the base film 11 without repelling the ceramic slurry, and the releasability of the release film 1 is improved.

<Photopolymerization initiator (C)>
The photopolymerization initiator (C) is a component that improves curability when the release layer forming material is cured using ultraviolet rays as active energy rays.

The photopolymerization initiator (C) is not particularly limited as long as the effects of the present invention are achieved. As the photopolymerization initiator (C), an α-aminoalkylphenone-based photopolymerization initiator is used from the viewpoint that the release layer forming material is excellent in curability in an air atmosphere and the release film 1 can be easily produced. preferable.
Examples of the α-aminoalkylphenone photopolymerization initiator include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopro from the viewpoint of excellent curability, solvent resistance, and releasability. Pan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone is preferred.

  The solid content of the photopolymerization initiator (C) in the release layer forming material is preferably 1% by mass or more and 20% by mass or less, and more preferably 3% by mass or more and 15% by mass or less. Thereby, even if the thickness of the release layer 12 is in a range where it is difficult to obtain curability due to oxygen inhibition, excellent curability, solvent resistance, and release properties can be obtained.

  In addition, as the release layer forming material, a material containing other components such as a sensitizer, an antistatic agent, a curing agent, and a reactive monomer can be used as long as the effects of the present invention are exhibited. As the sensitizer, 2,4-diethylthioxanthone and isopropylthioxanthone are preferable from the viewpoint of improving the curability of the release layer forming material. As solid content of another component, 0 mass% or more and 10 mass% or less are preferable.

  The thickness of the release layer 12 is preferably 0.3 μm or more and 2 μm or less. When the thickness of the release layer 12 is 0.3 μm or more, the surface of the release layer 12 is sufficiently smooth. For example, when used in the production of a green sheet, the pinhole and partial thickness of the green sheet Can be prevented. If the thickness of the release layer 12 is 2 μm or less, the release layer 12 can be prevented from shrinking when cured, and the release film 1 can be prevented from curling. Moreover, generation | occurrence | production of the blocking of the release film 1 can be prevented, the unwinding property of the release film 1 improves, and the charge amount at the time of unwinding can be reduced.

(Peeling layer 22)
The release layer 22 is not particularly limited as long as the effect of the present invention is achieved. As the release layer forming material used for forming the release layer 22, a re-peeling pressure-sensitive adhesive, a pseudo adhesive, or the like can be used.

  When the release layer forming material contains a re-peelable adhesive, adhesives such as silicone adhesives, acrylic adhesives, rubber adhesives, urethane adhesives, polyether adhesives, and polyester adhesives Is preferably used. Moreover, it is preferable to adjust adhesive force by containing an adhesive and a hardening | curing agent and making it harden | cure by a heat | fever or an active energy ray, or optimizing the molecular weight of an adhesive. Among these, urethane-based adhesives, silicone-based adhesives, and acrylic-based adhesives are preferable from the viewpoints of versatility and durability.

  Moreover, when the peeling layer forming material contains a pseudo adhesive, it is preferable to use, for example, a pseudo adhesive obtained by mixing a plurality of thermoplastic resins alone or in combination. Examples of the thermoplastic resin include polyolefin resins, polyester resins, acrylic resins, and polyvinyl acetate resins made of homopolymers or copolymers such as polyethylene, polypropylene, and polymethylpentene. In addition, various additives such as an antistatic agent, an ultraviolet absorber, a dye, a pigment, an antifoaming agent, a wetting agent, a lubricant, and a thickening agent can be added to the release layer forming material as necessary.

  The acrylic pressure-sensitive adhesive is preferably a polymer containing a structural unit derived from a (meth) acrylic acid ester monomer having an alkyl group having 1 to 20 carbon atoms, and a (meth) acrylic having an alkyl group having 1 to 20 carbon atoms. A blend of a copolymer obtained by copolymerization of an acid ester monomer with a copolymerizable monomer blended as necessary and a curing agent is preferred. The acrylic pressure-sensitive adhesive preferably has a glass transition temperature (Tg) of −70 ° C. or higher and 5 ° C. or lower.

  Examples of the (meth) acrylic acid ester monomer having an alkyl group with 1 to 20 carbon atoms include acrylics such as methyl acrylate, ethyl butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, and cyclohexyl acrylate. Acid alkyl esters and methacrylic acid alkyl esters such as butyl methacrylate, 2-ethylhexyl methacrylate and cyclohexyl methacrylate are used. In addition, as the acrylic pressure-sensitive adhesive, a commercially available acrylic pressure-sensitive adhesive (trade name “Olivein BPS5227-1”, manufactured by Toyochem Co., Ltd.) can be used.

  As the copolymerizable monomer, for example, vinyl acetate, vinyl propionate, vinyl ether, styrene, acrylonitrile are preferably used as monomers having no functional group. Moreover, examples of the copolymerizable monomer having a functional group include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, N-methylolacrylamide, hydroxyl group-containing monomers such as allyl alcohol, tertiary amino group-containing monomers such as dimethylaminopropyl (meth) acrylate, acrylamide, N N-substituted amide group-containing monomers such as methyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, and N-octylacrylamide, and epoxy group-containing monomers such as glycidyl methacrylate are preferably used.

  As the urethane pressure-sensitive adhesive, a polyurethane resin, a polyurethane urea resin, or the like can be used. Examples of the polyurethane resin include those obtained by adding an amine compound or the like to a urethane prepolymer obtained by reacting a polyol and a polyisocyanate. As the polyol, polyester polyol and polyether polyol are preferable, and those having two or more functional groups are preferably used. Examples of the polyisocyanate include aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate. These may be used alone or in combination of two or more. Moreover, as a urethane type adhesive, a commercially available urethane type adhesive type adhesive (Brand name "Siavine SH-101", the Toyochem company make) can also be used.

  Examples of the curing agent include isocyanate, epoxy, metal chelate compound, amine compound, hydrazine compound, aldehyde compound, metal alkoxide, and metal salt. Among these, isocyanate type and epoxy type are preferable. As the curing agent, a commercially available curing agent BXX8134 (manufactured by Toyochem) and a trimer of hexamethylene diisocyanate (trade name “Coronate 2030”, manufactured by Nippon Polyurethane Industry Co., Ltd.) can also be used.

  As a compounding quantity of the hardening | curing agent in the peeling layer forming material, 0.01 mass part or more and 20 mass parts or less are preferable with respect to 100 mass parts of adhesives, and 0.05 mass part or more and 10 mass parts or less are more. preferable.

  The thickness of the release layer 22 is preferably 1 μm to 200 μm, more preferably 2 μm to 100 μm, and still more preferably 3 μm to 50 μm.

(Support 21)
The support 21 is not particularly limited as long as the effect of the present invention is achieved, and the same material as the substrate film 11 described above can be used. Moreover, as thickness of the support body 21, 10 micrometers or more and 300 micrometers or less are preferable, 15 micrometers or more and 200 micrometers or less are more preferable, and 20 micrometers or more and 125 micrometers or less are still more preferable.

  Next, the manufacturing method of the release film 1 which concerns on this Embodiment is demonstrated. In the manufacturing method of the release film 1 according to the present embodiment, the base film 11 is formed on the release layer 22 of the application film 20 by the first step of producing the application film 20 by providing the release layer 22 on the support 21. A second step of fixing the second surface 11b to obtain an intermediate laminate, and a third step of providing the release layer 12 on the base film 11 of the laminate.

(First step)
In the first step, the release layer forming material is applied on one surface of the support 21 and, if necessary, dried and cured. As a result, the release layer 22 is formed on the support 21 to produce the application film 20.

In the case where the release layer forming material is a thermosetting type, for example, the release layer 22 is formed by heating and curing at 50 to 150 ° C. for 0.5 to 10 minutes. When the release layer forming material is an active energy ray-curable material, the release layer 22 is formed by irradiating the applied layer of the release layer forming material with an active energy ray and curing it. When the active energy ray is ultraviolet irradiation amount of ultraviolet rays, integrated light quantity is preferably from 50~1000mJ / cm ^2, and more preferably 100 to 500 mJ / cm ^2. When the active energy ray is an electron beam, the electron beam irradiation amount is preferably about 0.1 to 50 kGy.

  In the case where the release layer forming material is a heat melting type, for example, the release layer 22 is formed by melting at a temperature equal to or higher than the melting point of the release layer forming material, and cooling after application. As a method for applying the release layer forming material, for example, a gravure coating method, a bar coating method, a spray coating method, a knife coating method, a roll coating method, a die coating method, or the like can be used.

(Second step)
In the second step, an intermediate laminate is produced by laminating the release layer 22 of the obtained application film 20 and the second surface 11b of the base film 11 by lamination or the like.

(Third step)
In the third step, the release layer forming material is applied onto the first surface 11a of the base film 11 of the intermediate laminate, and is dried and cured as necessary. As a result, the release layer 12 is formed on the first surface 11a of the base film 11 of the intermediate laminate, and the release film 1 is produced.

In the case where the release layer forming material is a thermosetting type, for example, the release layer 12 is formed by heating and curing at 50 to 150 ° C. for 0.5 to 10 minutes. . When the release layer forming material is an active energy ray curable material, the release layer 12 is formed by irradiating and curing the active energy ray on the coating layer of the release layer forming material. . When the active energy ray is ultraviolet, the irradiation amount of integrated light quantity is preferably from 50~1000mJ / cm ^2, and more preferably 100 to 500 mJ / cm ^2. When the active energy ray is an electron beam, the electron beam irradiation amount is preferably about 0.1 to 50 kGy.

  In the case where the release layer forming material is a heat melting type, for example, the release layer 12 is formed by melting at a temperature equal to or higher than the melting point of the release layer forming material, and cooling after application. The release layer forming material forms the release layer 12 that is smoothed by filling the unevenness of the first surface 11 a of the base film 11. Examples of the method for applying the release layer forming material include a gravure coating method, a bar coating method, a spray coating method, a knife coating method, a roll coating method, and a die coating method.

  In addition, in embodiment mentioned above, although the application film 20 demonstrated the example comprised by the support body 21 and the peeling layer 22, it is not limited to this structure. The application film 20 may be configured only by the support 21 as long as the application film 20 can be smoothly peeled from the base film 11. Moreover, the peelability of the application film 20 can also be improved by providing a layer having a function of improving the peelability on the base film 11 side.

  Moreover, in embodiment mentioned above, although the base film 11 and the support body 21 demonstrated the example comprised by a single layer, it is not limited to this structure. The base film 11 and the support 21 may be configured as a laminate in which a plurality of films are laminated. In the case where the base film 11 and the support 21 are formed of a laminate, at least one layer may be an antistatic layer that prevents charging. Moreover, when the base film 11 is comprised with a laminated body, you may have a layer which improves the adhesiveness of the mold release layer 12 and the base film 11 in the surface layer by the side of the mold release layer 12. As shown in FIG. Moreover, the base film 11 may have a smooth layer that imparts smoothness to at least one of the surface layer on the release layer 12 side and the surface layer on the application film 20 side.

<Green sheet manufacturing method>
Next, with reference to FIG. 2A and FIG. 2B, the manufacturing method of the green sheet which concerns on this Embodiment is demonstrated. 2A and 2B are explanatory diagrams of the green sheet manufacturing method according to the present embodiment. The manufacturing method of the green sheet which concerns on this Embodiment provides the 1st process of providing the 1st laminated body 2 by providing the green sheet 31 on the release layer 12 of the release film 1 which concerns on the said embodiment, 1st A second step of removing the protective layer 20 from the laminate 2 to obtain the second laminate 3 and a third step of winding the second laminate 3 into a roll shape are included.

(First step)
As shown in FIG. 2A, in the first step, a ceramic slurry is applied and dried on the outer surface 12a of the release layer 12 of the release film 1 according to the above embodiment to provide a green sheet 31 to provide a first. A laminate 2 is obtained. As the ceramic slurry, for example, a ceramic powder, a dispersion medium (solvent), a dispersant, a binder, a plasticizer, and the like are blended in a desired ratio, and a medium type disperser such as a bead mill, a ball mill, an attritor, a paint shaker, or a sand mill. What was mixed and pulverized using can be used. Moreover, there is no restriction | limiting in particular as a coating method of ceramic slurry, For example, it is possible to apply to the mold release layer 12 by coating methods, such as a doctor blade method. The thickness of the green sheet 31 is not particularly limited, but is preferably 5 μm or less, more preferably 0.05 μm or more and 3 μm or less, and further preferably 0.1 μm or more and 3 μm or less.

(Second step)
In the second step, the protective layer 20 is peeled from the first laminate 2 to obtain the second laminate 3. The method for removing the protective layer 20 is not particularly limited as long as the method can peel the protective layer 20 from the first laminate 2.

(Third step)
In a 3rd process, the 2nd laminated body 3 in which the green sheet 31 was formed is wound up in roll shape around core materials (core material), such as paper, a plastics, or a metal. Since the 2nd surface 11b of the base film 11 is a smooth surface, the 2nd laminated body 3 is wound up in roll shape, and the outer surface of the green sheet 31 and the 2nd surface 11b of the base film 11 contact | abut. Even if it is a case, generation | occurrence | production of the pinhole in the surface of the green sheet 31 etc. can be suppressed.

<Method for producing multilayer ceramic electronic component>
Next, with reference to FIGS. 3-4D, the manufacturing method of the multilayer ceramic electronic component which concerns on this Embodiment is demonstrated. FIG. 3 is a schematic cross-sectional view of the multilayer ceramic capacitor according to the present embodiment, and FIGS. 4A to 4D are process diagrams of the method for manufacturing the multilayer ceramic capacitor according to the present embodiment. In the following, an example in which a multilayer ceramic capacitor is manufactured as a multilayer ceramic electronic component will be described. However, the present invention is applicable to manufacturing various electronic components other than the multilayer ceramic capacitor.

  As shown in FIG. 3, the multilayer ceramic capacitor 6 according to the present embodiment is formed by laminating a plurality of green sheets 31 and internal electrodes 32 provided on the green sheets 31. In the multilayer ceramic capacitor 6, a plurality of internal electrodes 32 are electrically connected by external electrodes 33 provided at both ends. Further, the plurality of internal electrodes 32 are electrically connected by a via hole (not shown) provided in the green sheet 31 and the internal electrode 32.

  The manufacturing method of the multilayer ceramic electronic component according to the present embodiment includes the green electrode 31 provided with the internal electrode 32 on the green sheet 31 manufactured by the manufacturing method of the green sheet 31 according to the above-described embodiment. It includes a laminating step for laminating sheets 31 to obtain an intermediate laminate, a molding step for molding the intermediate laminate into a desired shape, and an external electrode forming step for forming external electrodes on the intermediate laminate.

(Lamination process)
First, as shown to FIG. 4A, the carrier film 10 is removed from the green sheet 31 manufactured by the manufacturing method of the green sheet which concerns on the said embodiment. Next, a conductive paste or the like is applied on one main surface of the green sheet 31 to provide an internal electrode 32 to produce the internal electrode laminate 4. Next, as shown in FIG. 4B, the separately prepared internal electrode laminate 4 is sequentially laminated on the internal electrode 32 of the green sheet 31. Then, the intermediate laminate 5 is manufactured by laminating and pressing the green sheets 31 on which the electrodes are not disposed on the upper and lower surfaces of the internal electrode 32.

(Molding process)
In the molding step, as shown by the dotted line in FIG. 4C, the intermediate laminate is cut so as to have a desired shape (see FIG. 4D), and then the binder is removed and fired. The binder removal is performed by heat treatment in a nitrogen atmosphere. Firing is performed by heating to a predetermined temperature in a weakly reducing atmosphere.

(External electrode formation process)
Next, in the external electrode forming step, a conductive paste such as silver is applied and baked on both ends of the fired intermediate laminate 5 to form a conductive external electrode 33 that is electrically connected to the internal electrode 32. By doing so, a multilayer ceramic capacitor 6 as shown in FIG. 3 is obtained. Note that other multilayer ceramic electronic components such as a multilayer ceramic multilayer substrate can also be manufactured through a process of stacking green sheets to form a multilayer body, as in the case of the multilayer ceramic capacitor 6 described above.

  Hereinafter, the present invention will be described in more detail based on examples made to clarify the effects of the present invention. In addition, this invention is not limited at all by the following examples.

  The present inventors produced a release film according to the above embodiment and a film according to a comparative example, and evaluated the following items.

Example 1
As the support 21, a biaxially stretched polyethylene terephthalate film (thickness: 23 μm, arithmetic average roughness Ra of the first surface (inner surface): 40 nm, maximum protrusion height Rp of the first surface: 580 nm, arithmetic of the second surface The average roughness Ra was 40 nm, and the maximum protrusion height Rp of the second surface (outer surface 20a) was 580 nm.

  On this support 21, 100 parts by mass (solid content conversion) of acrylic adhesive (trade name “Olivein BPS5227-1”, manufactured by Toyochem Co., Ltd.) and 2 parts by mass of curing agent BXX8134 (manufactured by Toyochem Co., Ltd.) The release layer forming material mixed with the solid content is applied on the first surface of the support 21 with a die coater, dried and cured at 120 ° C. for 1 minute, and a thickness of 10 μm. A release layer 22 (adhesive layer) was formed to prepare an application film 20.

  As the base film 11, a biaxially stretched polyethylene terephthalate film (thickness: 38 μm, arithmetic average roughness Ra of the first surface 11a: 15 nm, maximum protrusion height Rp of the first surface 11a: 105 nm, arithmetic of the second surface 11b Average roughness Ra: 3 nm, maximum protrusion height Rp of second surface 11b: 15 nm) was used.

  Next, an intermediate laminate was produced by laminating the release layer 22 of the obtained application film 20 and the second surface 11b of the base film 11.

  Next, 94 parts by mass of dipentaerythritol hexaacrylate (solid content: 100% by mass) as the active energy ray-curable compound (A), and acrylic modified polydimethylsiloxane (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as the polyorganosiloxane (B) 1 part by weight of “X-22-164A”, solid content 100% by mass), and α-aminoalkylphenone photopolymerization initiator (C) as an α-aminoalkylphenone photopolymerization initiator (C), manufactured by BASF Name “IRGACURE907”, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, solid content of 100% by mass, 5 parts by mass of isopropyl alcohol / methyl ethyl ketone mixed solvent (mass ratio) 3/1) to obtain a release layer forming material having a solid content of 20% by mass.

The obtained release layer forming material was applied onto the first surface 11a of the base film 11 in the intermediate laminate with a bar coater, and dried at 80 ° C. for 1 minute to form a coating layer. This coating layer is irradiated with ultraviolet rays (integrated light quantity: 250 mJ / cm ² ) to form a release layer 12 (thickness: 1 μm), and a release film 1 (carrier film 10 and application film 20 as shown in FIG. 1). To obtain a laminate.

(Example 2)
As a release layer forming material, urethane-based pressure-sensitive adhesive (trade name “Siavine SH-101”, manufactured by Toyochem Co., Ltd.) 100 parts by mass (in terms of solid content) and hexamethylene diisocyanate trimer (trade name) A release film 1 was obtained in the same manner as in Example 1 except that 5 parts by mass (corresponding to solid content) of “Coronate 2030” manufactured by Nippon Polyurethane Industry Co., Ltd. was used.

(Example 3)
As the base film 11, a biaxially stretched polyethylene terephthalate film (thickness: 38 μm, arithmetic average roughness Ra of the first surface 11a: 15 nm, maximum protrusion height Rp of the first surface 11a: 98 nm, arithmetic average of the second surface 11b A release film 1 was obtained in the same manner as in Example 1 except that the roughness Ra: 15 nm and the maximum projection height Rp of the second surface 11b (Rp: 98 nm) were used.

Example 4
Biaxially stretched polyethylene terephthalate film (thickness: 23 μm, arithmetic average roughness Ra of the first surface (inner surface): 13 nm, maximum protrusion height Rp of the first surface: 88 nm, second surface (outer surface) A release film 1 was obtained in the same manner as in Example 1 except that the arithmetic average roughness Ra of 20a) was 13 nm and the maximum protrusion height Rp of the second surface was 88 nm.

(Comparative Example 1)
A carrier film was produced in the same manner as in Example 1 except that no application film was provided.

(Comparative Example 2)
Biaxially stretched polyethylene terephthalate film [thickness: 38 μm, first surface arithmetic average roughness Ra: 42 nm, first surface maximum protrusion height Rp: 619 nm, second surface arithmetic average roughness A carrier film was produced in the same manner as in Comparative Example 1 except that Ra: 42 nm and the maximum projection height Rp of the second surface Rp: 619 nm.

(Surface roughness)
For the surface roughness, the release film prepared in Example 1-4 and the carrier film prepared in Comparative Examples 1 and 2 were fixed on a double-sided tape affixed to a glass plate so that each measurement surface was on top. In accordance with JIS B0601-1994, the arithmetic average roughness Ra and the maximum protrusion height Rp were measured with a surface roughness measuring machine (SV3000S4 (stylus type), manufactured by Mitutoyo Corporation). For the surface roughness, the arithmetic average roughness Ra and the maximum protrusion height Rp on the outer surface of the release layer, the second surface of the base film, and the outer surface of the application film were measured. The measurement results are shown in Tables 1 and 2 below.

(Peelability evaluation)
The application film was peeled off from the release film of Example 1-4, and it was evaluated whether the application film could be normally peeled off. The evaluation results are shown in Table 3 below.
A: The application film could be smoothly peeled without tearing.
B: The application film was not broken, but it was slightly smooth but could be peeled off.
C: The application film is torn or cannot be peeled off.

(Handling evaluation)
The handling property when the release film of Example 1-4 and the carrier films of Comparative Examples 1 and 2 were wound into a roll was evaluated. The evaluation results are shown in Table 3 below.
A: The slipperiness was good, and the air release when forming into a roll shape was good, and the winding deviation of the release film could be prevented.
B: The slipperiness is slightly worse and the air escape is slightly worse when wound in a roll shape.
C: The slipperiness was poor, and the air was not easily removed when wound into a roll, and the winding deviation was noticeably generated.

(Blocking evaluation)
The release film of Example 1-4 and the carrier films of Comparative Examples 1 and 2 were wound into a roll having a width of 400 mm and a length of 3000 m. This film roll was stored for 30 days in an environment of 40 ° C. and a humidity of 50% or less, and the appearance of the roll was visually observed to evaluate the blocking property. The evaluation results are shown in Table 3 below. In addition, as shown in the following evaluation C, when blocking occurs due to adhesion between the front and back sides and the color changes over a wide area of the roll, the roll may not be unwound normally.
A: There was no change from when it was rolled up, and no blocking occurred.
B: There was a region where the color was partially different, and although some blocking occurred, it was usable.
C: Color was different over a wide area and blocking occurred.

(Unevenness defect evaluation 1)
A coating liquid prepared by dissolving polyvinyl butyral resin in a toluene / ethanol mixed solvent (mass ratio 6/4) was used as a release film of Example 1-4 and a release layer of the carrier film obtained in Comparative Examples 1 and 2. A polyvinyl butyral resin layer was formed by coating the film so that the thickness after drying was 3 μm, and drying at 80 ° C. for 1 minute. Next, a polyester tape was attached to the surface of the molded polyvinyl butyral resin layer, the release film was peeled off from the polyvinyl butyral resin layer, and the polyvinyl butyral resin layer was transferred to the polyester tape. Next, the surface of the polyvinyl butyral resin layer that had been in contact with the release layer of the release film (carrier film) was subjected to PSI mode using an optical interference type surface shape observation device (model number: WYKO-1100, manufactured by Veeco). The dents having a depth of 150 nm or more to which the shape of the release layer confirmed in the range of 91.2 × 119.8 μm was transferred were counted and evaluated at 50 magnifications. In addition, when a capacitor was produced with a green sheet having a dent of the following evaluation C, a short circuit due to a decrease in withstand voltage tended to occur. However, the test was not performed in the case of the evaluation C in the blocking property evaluation or the peelability evaluation.
A: When the number of dents is 0 B: When the number of dents is 1-5 C: When the number of dents is 6 or more

(Unevenness defect evaluation 2)
A coating solution prepared by dissolving polyvinyl butyral resin in a toluene / ethanol mixed solvent (mass ratio 6/4) was applied onto a PET film having a thickness of 50 μm so that the thickness after drying was 3 μm, and 80 ° C. And dried for 1 minute to form a polyvinyl butyral resin layer. The carrier film from which the application film was peeled and removed from the release film of Example 1-4 and the outer surface of the carrier film of Comparative Examples 1 and 2 (second surface of the base film) were in contact with the polyvinyl butyral resin layer. It bonded together to the polyvinyl butyral resin layer. The laminate was cut to 100 mm × 100 mm and then pressed with a load of 5 kg / cm ² to transfer the protrusion shape on the back of the carrier film to the polyvinyl butyral resin layer. Next, the carrier film was peeled from the polyvinyl butyral resin layer, and dents having a depth of 150 nm or more on the surface of the polyvinyl butyral resin film that was in contact with the back surface of the carrier film were counted and evaluated. In this evaluation, the second surface is confirmed in the range of 91.2 × 119.8 μm in the PSI mode at 50 magnifications using an optical interference type surface shape observation device (model number: WYKO-1100, manufactured by Veeco). The number of dents where the shape was transferred was counted. In addition, when a capacitor was produced with a green sheet having a dent of the following evaluation C, a short circuit due to a decrease in withstand voltage tended to occur. However, the test was not performed in the case of evaluation C in the blocking property evaluation.
A: When the number of dents is 0 B: When the number of dents is 1 to 3 C: When the number of dents is 4 or more

  As can be seen from Tables 1 to 3, when the application film (protective layer) 20 having a rough outer surface 20a is provided on the second surface 11b of the base film 11, peelability, handling properties, blocking properties, It turns out that a favorable evaluation result is obtained in any of the concavo-convex defects 1 and 2 (Example 1-4). As a result, the outer surface 20a of the application film (protective layer) 20 makes one main surface of the release film 1 an appropriate rough surface, so that the outer surface 20a of the application film (protective layer) 20 and the release layer 12 It is considered that an appropriate gap was formed between the outer surface 12a and the outer surface 12a, and the air escape during winding was good, and the outer surface 20a was in the range of an appropriate rough surface, so that the irregular defect did not occur.

  On the other hand, when there is no application film (protective layer), it can be seen that the evaluation of handling properties and blocking properties is significantly deteriorated (Comparative Example 1). This result is considered to be due to the fact that both sides of the carrier film are highly smooth, so that air escape during winding of the carrier film deteriorated and smooth surfaces blocked. Moreover, when the 2nd surface 11b of the base film 11 is simply made into the rough surface, it turns out that the evaluation of the uneven | corrugated defect 2 deteriorates (Comparative Example 2).

DESCRIPTION OF SYMBOLS 1 Release film 2 1st laminated body 3 2nd laminated body 4 Internal electrode laminated body 5 Intermediate laminated body 6 Multilayer ceramic capacitor (multilayer ceramic electronic component)
10 Carrier film 11 Base film (base material)
11a 1st surface 11b 2nd surface 12 Release layer 12a Outer surface 20 Application film (protective layer)
20a outer surface 21 support 22 peeling layer 31 green sheet 32 internal electrode 33 external electrode

Claims (7)

It is a release film that can be rolled up and stored on a core material,
A substrate having a first surface and a second surface;
A release layer provided on the first surface of the substrate;
A protective layer releasably fixed on the second surface of the base material,
A release film, wherein an outer surface of the protective layer is a rough surface.   2. The release film according to claim 1, wherein the protective layer has an arithmetic average roughness Ra of 10 nm to 200 nm and a maximum protrusion height Rp of 60 nm to 2000 nm.   3. The release film according to claim 1, wherein the release layer has an arithmetic average roughness Ra of an outer surface of less than 15 nm and a maximum protrusion height Rp of less than 100 nm.   The mold release according to any one of claims 1 to 3, wherein the base material has an arithmetic average roughness Ra of the second surface of less than 20 nm and a maximum protrusion height Rp of less than 150 nm. the film.   The said protective layer is any one of Claims 1-4 containing the support body and the peeling layer which was provided on the said support body, and was fixed to the said 2nd surface of the said base | substrate so that peeling was possible. The release film as described in the item. A first step of obtaining a first laminate by providing a green sheet on the release layer of the release film according to any one of claims 1 to 5;
A second step of removing the protective layer from the first laminate to obtain a second laminate;
And a third step of winding the second laminated body in a roll shape. A lamination step of providing an internal electrode on a green sheet produced by the method for producing a green sheet according to claim 6, and laminating the green sheet provided with the internal electrode to obtain an intermediate laminate,
A molding step of molding the intermediate laminate into a desired shape;
And an external electrode forming step of forming an external electrode on the intermediate laminate. A method for producing a multilayer ceramic electronic component, comprising:

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