Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B28—WORKING CEMENT, CLAY, OR STONE
  • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
  • B28B1/00—Producing shaped prefabricated articles from the material
  • B28B1/30—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B28—WORKING CEMENT, CLAY, OR STONE
  • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
  • B28B13/00—Feeding the unshaped material to moulds or apparatus for producing shaped articles; Discharging shaped articles from such moulds or apparatus
  • B28B13/04—Discharging the shaped articles
  • B28B13/06—Removing the shaped articles from moulds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
  • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
  • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
  • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
  • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/002—Details
  • H01G4/018—Dielectrics
  • H01G4/06—Solid dielectrics
  • H01G4/08—Inorganic dielectrics
  • H01G4/12—Ceramic dielectrics
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G4/00—Fixed capacitors; Processes of their manufacture
  • H01G4/30—Stacked capacitors
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
  • B32B2250/244—All polymers belonging to those covered by group B32B27/36
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/746—Slipping, anti-blocking, low friction
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2457/00—Electrical equipment
  • B32B2457/16—Capacitors

Definitions

• the present invention relates to a release film for manufacturing a ceramic green sheet, and more specifically, it is possible to suppress the occurrence of process defects such as flatness defects and peeling defects during the production of an ultrathin layer ceramic green sheet, and the release film is low.
• the present invention relates to an ultra-thin layer ceramic green sheet production release film capable of reducing the adhesion of foreign matter to the release film and suppressing the mixing of foreign matter into the ceramic green sheet by setting the amount of charge.
• a release film using a polyester film as a base material and a release layer laminated on it is used for molding ceramic green sheets such as multilayer ceramic capacitors and ceramic substrates.
• ceramic green sheets such as multilayer ceramic capacitors and ceramic substrates.
• the ceramic green sheet is molded by applying a slurry containing a ceramic component such as barium titanate and a binder resin to a release film and drying it.
• a laminated ceramic capacitor is manufactured by printing an electrode on a molded ceramic green sheet, peeling it from a release film, laminating and pressing the ceramic green sheet, firing, and applying an external electrode.
• Patent Document 1 When a ceramic green sheet is molded on the surface of the release layer of a polyester film, there is a problem that minute protrusions on the surface of the release layer affect the molded ceramic green sheet, which tends to cause defects such as cissing and pinholes. there were. Therefore, various methods for realizing a release layer surface having excellent flatness have been developed (for example, Patent Document 1).
• Patent Documents 4 and 5 As a method of suppressing the charge of the release film, a method of incorporating an antistatic agent in the release layer, an antistatic coating layer on the surface opposite to the release layer or an intermediate layer between the release layer and the base film (For example, Patent Documents 4 and 5).
• an antistatic agent when an antistatic agent is contained in the release layer as in Patent Document 4, the antistatic agent having poor compatibility with the release component may aggregate to form coarse protrusions. Also. The surface properties and curability were adversely affected, and the peelability of the ultrathin ceramic green sheet was likely to be insufficient.
• Patent Document 5 when an antistatic layer is provided on the surface opposite to the release layer or the intermediate layer between the release layer and the base film as in Patent Document 5, the number of processing steps is increased, and an antistatic agent is generally used. Since it is expensive, the cost is increased and there is a big economic problem.
• the present invention has been made against the background of the problems of the prior art. That is, while maintaining high smoothness of the release layer surface of the release film, the release force is low and uniform, the charge amount of the release film is low, and there are few defects even in an ultrathin layer product having a thickness of 1 ⁇ m or less. It is an object of the present invention to provide a release film for producing a ceramic green sheet capable of molding a ceramic green sheet.
• the present inventors have used a polyester film and have a composition containing a specific release agent and a melamine-based compound directly on the surface layer A of the polyester film or via another layer. It has been found that by providing a release layer obtained by curing an object, it is possible to provide a release film for producing a ceramic green sheet, which is excellent in smoothness and peelability of the ceramic green sheet and has a small amount of charge.
• the present invention has the following configuration. 1.
• a layer using a polyester film as a base material and forming one surface of the base material is used as a surface layer A and a layer forming the other surface is used as a surface layer B
• the layer directly on the surface layer A is a release film in which a release layer is laminated via another layer, and the release layer and the surface layer B are brought into contact with each other and held in an atmosphere of 50 ° C. under a pressure of 10 kPa for 48 hours.
• a release film for producing a ceramic green sheet in which the charge amount of the release layer when the release layer and the surface layer B are peeled off is ⁇ 5 kV or less. 2.
• the weight average degree of polymerization of the first is 1.7 or less, and the content of the melamine compound in the release layer is 80% by mass or more with respect to the solid content of the release layer forming composition.
• the first to sixth surfaces wherein the surface layer B contains particles, at least a part of the particles are silica particles and / or calcium carbonate particles, and the total content of the particles with respect to the mass of the surface layer B is 5000 to 15000 ppm.
• a release film for manufacturing a ceramic green sheet according to any one of. 8 A method for producing a ceramic green sheet by molding a ceramic green sheet using the release film for producing a ceramic green sheet according to any one of the above 1 to 7, wherein the molded ceramic green sheet is 0.2 ⁇ m or more. A method for producing a ceramic green sheet having a thickness of 1.0 ⁇ m. 9. A method for manufacturing a ceramic capacitor, which employs the method for manufacturing a ceramic green sheet according to the eighth item.
• the release film for manufacturing an ultra-thin ceramic green sheet of the present invention has a small amount of charge, the surface of the release layer is smooth, and the ceramic green sheet has excellent peelability. Therefore, foreign matter is mixed into the ceramic green sheet. And the occurrence of defects can be suppressed, and an ultrathin layer ceramic green sheet having a thickness of 0.2 to 1.0 ⁇ m can be efficiently produced.
• the release layer is laminated on the surface layer A of the polyester film as a base material directly or via another layer, and the surface layer A and the surface layer A are different from each other. It is preferable that the surface layer B on the opposite side is not provided with an antistatic layer.
• the release layer is preferably formed by curing a composition containing at least a melamine compound and polyorganosiloxane without containing an antistatic agent.
• the release film for producing a ceramic green sheet of the present invention preferably has a release layer that is difficult to be charged. More specifically, in the release film manufacturing process, when the film is wound up after the release layer processing and stored in a roll shape, the charge increasing with time may become a problem. For example, when the amount of charge of the roll-shaped film is large, in the slitting process and the ceramic green sheet molding process, extremely minute environmental foreign substances in the process and film debris generated at the time of slitting tend to adhere to the film. A release film having a release layer that is difficult to be charged is preferable because these foreign substances adhering to the film may be mixed into the ceramic green sheet, which may lead to defects.
• evaluating the difficulty of charging it can be confirmed by evaluating the amount of charge of the release layer after the release layer and the surface layer B are brought into contact with each other and held for a certain period of time under a load.
• this evaluation method it is possible to modelly evaluate the amount of charge that increases with time when the film is stored in a roll shape. The detailed evaluation method will be described later.
• the charge amount of the release layer measured by the evaluation method described later is preferably ⁇ 5 kV or less, for example, ⁇ 3.4 or less, more preferably ⁇ 3 kV or less, and the smaller the absolute value, the more preferable. .. It is preferable that the charge amount of the release layer is ⁇ 5 kV or less because the increase in the charge amount with time when the film is stored in a roll form is small and foreign matter is hard to adhere to the film. The smaller the charge amount of the release layer is, the more preferable it is, but it may be 0.1 kV or more, or 0.3 kV or more.
• the antistatic agent is intended to impart conductivity to an ionic conductive polymer compound, a ⁇ -electron conjugated polymer compound, a conductive filler, a metal layer, a metal oxide layer, and the like.
• the ionic conductive polymer compound include an ammonium group-containing compound, a polyether compound, a sulfonic acid compound, and a betaine compound.
• examples thereof include ⁇ -electron conjugated polymer compounds polyacetylene, polyphenylene, polyaniline, polypyrrole, polyisotianaften, polythiophene and the like.
• Conductive fillers include metals such as gold, silver, copper, aluminum, nickel, titanium, iron, zinc, tin, fillers and fibers of these alloys, and metal oxide fillers (silica, titania, etc., exclusively slippery). (Excluding those used for purposes other than conductivity), metal-coated synthetic fibers, conductive carbon fibers such as carbon nanotubes, and the like.
• the antistatic layer means a layer containing the above-mentioned antistatic agent and exerting an antistatic effect.
• polyester film The polyester constituting the polyester film used as the base material in the present invention is not particularly limited, and a film-molded polyester usually generally used as a base material for a release film can be used, but preferably. It is preferable to use a crystalline linear saturated polyester composed of an aromatic dibasic acid component and a diol component, for example, polyethylene terephthalate, polyethylene − 2,6 − naphthalate, polybutylene terephthalate, polytrimethylene terephthalate. Alternatively, a copolymer containing the constituent components of these resins as a main component is more preferable, and a polyester film formed from polyethylene terephthalate is particularly preferable.
• the repeating unit of ethylene terephthalate is preferably 90 mol% or more, more preferably 95 mol% or more, and other dicarboxylic acid components and diol components may be copolymerized in a small amount, but from the viewpoint of cost. , Preferably made only from terephthalic acid and ethylene glycol. Further, known additives such as antioxidants, light stabilizers, ultraviolet absorbers, crystallization agents and the like may be added as long as the effects of the film of the present invention are not impaired.
• the polyester film is preferably a biaxially oriented polyester film because of its high bidirectional elastic modulus and the like.
• the intrinsic viscosity of the polyester film is preferably 0.50 to 0.70 dl / g, more preferably 0.52 to 0.62 dl / g.
• the intrinsic viscosity is 0.50 dl / g or more, it is preferable because many breaks do not occur in the stretching step. On the contrary, when it is 0.70 dl / g or less, it is preferable because the cutability when cutting to a predetermined product width is good and dimensional defects do not occur. Further, it is preferable that the raw material pellets are sufficiently vacuum dried.
• the method for producing the polyester film in the present invention is not particularly limited, and a method generally used in the past can be used.
• the polyester can be melted by an extruder, extruded into a film, cooled by a rotary cooling drum to obtain an unstretched film, and the unstretched film can be obtained by uniaxially or biaxially stretching.
• the biaxially stretched film can be obtained by a method of sequentially biaxially stretching a longitudinally or laterally uniaxially stretched film in the lateral or longitudinal direction, or a method of simultaneously biaxially stretching an unstretched film in the longitudinal and horizontal directions. You can.
• the stretching temperature at the time of stretching the polyester film is equal to or higher than the secondary transition point (Tg) of the polyester. It is preferable to stretch 1 to 8 times, particularly 2 to 6 times in each of the vertical and horizontal directions.
• the thickness of the polyester film is preferably 12 to 50 ⁇ m, more preferably 15 to 38 ⁇ m, and even more preferably 19 ⁇ m to 33 ⁇ m.
• the thickness of the film is 12 ⁇ m or more, it is preferable because there is no possibility of deformation due to heat during film production, processing process of release layer, molding of ceramic green sheet and the like.
• the thickness of the film is 50 ⁇ m or less, the amount of the film discarded after use does not become extremely large, which is preferable in reducing the environmental load.
• the polyester film base material may be a single layer, but is preferably a multilayer of two or more layers.
• the surface layer A does not substantially contain inorganic particles.
• the surface layer B preferably contains particles and the like.
• the layer structure in the thickness direction is A laminated structure such as a release layer / A / B or a release layer / A / C / B can be mentioned.
• the layer C may have a plurality of layer configurations.
• the surface layer B may be a layer formed of polyester as the main constituent resin together with the surface layer A by a so-called coextrusion method, but is provided as a coating layer on the surface opposite to the surface layer A of the polyester film. It may be a thing.
• the surface layer B is the coating layer, the surface layer B is preferably composed of a binder resin and particles. In this case, the surface layer B can be said to be an easy-slip coating layer.
• the surface layer A forming the surface to which the release layer is applied does not substantially contain inorganic particles.
• the region surface average roughness (Sa) of the surface layer A is preferably 7 nm or less.
• Sa is 7 nm or less, pinholes and the like are less likely to occur during molding of the ultra-thin ceramic green sheet to be laminated, which is preferable. It can be said that the smaller the region surface average roughness (Sa) of the surface layer A is, the more preferable it is, but it may be 0.1 nm or more.
• the coat layer does not substantially contain inorganic particles, and the region surface average roughness (Sa) after laminating the coat layer is in the above range. It is preferable to enter.
• substantially free of inorganic particles means a content of 50 ppm or less, preferably 10 ppm or less, and most preferably detection limit or less when the inorganic element is quantified by Keiko X-ray analysis. To do. This means that even if inorganic particles are not actively added to the film, contaminant components derived from foreign substances and stains attached to the raw material resin or the line or device in the film manufacturing process are peeled off and mixed into the film. This is because there are cases.
• the surface layer B forming the opposite surface to the surface to which the release layer is applied preferably contains particles from the viewpoint of the slipperiness of the film and the ease with which air can escape. It is preferable to use silica particles and / or calcium carbonate particles.
• the total amount of particles contained in the surface layer B is preferably 5000 to 15000 ppm.
• the region surface average roughness (Sa) of the film of the surface layer B is preferably in the range of 1 to 40 nm. More preferably, it is in the range of 5 to 35 nm.
• the total amount of silica particles and / or calcium carbonate particles is 5000 ppm or more and Sa is 1 nm or more, air can be released uniformly when the film is rolled up, and the rolled shape is good and the flatness is good. , Suitable for manufacturing ultra-thin ceramic green sheets. Further, when the total amount of silica particles and / or calcium carbonate particles is 15,000 ppm or less and Sa is 40 nm or less, the lubricant is less likely to aggregate and coarse protrusions cannot be formed, so that the quality is stable during the production of an ultrathin ceramic green sheet. It is preferable.
• inactive inorganic particles and / or heat-resistant organic particles other than silica and / or calcium carbonate can be used. From the viewpoint of transparency and cost, it is more preferable to use silica particles and / or calcium carbonate particles, but other inorganic particles that can be used include alumina-silica composite oxide particles and hydroxyapatite particles.
• the heat-resistant organic particles include crosslinked polyacrylic particles, crosslinked polystyrene particles, and benzoguanamine particles.
• porous colloidal silica is preferable, and when calcium carbonate particles are used, light calcium carbonate surface-treated with a polyacrylic acid-based polymer compound is preferable from the viewpoint of preventing the lubricant from falling off. ..
• the average particle size of the particles added to the surface layer B is preferably 0.1 ⁇ m or more and 2.0 ⁇ m or less, and particularly preferably 0.5 ⁇ m or more and 1.0 ⁇ m or less.
• the average particle size of the particles is 0.1 ⁇ m or more, the slipperiness of the release film is good, which is preferable.
• the average particle size is 2.0 ⁇ m or less, pinholes are not likely to occur in the ceramic green sheet due to the coarse particles on the surface of the release layer, which is preferable.
• the surface layer B may contain two or more types of particles made of different materials. Further, particles of the same type having different average particle diameters may be contained.
• the above-mentioned easy-slip coating layer is provided as the surface layer B on the surface opposite to the surface layer A, it is preferably provided by an in-line coating that is applied during the film formation of the polyester film. Even when the easy-slip coating layer is provided, the region surface average roughness (Sa) of the surface layer B due to the easy-slip coating layer is in the range of 1 to 40 nm for the same reason as described above. Is preferable.
• the film thickness of the surface layer B by the easy-slip coating layer is preferably 2 ⁇ m or less, more preferably 1 ⁇ m or less, further preferably 0.8 ⁇ m or less, and particularly preferably 0.5 ⁇ m or less.
• the film thickness of the coating layer is 2 ⁇ m or less, blocking may not occur, which is preferable.
• the binder resin constituting the slippery coating layer is not particularly limited, but specific examples of the polymer include polyester resin, acrylic resin, urethane resin, polyvinyl-based resin (polyvinyl alcohol, etc.), polyalkylene glycol, polyalkyleneimine, and methyl cellulose. , Hydroxycellulose, polymers and the like. Among these, it is preferable to use polyester resin, acrylic resin, or urethane resin from the viewpoint of particle retention and adhesion. Further, when considering the hardness of the easy-slip coating layer, an acrylic resin is particularly preferable. Further, as another preferable binder resin constituting the easy-slip coating layer on the polyester base film, polyester resin and urethane resin can be mentioned.
• the polyester resin is preferably a copolymerized polyester.
• the polyester resin may be modified with polyurethane.
• examples of the urethane resin include polycarbonate polyurethane resin.
• acrylic resin, polyester resin, and polyurethane resin may be used in combination, or other binder resins described above may be used in combination.
• the easy-slip coating layer may be formed by containing a cross-linking agent.
• a cross-linking agent By containing a cross-linking agent, the hardness of the I Ching coating layer can be further improved.
• the cross-linking agent include urea-based, epoxy-based, melamine-based, isocyanate-based, oxazoline-based, and carbodiimide-based.
• oxazoline-based and carbodiimide-based cross-linking agents are particularly preferable in that the cross-linking density can be improved.
• a catalyst or the like can be appropriately used as needed.
• the easy-to-slip coating layer forming the surface layer B preferably contains lubricant particles in order to impart slipperiness to the surface.
• the particles may be inorganic particles or organic particles, and are not particularly limited.
• the surface layer A which is the layer on which the release layer is provided, in order to prevent particles such as lubricant from being mixed.
• the thickness ratio of the surface layer A which is the layer on which the release layer is provided, is preferably 20% or more and 50% or less of the total thickness of the base film. If it is 20% or more, it is not easily affected by the particles contained in the surface layer B or the like from the inside of the film, and it is easy for the region surface average roughness Sa to satisfy the above range, which is preferable. When it is 50% or less of the thickness of all the layers of the base film, the ratio of the recycled raw material used in the surface layer B by coextrusion and the above-mentioned intermediate layer C can be increased, and the environmental load is reduced, which is preferable.
• the type and amount of the lubricant contained in the surface layer B, the particle size, and the region surface average roughness (Sa) satisfy the above ranges.
• a coat layer is provided on the surface of the surface layer A and / or the surface layer B on the film before or after stretching in the film forming process. It is also possible to apply corona treatment or the like.
• the surface layer A and the surface layer B do not have an antistatic layer, and it is preferable that the surface layer A and the surface layer B do not contain an antistatic agent.
• the intermediate layer C it is preferable that the intermediate layer C also does not contain an antistatic agent.
• the release layer in the present invention does not contain an antistatic agent and is obtained by curing a composition containing at least a melamine compound and a polyorganosiloxane.
• the release layer in the present invention preferably has a high crosslink density and a high elastic modulus in order to suppress deformation of the release layer that occurs during peeling and to make the peeling force low and uniform.
• the elastic modulus of the release layer refers to the elastic modulus in the compression direction.
• Increasing the elastic modulus of the release layer improves the slipperiness of the surface layer B that comes into contact with the release layer during roll storage (it becomes easier to slip).
• the release layer becomes slippery, the pressure applied in the direction perpendicular to the film surface easily escapes in the horizontal direction, so that the adhesion with the surface layer B when stored in a roll shape can be reduced, and charging can be performed. It is preferable because it can be suppressed.
• crosslink density of the release layer it was also found that it is important to increase the crosslink density of the release layer in order to suppress the amount of charge. Increasing the crosslink density of the release layer facilitates electron transfer between the melamine resins existing in the release layer and makes it difficult to charge, which is preferable. In order to increase the crosslink density of the release layer, it is preferable to increase the reactivity of the melamine compound.
• the highly reactive melamine compound will be described in detail later.
• melamine compound used for the release layer in the present invention general compounds can be used and are not particularly limited, but are obtained by condensing melamine and formaldehyde, and a triazine ring, a methylol group and / or an alkoxy in one molecule. It is preferable that each has one or more methyl groups.
• a compound obtained by subjecting a methylol melamine derivative obtained by condensing melamine and formaldehyde with a dehydration condensation reaction of methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol or the like as a lower alcohol to etherify is preferable.
• methylolated melamine derivative examples include monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, and hexamethylol melamine.
• One type may be used or two or more types may be used.
• hexamethylol melamine or hexaalkoxymethyl melamine having more cross-linking points in one molecule it is preferable to use hexamethylol melamine or hexaalkoxymethyl melamine having more cross-linking points in one molecule, but the reactivity is more excellent. Hexaalkoxymethylmelamine is more preferable, and hexamethoxymethylmelamine is particularly preferable.
• the hexamethylol melamine is intended in the following formula (a), X is a methylol group (-CH 2 -OH).
• hexa-alkoxymethyl melamine which was allowed to dehydration condensation reaction with an alcohol to methylol melamine derivative, X is (-CH 2 -OR, R is an alkyl group having 1 to 4 carbon atoms) are those wherein.
• the hexamethoxymethylmelamine are those wherein X is (-CH 2 -OMe).
• the Xs in (a) above may be the same or different. Further, the above Rs may be the same or different. Further, X may be ( ⁇ H).
• the melamine-based compound used in the present invention is preferably not a single compound but a mixture of a plurality of compounds.
• hexamethoxymethylmelamine (CAS No. 3089-11-0) in which R is a methyl group is used.
• the melamine compound used for the release layer in the present invention preferably has a weight average molecular weight of 250 or more and 1000 or less. More preferably, the weight average molecular weight is 300 or more and 900 or less, and further preferably 400 or more and 800 or less. When the weight average molecular weight is 1000 or less, the cross-linking reaction easily proceeds, a film having a higher cross-linking density can be formed, and a release layer having a light peeling and a low charge amount is obtained, which is preferable. When the weight average molecular weight is 250 or more, the crosslink density does not become excessively large and the curl does not deteriorate, which is preferable.
• the weight average molecular weight in the present specification is a standard polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method.
• the weight average molecular weight of the melamine compound is 250 to 1000, which means that the melamine compound used in the present invention contains a large amount of mononuclear compounds. Since the mononuclear body has more cross-linking points and is excellent in reactivity than the polynuclear body formed by condensing two or more melamine derivatives, it can be a release layer having a high cross-linking density and excellent peelability. The higher the content of mononuclear bodies, the more preferable, and it is most preferable to use a melamine-based compound consisting of only mononuclear bodies.
• the weight average molecular weight can also be expressed by the weight average degree of polymerization.
• the weight average degree of polymerization of the melamine-based compound used is preferably 1.7 or less, more preferably 1.5 or less, further preferably 1.3 or less, and the smaller the degree, the more preferably it can be used. ..
• the weight average degree of polymerization is 1.7 or less, the content of the mononuclear compound contained in the melamine compound increases, so that the release layer has excellent reactivity, excellent peelability, and is hard to be charged. It is preferable because it can be done.
• the weight average degree of polymerization in the present specification is a value calculated based on the weight average molecular weight obtained by gel permeation chromatography in terms of standard polystyrene.
• Melamine compounds may contain imino groups (-NH 2- ) or polynuclear compounds in the process of their synthesis. Even if these melamine derivatives are mixed, if the weight average molecular weight (that is, the weight average degree of polymerization) of the melamine compound is within the above range, the reactivity is excellent and each of them can be preferably used.
• the release layer in the present invention preferably contains a melamine compound in an amount of 80% by mass or more and 99.9% by mass or less, more preferably 90% by mass or more, based on the solid content of the release layer forming composition. It is 99.9% by mass or less, more preferably 95% by mass or more and 99.9% by mass or less.
• the release layer can obtain a high cross-linking density by self-crosslinking of the melamine compound, and the release layer has a high elastic modulus, which is preferable.
• the solid content of the release layer forming composition is substantially the total value of the solid content of the melamine compound and the release agent because the solvent and the acid catalyst partially evaporate during the drying process. You can consider it as.
• an acid catalyst to the release layer in the present invention in order to promote the cross-linking reaction of the melamine compound, and it is possible to add an acid catalyst to the release layer forming composition, apply it, and cure it.
• an acid catalyst to be used it is preferable to use a sulfonic acid-based catalyst.
• sulfonic acid-based catalyst for example, p-toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, trifluoromethanesulfonic acid and the like can be preferably used, but the reaction From the viewpoint of properties, p-toluenesulfonic acid can be particularly preferably used.
• sulfonic acid-based catalyst used in the present invention a commercially available catalyst can also be used.
• examples of commercially available products include dryer (registered trademark) 900 (p-toluenesulfonic acid, manufactured by Hitachi Kasei), NACURE (registered trademark) DNNDSA series (dinonylnaphthalenedisulfonic acid, manufactured by Kusumoto Kasei), and DNNSA series (registered trademark).
• the release layer can be processed at a lower temperature. Therefore, it is preferable because it is possible to suppress deterioration of the flatness of the film due to heat during processing and deterioration of the rolled appearance.
• the amount of the acid catalyst added is preferably 0.1 to 10% by mass with respect to the melamine compound contained in the release layer. More preferably, it is 0.5 to 8% by mass. More preferably, it is 0.5 to 5% by mass. When it is 0.1% by mass or more, the curing reaction easily proceeds, which is preferable. On the other hand, when it is 10% by mass or less, there is no possibility that the acid catalyst is transferred to the ceramic green sheet to be molded, and there is no possibility of adversely affecting it, which is preferable.
• the release agent used for the release layer (additive for improving the release property of the release layer) in the present invention general ones can be used without particular limitation, but carboxyl group, hydroxyl group, amino group and thiol can be used. It is preferable to use a polyorganosiloxane having a functional group capable of reacting with a melamine-based compound such as a group. Among them, it is more preferable to use a polyorganosiloxane having a hydroxyl group and a carboxyl group, and it is most preferable to use a polyorganosiloxane containing a carboxyl group from the viewpoint of peelability and antistatic. Among the polyorganosiloxane structures, those having a polydimethylsiloxane structure (abbreviation, PDMS) can be preferably used.
• PDMS polydimethylsiloxane structure
• the release agent polyorganosiloxane contains a carboxyl group, the release agent does not show a strong interaction with the melamine compound in the drying process, and easily orients on the surface of the release layer, resulting in good release. can get. Therefore, it is preferable to use a polyorganosiloxane containing a carboxyl group because the release property can be satisfied even if the amount of the release agent added is small. Further, it is preferable that the release layer surface is easily oriented so that the release layer surface is more slippery and less likely to be charged.
• the carboxyl group may be introduced at one end of the polyorganosiloxane, or may be both ends or a side chain. Further, the number of positions to be introduced may be one or a plurality.
• the carboxyl group-modified polyorganosiloxane may have a carboxyl group directly bonded to the silicon atom of the polyorganosiloxane, but a carboxyl group bonded to the polyorganosiloxane via an alkyl group or an aryl group. There may be. However, those in which a carboxyl group is bonded to polyorganosiloxane via an organic group having a repeating structure such as polyether, polyester, or polyurethane are not so preferable.
• one molecule may have another functional group other than the carboxyl group, but only the carboxyl group is preferable. If a functional group other than the carboxyl group is contained, the intermolecular interaction with the melamine compound may be increased more than necessary and it may be difficult to orient the release layer on the surface, which is not preferable.
• Polyorganosiloxane modified with a hydroxyl group that shows a strong interaction with the melamine compound reacts rapidly with the melamine compound in the drying process, so it is difficult to align with the release layer surface and the releasability is difficult to develop. There is. Therefore, it is necessary to increase the amount of addition in order to have sufficient releasability, but in that case, the elastic modulus of the releasing layer may decrease and the peeling force may increase. Further, when the amount of polyorganosiloxane added is increased, the coatability at the time of molding the ceramic green sheet may be deteriorated, which is not preferable.
• the carboxyl group-containing polyorganosiloxane used in the present invention preferably has a weight average molecular weight of 40,000 or less. More preferably, it is 30,000 or less. When the weight average molecular weight is 40,000 or less, the polyorganosiloxane containing a carboxyl group is likely to segregate on the surface of the release layer, which is preferable from the viewpoint of peelability and charge amount.
• the carboxyl group-containing polyorganosiloxane is more preferably a carboxyl group-containing polydimethylsiloxane.
• the polydimethylsiloxane containing a carboxyl group include X22-3701E (side chain carboxyl-modified polydimethylsiloxane, manufactured by Shinetsu Chemical Industry Co., Ltd.), X22-3710 (one-terminal carboxyl-modified polydimethylsiloxane, manufactured by Shinetsu Chemical Industry Co., Ltd.), and X22.
• -162C both-terminal carboxyl-modified polydimethylsiloxane, manufactured by Shinetsu Chemical Industry Co., Ltd.
• BY16-750 both-terminal carboxyl-modified polydimethylsiloxane, manufactured by Toray Corning
• BY16-880 side chain carboxyl-modified polydimethylsiloxane, manufactured by Toray) Dow Corning Co., Ltd.
• Magnasoft 800L both-terminal carboxyl-modified polydimethylsiloxane, Momentive Co., Ltd.
• the carboxyl group-containing polydimethylsiloxane in the present invention may be an acrylic resin in which polydimethylsiloxane is introduced into the side chain of the carboxyl group-containing acrylic main chain.
• acrylic resin in which polydimethylsiloxane is introduced into the side chain of the acrylic main chain containing a carboxyl group Cymac (registered trademark) US-350, US-352, US-380 (all manufactured by Toagosei Co., Ltd.) and the like are used. Can be used.
• an acrylic resin in which polydimethylsiloxane is introduced into a side chain of an acrylic main chain containing a carboxyl group and a hydroxyl group in one molecule may be used.
• Acrylic resins in which polydimethylsiloxane is introduced into the side chain of an acrylic main chain containing a carboxyl group and a hydroxyl group in one molecule include Cymac (registered trademark) US-450 and US-480 (all manufactured by Toagosei Co., Ltd.). ) Etc. can be used.
• the release layer in the present invention preferably contains a release agent in an amount of 0.05% by mass or more and 5% by mass or less with respect to the solid content of the release layer forming composition. More preferably, it is 0.1% by mass or more and 3% by mass or less, and further preferably 0.1% by mass or more and 1% by mass or less.
• a release agent in an amount of 0.05% by mass or more and 5% by mass or less with respect to the solid content of the release layer forming composition. More preferably, it is 0.1% by mass or more and 3% by mass or less, and further preferably 0.1% by mass or more and 1% by mass or less.
• it is 0.05% by mass or more, not only the peelability is improved, but also the release layer becomes slippery and it becomes difficult to be charged, which is preferable.
• the elastic modulus of the entire release layer does not decrease too much, which is preferable.
• the solid content of the release layer forming composition is substantially the total value of the solid content of the melamine compound and the release agent because the solvent and the acid catalyst partially evaporate during the drying process. You can consider it as.
• the release layer in the present invention can contain particles having a particle size of 1 ⁇ m or less, but it is preferable not to contain particles or other particles that form protrusions from the viewpoint of pinhole generation.
• the release layer in the present invention may be added to the release layer in the present invention as long as the effects of the present invention are not impaired, but it is preferable that the release layer does not contain an antistatic agent. It is preferable to use a release layer that does not contain an antistatic agent because the compatibility with the release agent and the melamine compound is deteriorated, and there is no possibility that agglomerates are generated and the smoothness of the release layer is impaired. Further, it is preferable because the release layer can be formed more economically.
• the thickness of the release layer may be set according to the purpose of use and is not particularly limited, but preferably, the weight of the release coating layer after curing is in the range of 0.01 to 1.0 ⁇ m. It is better, more preferably 0.05 to 0.8 ⁇ m, still more preferably 0.1 to 0.6 ⁇ m, and even more preferably 0.1 to 0.4 ⁇ m.
• the thickness of the release layer is 0.01 ⁇ m or more, peeling performance can be obtained, which is preferable.
• the curing time can be shortened, the flatness of the release film can be maintained, and uneven thickness of the ceramic green sheet can be suppressed, which is preferable.
• the smaller the thickness of the release layer the less likely it is to be charged, which is preferable.
• the release layer surface of the release film of the present invention is preferably flat so as not to cause defects in the ceramic green sheet coated and molded on the release layer surface, and the region surface average roughness (Sa) is 7 nm or less and the maximum.
• the protrusion height (P) is preferably 100 nm or less. Further, it is more preferable that the region surface average roughness is 5 nm or less and the maximum protrusion height is 80 nm or less. For example, the maximum protrusion height (P) may be 45 nm or less. When the region surface roughness is 7 nm or less and the maximum protrusion height is 100 nm or less, defects such as pinholes do not occur when the ceramic green sheet is formed, and the yield is good, which is preferable.
• the release film of the present invention it is preferable to use a base film in which the surface layer A is highly flattened, and even if the thickness of the release layer is thinner than 0.5 ⁇ m and further thinner than 0.2 ⁇ m, the release film is released.
• the surface of the mold layer can be smoothed. Therefore, even in the release layer using a highly reactive melamine compound, the generation of curl can be suppressed.
• the amount of solvent and resin used can be reduced, which is environmentally friendly, and a release film for molding an ultrathin layer ceramic green sheet can be produced at low cost.
• the release film of the present invention preferably has a peeling force of 0.5 mN / mm or more and 2.0 mN / mm or less when peeling the ceramic green sheet. More preferably, it is 0.5 mN / mm or more and 1.5 mN / mm or less.
• the peeling force is 0.5 mN / mm or more, the peeling force is not too light and there is no possibility that the ceramic green sheet will be lifted during transportation, which is preferable.
• the peeling force is 2.0 mN / mm or less, the ceramic green sheet is not likely to be damaged during peeling, which is preferable.
• the release film of the present invention can satisfactorily peel off the ceramic green sheet.
• the release film of the present invention preferably has a static friction coefficient of less than 0.30 when the release layer and the surface layer B are superposed, for example, 0.25 or less and less than 0.25. Is more preferable. If the coefficient of static friction is less than 0.30, the adhesion between the release layer and the surface layer B decreases, so that the film is charged due to tightening or vibration during transportation when the film is stored in a roll shape. Is preferable because it can suppress. The smaller the coefficient of static friction is, the more the charge can be suppressed, which is preferable. However, it is preferably 0.01 or more, and more preferably 0.03 or more.
• the release film of the present invention preferably has a curl of 3 mm or less, more preferably 1 mm or less, after being heated at 80 ° C. for 5 minutes without applying tension. Of course, it is also preferable not to curl at all. It is preferable that the thickness is 3 mm or less because curling is small and printing accuracy can be improved when the ceramic green sheet is molded and the electrodes are printed.
• the method for forming the release layer is not particularly limited, and a coating liquid in which a releaseable resin is dissolved or dispersed is developed by coating or the like on one surface of a polyester film of a base material, and a solvent or the like is formed. Is removed by drying, and then heat-dried and heat-cured. At this time, the drying temperatures during solvent drying and thermosetting are preferably 100 ° C. or higher and 180 ° C. or lower, more preferably 100 ° C. or higher and 160 ° C. or lower, and 100 ° C. or higher and 140 ° C. or lower. Is most preferable.
• the heating time is preferably 30 seconds or less, more preferably 20 seconds or less. When the temperature is 180 ° C.
• the flatness of the film is maintained and the possibility of causing uneven thickness of the ceramic green sheet is small, which is preferable.
• the temperature is 140 ° C. or lower, the film can be processed without impairing the flatness of the film, and the possibility of causing uneven thickness of the ceramic green sheet is further reduced, which is particularly preferable. If it is lower than 100 ° C., the curing reaction of melamine does not proceed sufficiently and the elastic modulus of the release layer decreases, which is not preferable.
• the coating liquid for applying the release coating layer is not particularly limited, but it is preferable to add a solvent having a boiling point of 90 ° C. or higher.
• a solvent having a boiling point of 90 ° C. or higher bumping during drying can be prevented, the coating film can be leveled, and the smoothness of the coating film surface after drying can be improved.
• the amount to be added is preferably about 10 to 80% by mass with respect to the entire coating liquid.
• any known coating method can be applied as the coating method, for example, a roll coating method such as a gravure coating method or a reverse coating method, a bar coating method such as a wire bar, a die coating method, a spray coating method, or an air knife. Conventionally known methods such as the coating method can be used.
• a multilayer ceramic capacitor has a rectangular parallelepiped ceramic element. Inside the ceramic body, first internal electrodes and second internal electrodes are alternately provided along the thickness direction. The first internal electrode is exposed on the first end face of the ceramic body. A first external electrode is provided on the first end face. The first internal electrode is electrically connected to the first external electrode at the first end face. The second internal electrode is exposed on the second end face of the ceramic element. A second external electrode is provided on the second end face. The second internal electrode is electrically connected to the second external electrode at the second end face.
• the release film for manufacturing a ceramic green sheet of the present invention is used for manufacturing such a multilayer ceramic capacitor.
• it is manufactured as follows. First, the release film of the present invention is used as a carrier film, and a ceramic slurry for forming a ceramic element is applied and dried. An ultra-thin product having a thickness of 0.2 to 1.0 ⁇ m has been required for the ceramic green sheet. A conductive layer for forming the first or second internal electrode is printed on the coated and dried ceramic green sheet. A ceramic green sheet, a ceramic green sheet on which a conductive layer for forming a first internal electrode is printed, and a ceramic green sheet on which a conductive layer for forming a second internal electrode is printed are appropriately laminated and pressed.
• a mother laminate is obtained.
• the mother laminate is divided into a plurality of pieces to prepare a raw ceramic body.
• a ceramic body is obtained by firing a raw ceramic body.
• the multilayer ceramic capacitor can be completed by forming the first and second external electrodes.
• the slurry composition I made of the following materials was stirred and mixed for 10 minutes, and dispersed with zirconia beads having a diameter of 0.5 mm for 10 minutes using a bead mill to obtain a primary dispersion.
• Secondary dispersion was performed with 5.5 mm zirconia beads for 10 minutes to obtain a ceramic slurry.
• the slurry composition I made of the following materials was stirred and mixed for 10 minutes, and dispersed with zirconia beads having a diameter of 0.5 mm for 10 minutes using a bead mill to obtain a primary dispersion.
• Secondary dispersion was performed with 5.5 mm zirconia beads for 10 minutes to obtain a ceramic slurry.
• the release surface of the obtained release film sample was coated with an applicator so that the dried slurry had a thickness of 1.0 ⁇ m, dried at 60 ° C. for 1 minute, and a ceramic green sheet was molded on the release film. did.
• a peeling tester Kyowa Interface Science, VPA-3, load cell load 0.1N was used. The peeling angle was 90 degrees, the peeling temperature was 25 ° C., and the peeling speed was 10 m / min.
• a double-sided adhesive tape Nito Denko Co., Ltd., No.
• ⁇ 0.5 mN / mm or more, 1.5 mN / mm or less ⁇ : Larger than 1.5 mN / mm, 2.0 mN / mm or less ⁇ : Less than 0.5 mN / mm, larger than 2.0 mN / mm
• the release film sample was cut into a size of 10 cm ⁇ 10 cm, and heat-treated at 80 ° C. for 5 minutes in a hot air oven so that tension was not applied to the release film. Then, after taking out from the oven and cooling to room temperature, the release film sample was placed on the glass plate so that the release surface was facing up, and the heights of the portions floating from the glass plates at the four corners were measured. The average value of the floating amounts of the four corners measured at this time was taken as the curl amount.
• the curl property was evaluated according to the following criteria. ⁇ : The curl was 1 mm or less and hardly curled. ⁇ : The curl was larger than 1 mm and 3 mm or less, and a little curl was observed. X: The curl was larger than 3 mm, and curl was observed.
• the weight average molecular weight was calculated in terms of polystyrene, and the weight average degree of polymerization was calculated based on that value.
• PStQuick C TOSOH
• a sample film was prepared by cutting out from a release film roll into an area of 8 cm ⁇ 5 cm. This was fixed to the bottom surface of a metal rectangular parallelepiped having a size of 6 cm ⁇ 5 cm and a weight of 4.4 kg so that the surface layer B appeared on the surface. At this time, the 5 cm width direction of the sample film and the 5 cm width direction of the metal rectangular parallelepiped were aligned, one side of the sample film in the longitudinal direction was bent, and the sample film was fixed to the side surface of the metal rectangular parallelepiped with adhesive tape.
• a sample film was cut out from the same release film roll into an area of 20 cm ⁇ 10 cm, and the longitudinal end was fixed with adhesive tape on a flat metal plate so that the surface of the release layer was exposed.
• the measurement surface of the metal rectangular parallelepiped to which the sample film was attached was placed in contact with the measurement surface, and the measurement was performed under the conditions of a tensile speed of 100 mm / min, 23 ° C., and 65% RH. The measurement was performed three times, and the average value was adopted as the static friction coefficient ( ⁇ s).
• the measurement was performed using a Tencilon universal testing machine RTG-1210 manufactured by A & D Company.
• PET polyethylene terephthalate pellets
• esterification reaction device a continuous esterification reaction device consisting of a stirrer, a splitter, a raw material charging port, and a three-stage complete mixing tank having a raw material charging port and a product outlet was used.
• TPA terephthalic acid
• EG ethylene glycol
• antimony trioxide was set to an amount of 160 ppm of Sb atoms with respect to the PET produced, and these slurries were esterified.
• the reaction product in the first esterification reaction can is continuously taken out of the system and supplied to the second esterification reaction can, and distilled off from the first esterification reaction can in the second esterification reaction can.
• EG is supplied in an amount of 8% by mass with respect to the produced PET, and an EG solution containing an amount of magnesium tetrahydrate having an amount of Mg atoms of 65 ppm with respect to the produced PET and 40 ppm of P atoms with respect to the produced PET.
• PET (I) After filtering with a filter, ultrafiltration was performed, the mixture was extruded into water, cooled, and then cut into chips to obtain PET chips having an intrinsic viscosity of 0.60 dl / g (hereinafter abbreviated as PET (I)). ..
• PET (I) dl / g
• the lubricant content in the PET chip was 0.6% by mass.
• PET (II) Preparation of polyethylene terephthalate pellets (PET (II))
• PET (II) a PET chip having an intrinsic viscosity of 0.62 dl / g containing no particles such as calcium carbonate and silica was obtained (hereinafter, abbreviated as PET (II)).
• layer A separation surface side layer
• extruded casting
• An unstretched polyethylene terephthalate sheet having an intrinsic viscosity of 0.59 dl / g was obtained.
• the unstretched sheet was heated with an infrared heater and then stretched 3.5 times in the vertical direction at a roll temperature of 80 ° C. due to the speed difference between the rolls.
• E5101 (Toyobo ester (registered trademark) film, manufactured by Toyobo Co., Ltd.) having a thickness of 25 ⁇ m was used.
• E5101 has a structure in which particles are contained in the surface layer A and the surface layer B.
• the Sa of the surface layer A of the laminated film X2 was 24 nm, and the Sa of the surface layer B was 24 nm.
• solvent phenol / tetrachloroethane
• This unstretched PET sheet was heated to 100 ° C. with a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction with a roll group having a difference in peripheral speed to obtain a uniaxially stretched PET film.
• the I Ching coating liquid having the composition shown below was applied to one side of the PET film with a bar coater, and then dried at 80 ° C. for 15 seconds.
• the coating amount after final stretching and drying was adjusted to 0.1 ⁇ m.
• the film was stretched 4.0 times in the width direction at 150 ° C., and with the length of the film fixed in the width direction, heated at 230 ° C. for 0.5 seconds, and further at 230 ° C. for 10 seconds 3
• the relaxation treatment in the width direction of% was carried out to obtain a laminated film X3 having a thickness of 31 ⁇ m.
• the laminated film X3 has a structure in which the surface layer A does not substantially contain inorganic particles and has an easy-to-slip coating layer on the surface opposite to the surface layer A.
• the slippery coating layer is the surface layer B.
• the Sa of the surface layer A was 1 nm, and the Sa of the surface layer B was 2 nm.
• composition of I Ching coating liquid Water 41.86 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin (solid content concentration 20% by mass) 16.57 parts by mass Oxazoline-based cross-linking agent (solid content concentration 25% by mass) 5.68 parts by mass Colloidal silica 0. 59 parts by mass (manufactured by Nissan Chemical Co., Ltd., trade name MP2040, average particle size 200 nm, solid content concentration 40% by mass) Fluorine-based surfactant (solid content concentration 10% by mass) 0.30 parts by mass
• MMA methyl methacrylate
• HEMA hydroxyethyl methacrylate
• MAA methacrylic acid
• Example 1 A coating solution was prepared by mixing a release layer formation having the following composition (described in terms of solid content, the same applies hereinafter) with a mixed solvent of methyl ethyl ketone, toluene and isopropyl alcohol. This coating liquid is applied onto the surface layer A of the laminated film X1 using reverse gravure so that the release layer thickness after drying is 0.5 ⁇ m, and dried at 130 ° C. for 15 seconds to make it ultra-thin. A release film for producing a layered ceramic green sheet was obtained. With respect to the obtained release film, the charge amount, slipperiness, surface roughness, ceramic sheet peelability, ceramic sheet coatability, curl, and pinhole of the release layer were evaluated, and good evaluation results were obtained. ..
• Melamine compound 99.7 parts by mass full ether type methylated melamine, manufactured by Sanwa Chemical Co., Ltd., trade name: Nicarac MW-30M, weight average degree of polymerization 1.3, main component is hexamethoxymethylmelamine
• Release agent 0.3 parts by mass one-ended carboxyl-modified PDMS, manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: X22-3710, alkyl group intervenes between dimethylsiloxane and carboxyl group
• Example 2 A release film for producing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1 except that the contents of the melamine compound and the one-terminal carboxyl-modified PDMS were changed to the amounts shown in Table 1.
• Example 4 Ultra-thin as in Example 1 except that the release agent was changed to both-terminal carboxyl-modified PDMS (manufactured by Shin-Etsu Chemical Industry Co., Ltd., trade name: X22-162C, an alkyl group was interposed between dimethylsiloxane and the carboxyl group). A release film for producing a layered ceramic green sheet was obtained.
• Example 5 The content of the melamine compound is 99.9 parts by mass, and the release agent is a carboxyl-modified PDMS at both ends (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name: X22-162C, an alkyl group is interposed between dimethylsiloxane and the carboxyl group).
• a release film for producing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1 except that the amount was changed to 1 part by mass.
• Example 6 Ultra-thin as in Example 1 except that the release agent was changed to side chain carboxyl-modified PDMS (manufactured by Shinetsu Chemical Industry Co., Ltd., trade name: X22-3701E, alkyl group intervened between dimethylsiloxane and carboxyl group). A release film for producing a layered ceramic green sheet was obtained.
• Example 7 A release film for manufacturing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1 except that the release agent was changed to COOH-modified copolymer acrylic silicone (manufactured by Toagosei Co., Ltd., trade name: Cymac US-352). It was.
• Example 8 Example 1 except that the melamine compound was changed to full ether type methylated melamine (manufactured by Sanwa Chemical Co., Ltd., trade name: Nicarac MW-30, weight average degree of polymerization 1.5, main component is hexamethoxymethylmelamine). In the same manner as above, a release film for producing an ultrathin ceramic green sheet was obtained.
• full ether type methylated melamine manufactured by Sanwa Chemical Co., Ltd., trade name: Nicarac MW-30, weight average degree of polymerization 1.5, main component is hexamethoxymethylmelamine.
• Example 9 Example 1 and Example 1 except that the melamine compound was changed to full ether type methylated melamine (manufactured by Sanwa Chemical Co., Ltd., trade name: Nicarac MW-390, weight average degree of polymerization 1.0, main component is hexamethoxymethylmelamine). In the same manner, a release film for producing an ultrathin ceramic green sheet was obtained.
• full ether type methylated melamine manufactured by Sanwa Chemical Co., Ltd., trade name: Nicarac MW-390, weight average degree of polymerization 1.0, main component is hexamethoxymethylmelamine.
• Example 10 Except for changing to full ether type methylated melamine (weight average degree of polymerization 1.1, main component is hexamethoxymethylmelamine) obtained by recrystallizing the melamine compound (MW-30M) of Example 1 in isopropanol. , A release film for producing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1.
• Example 11 A release film for producing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1 except that the film thickness of the release layer was changed to the film thickness shown in Table 1.
• Example 13 A mold release film for manufacturing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1 except that the laminated film X2 was coated on the surface layer A.
• Example 14 A release film for producing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1 except that the laminated film X3 was coated on the surface layer A.
• Example 15 A mold release film for producing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1 under the conditions shown in Table 1B except that one-terminal hydroxyl group-modified PDMS was used as the mold release agent.
• the amount of charge of the obtained release film was 3.5 kV, the coefficient of static friction was 0.28, the amount of floating was 0.7, and the ceramic sheet was easily coated.
• the obtained release film showed the same peeling force as the release film obtained in Example 7, and almost no pinholes were generated.
• Example 16 A mold release film for producing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1 under the conditions shown in Table 1B except that one-terminal amino group-modified PDMS was used as the mold release agent. Under the conditions shown in Table 1B, a release film for producing an ultrathin ceramic green sheet was obtained in the same manner as in Example 1. The amount of charge of the obtained release film was 3.9 kV, the coefficient of static friction was 0.26, and the amount of floating was 0.7, and it had good ceramic sheet coatability. In addition, the obtained release film showed the same peeling force as the release film obtained in Example 7, and almost no pinholes were generated.
• the melamine-based compound is an imino-type melamine resin (manufactured by Sanwa Chemical Co., Ltd., trade name: Nicarax MX-730, weight average degree of polymerization 2.4) 99.5 parts by mass, and the release agent is PDMS containing a polyether-modified hydroxyl group (Big Chemie. Made by Japan, trade name: BYK-377) Manufacture of ultra-thin ceramic green sheet in the same manner as in Example 1 except that it was changed to 0.5 parts by mass and coated so that the film thickness was 1.0 ⁇ m. A release film was obtained.
• Example 2 Ultra-thin ceramic green sheet in the same manner as in Example 1 except that the melamine compound was changed to imino-type melamine resin (manufactured by Sanwa Chemical Co., Ltd., trade name: Nicarac MX-730, weight average degree of polymerization 2.4). A release film for production was obtained.
• imino-type melamine resin manufactured by Sanwa Chemical Co., Ltd., trade name: Nicarac MX-730, weight average degree of polymerization 2.4.
• the amount of charge of all the release films obtained in the comparative examples was outside the range of the present invention. For this reason, there was a tendency for extremely small environmental foreign substances during the process to adhere to the release film.
• the surface of the release layer is highly smooth, the ceramic green sheet can be peeled off uniformly and with a low force, and the release layer is hard to be charged, so that foreign matter is hard to adhere to the film, and the thickness is 1 ⁇ m.
• the following ultra-thin ceramic green sheets can be manufactured without substantially causing defects caused by foreign substances.

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