JP7318695B2 - Release film for manufacturing ceramic green sheets - Google Patents

Description

TECHNICAL FIELD The present invention relates to a release film for manufacturing ceramic green sheets, and more particularly, it is possible to suppress the occurrence of process defects such as flatness defects and peeling defects when manufacturing ultra-thin ceramic green sheets, and to reduce the release film. The present invention relates to a release film for manufacturing an ultra-thin ceramic green sheet, which can reduce adhesion of foreign matter to the release film by adjusting the amount of charge, and can suppress contamination of the ceramic green sheet with foreign matter.

Conventionally, a release film obtained by laminating a release layer on a polyester film as a base material has been used for molding ceramic green sheets such as laminated ceramic capacitors and ceramic substrates. In recent years, along with miniaturization and increase in capacity of laminated ceramic capacitors, the thickness of ceramic green sheets tends to be reduced. A ceramic green sheet is formed by coating a release film with a slurry containing a ceramic component such as barium titanate and a binder resin and drying the slurry. After electrodes are printed on the molded ceramic green sheets and separated from the release film, the ceramic green sheets are laminated, pressed, fired, and external electrodes are applied to manufacture the laminated ceramic capacitor. When molding a ceramic green sheet on the release layer surface of a polyester film, there is a problem that microscopic projections on the surface of the release layer affect the molded ceramic green sheet, making defects such as repelling and pinholes more likely to occur. there were. Therefore, various techniques have been developed for realizing a release layer surface having excellent flatness (for example, Patent Document 1).

However, in recent years, the thickness of ceramic green sheets has been further reduced, and ceramic green sheets having a thickness of 1.0 μm or less, more specifically, a thickness of 0.2 μm to 1.0 μm have been required. Therefore, there is a possibility that the very slight unevenness existing on the surface of the release layer is transferred to the molded ceramic green sheet, resulting in unevenness in thickness and leading to defects.

Therefore, in recent years, various techniques have been developed for achieving smoothness of the release layer. For example, there is a technique of providing a smoothing layer between the release layer and the base material to fill in irregularities caused by particles contained in the base material, thereby improving the smoothness of the surface of the release layer (for example, Patent Document 2). . Further, it has been proposed to increase the smoothness of the surface of the release layer by making the surface of the substrate on which the release layer is provided substantially free of particles (for example, Patent Document 3).

However, the methods of Patent Documents 2 and 3 have a problem that the release film is easily charged because the release layer is smoothed. More specifically, when the film is wound into a roll, the contact area between the release layer and the opposite side (back side) increases, so the film may be rolled tightly or may be damaged by vibrations during transportation. , the surface opposite to the release layer (rear surface) was rubbed against each other and tended to be more easily electrified. When the release film is charged, minute environmental foreign matter during the process and film scraps generated at the time of slitting tend to adhere to the ceramic green sheet due to static electricity, which may lead to defects.

As a method for suppressing the charge of the release film, there is a method of incorporating an antistatic agent in the release layer, and an antistatic coating layer on the side opposite to the release layer or on the intermediate layer between the release layer and the base film. (For example, Patent Documents 4 and 5). However, 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 and form coarse projections. again. There is a risk that the surface characteristics and curability will be adversely affected, and that the peelability of the ultra-thin ceramic green sheet will be insufficient. In addition, when an antistatic layer is provided on the surface opposite to the release layer or on the intermediate layer between the release layer and the base film as in Patent Document 5, the number of processing steps increases, and the antistatic agent is generally used. Since it is expensive, the cost has increased, and there was a big problem in terms of economy.

JP-A-2000-117899 JP 2009-208236 A JP 2015-033811 A JP 2014-189007 A WO2016/133092

The present invention has been made against the background of such 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 even an ultra-thin layer product with a thickness of 1 μm or less has few defects. An object of the present invention is to provide a release film for manufacturing a ceramic green sheet, which can be molded into a ceramic green sheet.

As a result of intensive studies by the present inventors in order to solve the above problems, a composition containing a specific release agent and a melamine compound is directly or via another layer on the surface layer A of the polyester film using a polyester film. It has been found that a release film for manufacturing a ceramic green sheet can be provided which is excellent in smoothness and releasability of the ceramic green sheet and has a small amount of charge by providing a release layer formed by curing a material.

That is, the present invention consists of the following configurations.
1. When a polyester film is used as a base material, a layer forming one surface of the base material is a surface layer A, and a layer forming the other surface is a surface layer B, directly on the surface layer A Or a release film in which a release layer is laminated via another layer, the release layer and the surface layer B are brought into contact, and held under an atmosphere of 50 ° C. and a pressure of 10 kPa for 48 hours, A release film for producing a ceramic green sheet, wherein the charge amount of the release layer when the release layer and the surface layer B are separated is ±5 kV or less.
2. 1. The release film for manufacturing a ceramic green sheet according to 1 above, wherein the static friction coefficient μs when the release layer and the surface layer B are superimposed is less than 0.30.
3. 3. For producing a ceramic green sheet according to the above 1 or 2, wherein no antistatic layer is provided on the surfaces of the surface layer A and the surface layer B, and the surface layer A and the surface layer B do not contain an antistatic agent. release film.
4. The release layer is obtained by curing a composition containing at least a release agent and a melamine compound, the release layer forming composition does not contain an antistatic agent, and the melamine compound is 1.7 or less, and the content of the melamine compound in the release layer is 80% by mass or more based on the solid content of the release layer-forming composition. 3. A release film for producing a ceramic green sheet according to any one of 1 to 3.
5. 4. The release film for producing a ceramic green sheet according to any one of the above 1 to 4, wherein the release agent contained in the release layer-forming composition is polyorganosiloxane containing carboxyl groups.
6. 5. The release film for producing a ceramic green sheet according to any one of 1st to 5th above, wherein the surface layer A does not substantially contain inorganic particles.
7. The first to sixth above, wherein the surface layer B contains particles, at least 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 producing 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 first to seventh items, wherein the molded ceramic green sheet has a thickness of 0.2 μm to 0.2 μm. A method for producing a ceramic green sheet having a thickness of 1.0 μm.
9. A method for manufacturing a ceramic capacitor employing the method for manufacturing a ceramic green sheet according to the eighth above.

The release film for manufacturing an ultra-thin ceramic green sheet of the present invention has a small amount of charge, a smooth surface of the release layer, and excellent peelability of the ceramic green sheet. It is possible to suppress the occurrence of defects and defects, and to efficiently produce an ultra-thin ceramic green sheet having a thickness of 0.2 to 1.0 μm.

The present invention will be described in detail below.

In the release film for producing a ceramic green sheet of the present invention, a release layer is laminated directly or via another layer on the surface layer A of the polyester film as a base material, and the surface layer A and the surface layer A It is preferable that the surface layer B on the opposite side is not provided with an antistatic layer. The release layer preferably does not contain an antistatic agent and is formed by curing a composition containing at least a melamine compound and polyorganosiloxane.

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 production process, after the release layer has been processed, the film is wound up and stored in a roll form, which may cause a problem of charge increase over time. For example, if the amount of electrification of the roll-shaped film is large, minute environmental foreign matter during the slitting process or the ceramic green sheet forming process and film waste generated during the slitting process tend to adhere to the film. These foreign substances attached to the film may be mixed into the ceramic green sheet, which may lead to defects. Therefore, the release film preferably has a release layer that is difficult to be charged.

As an example of evaluating the difficulty of charging, it can be confirmed by contacting the release layer and the surface layer B, applying a load and holding the layer for a certain period of time, and then evaluating the charge amount of the release layer. In this evaluation method, it is possible to model-evaluate the amount of charge that increases with time when the film is stored in a roll form. A 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 better. . By setting the charge amount of the release layer to ±5 kV or less, the increase in the charge amount over time when the film is stored in a roll form is small, and foreign matter is less likely to adhere to the film, which is preferable. The smaller the charge amount of the release layer, the better, but it may be 0.1 kV or more, or may be 0.3 kV or more.

In the present invention, the antistatic agent is an ion-conductive polymer compound, a π-electron conjugated polymer compound, etc., as well as a conductive filler, a metal layer, a metal oxide layer, etc. for the purpose of imparting conductivity. It means the substance used. Examples of ion-conducting polymer compounds include ammonium group-containing compounds, polyether compounds, sulfonic acid compounds, betaine compounds, and the like. π-electron conjugated polymer compounds polyacetylene, polyphenylene, polyaniline, polypyrrole, polyisothianaphthene, polythiophene, and the like. Conductive fillers include metals such as gold, silver, copper, aluminum, nickel, titanium, iron, zinc, and tin, fillers and fibers of alloys thereof, metal oxide fillers (silica, titania, etc., which are exclusively slippery). etc., excluding those used for purposes other than conductivity), metal-coated synthetic fibers, conductive carbon fibers such as carbon nanotubes, and the like. In the present invention, the term "antistatic layer" means a layer containing an antistatic agent as described above and exhibiting an antistatic effect.

(polyester film)
The polyester that constitutes the polyester film used as the base material in the present invention is not particularly limited, and it is possible to use a film-formed polyester that is commonly used as a base material for a release film. It is preferably a crystalline linear saturated polyester comprising an aromatic dibasic acid component and a diol component, such as polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, polytrimethylene terephthalate, or resins thereof. Component-based copolymers are more preferred, and polyester films formed from polyethylene terephthalate are particularly preferred. In polyethylene terephthalate, the repeating unit of ethylene terephthalate is preferably 90 mol % or more, more preferably 95 mol % or more, and may be copolymerized with a small amount of other dicarboxylic acid component or diol component, but from the viewpoint of cost. , preferably made only from terephthalic acid and ethylene glycol. In addition, known additives such as antioxidants, light stabilizers, ultraviolet absorbers, crystallization agents, etc. may be added within limits that do not impair the effects of the film of the present invention. The polyester film is preferably a biaxially oriented polyester film because of its high bidirectional elastic modulus.

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. When the intrinsic viscosity is 0.50 dl/g or more, it is preferable because many breakages do not occur in the stretching process. Conversely, when it is 0.70 dl/g or less, the cutting performance is good when cutting into a predetermined product width, and dimensional defects do not occur, which is preferable. Moreover, it is preferable to sufficiently vacuum-dry the raw material pellets.

The method for producing the polyester film in the present invention is not particularly limited, and conventionally generally used methods can be used. For example, the polyester is melted with an extruder, extruded into a film, cooled with a rotating cooling drum to obtain an unstretched film, and the unstretched film is uniaxially or biaxially stretched. I can. The biaxially stretched film can be obtained by a method of sequentially biaxially stretching a longitudinally or laterally uniaxially stretched film in the lateral direction or longitudinal direction, or by a method of simultaneously biaxially stretching an unstretched film in the longitudinal direction and the lateral direction. I can.

In the present invention, the stretching temperature during stretching of the polyester film is preferably higher than the secondary transition point (Tg) of the polyester. It is preferable that the film is stretched 1 to 8 times, particularly 2 to 6 times, in each of the longitudinal and transverse directions.

The polyester film preferably has a thickness of 12 to 50 μm, more preferably 15 to 38 μm, more preferably 19 to 33 μm. If the thickness of the film is 12 μm or more, it is preferable because there is no risk of deformation due to heat during film production, the process of releasing the release layer, or the molding of ceramic green sheets. On the other hand, if the thickness of the film is 50 μm or less, the amount of the film to be discarded after use is not excessively increased, which is preferable for reducing the environmental load.

The polyester film substrate may be a single layer, but preferably a multilayer of two or more layers. A mode in which a layer forming one surface of the polyester film substrate is a surface layer A, a layer forming the other surface is a surface layer B, and a release layer is laminated on the surface layer A. will be explained below. Preferably, the surface layer A does not substantially contain inorganic particles. On the other hand, the surface layer B preferably contains particles and the like. As the laminated structure of the release film, the layer on the side to which the release layer is applied is the surface layer A, the layer on the opposite side is the surface layer B, and the intermediate layer other than these is the layer C. The layer structure in the thickness direction is Laminated structures such as release layer/A/B or release layer/A/C/B may be mentioned. As a matter of course, the layer C may be composed of a plurality of layers.

The surface layer B may be a layer formed by a so-called co-extrusion method using a polyester as a main component resin together with the surface layer A, but it is provided as a coating layer on the surface opposite to the surface layer A of the polyester film. can be anything. When the surface layer B is the coating layer described above, it is preferable that the surface layer B contains a binder resin and particles.

In the polyester film substrate of the present invention, the surface layer A forming the surface to be coated with the release layer preferably does not substantially contain inorganic particles. At this time, the area surface average roughness (Sa) of the surface layer A is preferably 7 nm or less. When Sa is 7 nm or less, pinholes and the like are less likely to occur during molding of laminated ultra-thin ceramic green sheets, 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. Here, when the below-described anchor coat layer or the like is provided on the surface layer A, it is preferable that the coat layer does not substantially contain inorganic particles, and the region surface average roughness (Sa) after lamination of the coat layer is within the above range. It is preferable to enter In the present invention, "substantially free of inorganic particles" means a content of 50 ppm or less, preferably 10 ppm or less, most preferably a detection limit or less when the inorganic elements are quantified by fluorescence X-ray analysis. do. This is because even if inorganic particles are not positively added to the film, contaminants derived from foreign substances and dirt adhering to the lines and equipment in the raw material resin or film manufacturing process peel off and mix into the film. This is because there are cases.

In the polyester film substrate of the present invention, the surface layer B, which forms the surface opposite 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. Silica particles and/or calcium carbonate particles are preferably used. The content of the particles contained in the surface layer B is preferably 5000 to 15000 ppm in total. At this time, the area average surface 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. When the total amount of silica particles and/or calcium carbonate particles is 5000 ppm or more and Sa is 1 nm or more, when the film is wound into a roll, air can escape uniformly, resulting in a good roll shape and good flatness. , suitable for the production of ultra-thin ceramic green sheets. In addition, when the total amount of silica particles and/or calcium carbonate particles is 15000 ppm or less and Sa is 40 nm or less, aggregation of the lubricant is difficult to occur and coarse protrusions cannot be formed, so that the quality is stable when manufacturing an ultra-thin ceramic green sheet. and preferred.

As the particles contained in the surface layer B, inert inorganic particles and/or heat-resistant organic particles can be used in addition to silica and/or calcium carbonate. Silica particles and/or calcium carbonate particles are preferably used from the viewpoint of transparency and cost, but other usable inorganic particles include alumina-silica composite oxide particles and hydroxyapatite particles. Examples of heat-resistant organic particles include crosslinked polyacrylic particles, crosslinked polystyrene particles, and benzoguanamine particles. When silica particles are used, 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 diameter of the particles added to the surface layer B is preferably 0.1 μm or more and 2.0 μm or less, and particularly preferably 0.5 μm or more and 1.0 μm or less. If the average particle size of the particles is 0.1 μm or more, the slipperiness of the release film is good, which is preferable. In addition, if the average particle size is 2.0 μm or less, it is preferable because there is no fear of generating pinholes in the ceramic green sheet due to coarse particles on the surface of the release layer.

The surface layer B may contain two or more kinds of particles made of different materials. Further, particles of the same type but different in average particle diameter may be contained.

When the slippery coating layer described above is provided as the surface layer B on the opposite side of the surface layer A, it is preferably provided by in-line coating during film formation of the polyester film. Even when an easy-slip coating layer is provided, the area 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 preferred.

The film thickness of the surface layer B of the smooth coating layer is preferably 2 μm or less, more preferably 1 μm or less, still more preferably 0.8 μm or less, and particularly preferably 0.5 μm or less. When the film thickness of the coating layer is 2 μm or less, blocking is not likely to occur, which is preferable.

The binder resin constituting the easy-smooth coating layer is not particularly limited, but specific examples of polymers include polyester resins, acrylic resins, urethane resins, polyvinyl resins (polyvinyl alcohol, etc.), polyalkylene glycol, polyalkyleneimine, and methyl cellulose. , hydroxycellulose, starches, and the like. Among these resins, polyester resins, acrylic resins, and urethane resins are preferably used from the viewpoint of particle retention and adhesion. In addition, acrylic resin is particularly preferable when the hardness of the easy-slip coating layer is taken into consideration. Further, other preferred binder resins constituting the easy-slip coating layer on the polyester base film include polyester resins and urethane resins. Copolyester is preferable as the polyester resin. Incidentally, the polyester resin may be modified with polyurethane. Urethane resins include polycarbonate polyurethane resins. Furthermore, an acrylic resin, a polyester resin, and a polyurethane resin may be used in combination, and other binder resins may be used in combination.

In the present invention, in order to form a crosslinked structure in the slippery coating layer forming the surface layer B, the slippery coating layer may contain a cross-linking agent. By containing a cross-linking agent, it becomes possible to further improve the hardness of the easy-slip coating layer. Specific cross-linking agents include urea-based, epoxy-based, melamine-based, isocyanate-based, oxazoline-based, carbodiimide-based, and the like. Oxazoline-based and carbodiimide-based cross-linking agents are particularly preferred because they can improve the cross-linking density. In addition, a catalyst or the like can be appropriately used as necessary in order to accelerate the cross-linking reaction.

The easy-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, and include (1) silica, kaolinite, talc, light calcium carbonate, heavy calcium carbonate, zeolite, alumina, Barium sulfate, carbon black, zinc oxide, zinc sulfate, zinc carbonate, zirconium oxide, titanium dioxide, satin white, aluminum silicate, diatomaceous earth, calcium silicate, aluminum hydroxide, hydrated halloysite, calcium carbonate, magnesium carbonate, calcium phosphate, hydroxide inorganic particles such as magnesium and barium sulfate; Examples include organic particles such as isoprene, methyl methacrylate/butyl methacrylate, melamine, polycarbonate, urea, epoxy, urethane, phenol, diallyl phthalate, and polyester. Silica is particularly preferably used to impart lubricity.

From the viewpoint of reducing pinholes, it is preferable not to use recycled raw materials in 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 layer thickness of the base film. If it is 20% or more, the inside of the film is less likely to be affected by the particles contained in the surface layer B, etc., and it is easy for the region surface average roughness Sa to satisfy the above range, which is preferable. When the total thickness of the substrate film is 50% or less of the thickness of all layers of the substrate film, the ratio of the recycled raw material used in the surface layer B and the intermediate layer C described above can be increased, which is preferable because the environmental load is reduced.

From the viewpoint of economy, the layers other than the surface layer A (the surface layer B or the intermediate layer C described above) may contain 50 to 90% by mass of recycled film scraps and PET bottle raw materials. Even in this case, the type and amount of lubricant contained in the surface layer B, the particle size, and the area surface average roughness (Sa) preferably satisfy the above ranges.

In addition, a coat layer is provided on the surface of the surface layer A and/or the surface layer B before stretching in the film forming process or after uniaxial stretching in order to improve the adhesion of a release layer to be applied later. It is also possible to apply corona treatment or the like.

However, it is preferable that 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. When the intermediate layer C is provided, the intermediate layer C also preferably does not contain an antistatic agent. By adopting a configuration that does not have an antistatic layer or an antistatic agent, it is possible to provide a release film with low peeling force at low cost.

(Structure of release layer)
The release layer in the present invention preferably does not contain an antistatic agent and is formed by curing a composition containing at least a melamine compound and polyorganosiloxane.

The release layer in the present invention preferably has a high crosslink density and a high elastic modulus in order to suppress the deformation of the release layer that occurs during peeling and to make the peel force low and uniform. Here, the elastic modulus of the release layer refers to the elastic modulus in the compression direction. In addition, it is preferable to use a release layer having a high cross-linking density and a high elastic modulus, because it suppresses an increase in the charge amount over time when the film is stored in a roll form. When the elastic modulus of the release layer is increased, the slipperiness with the surface layer B in contact with the release layer during roll storage is improved (easily slippery). When the release layer becomes slippery, the pressure applied in the vertical direction to the film surface can be easily released in the horizontal direction. It is preferable because it can be suppressed.

Further, the inventors have found that it is important to increase the cross-linking density of the release layer in order to suppress the amount of charge. By increasing the cross-linking density of the release layer, electron transfer between melamine resins present in the release layer becomes easier, and charging becomes difficult, 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 later in detail.

As the melamine-based compound used in the release layer in the present invention, a general one can be used without particular limitation, but it is obtained by condensing melamine and formaldehyde, and has a triazine ring and a methylol group and / or alkoxy in one molecule. Each preferably has one or more methyl groups. Specifically, a methylolmelamine derivative obtained by condensing melamine and formaldehyde is preferably etherified by dehydration condensation reaction with a lower alcohol such as methyl alcohol, ethyl alcohol, isopropyl alcohol, or butyl alcohol. Examples of methylolated melamine derivatives include monomethylolmelamine, dimethylolmelamine, trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine, and hexamethylolmelamine. One type may be used, or two or more types may be used.

In order to increase the reactivity of the melamine compound and increase the elastic modulus of the release layer, it is preferable to use hexamethylolmelamine or hexaalkoxymethylmelamine, which have more cross-linking points in one molecule. Hexaalkoxymethylmelamine is more preferred, and hexamethoxymethylmelamine is particularly preferred. At this time, hexamethylolmelamine is one in which X is a methylol group ( _--CH.sub.2 --OH) in the following formula (a). Hexaalkoxymethylmelamine is a product obtained by subjecting a methylolmelamine derivative to a dehydration condensation reaction using an alcohol, and X is ( _--CH.sub.2 --OR, R is an alkyl group having 1 to 4 carbon atoms). Hexamethoxymethylmelamine is one in which X is ( _--CH.sub.2 --OMe).

X in the above (a) may be the same or different. Moreover, the above Rs may be the same or different. Also, X may be (-H).

The melamine compound used in the present invention is preferably a mixture of multiple compounds rather than a single compound. From the structure of the compound that is the main component in the melamine-based compound, full ether type (X=-- _CH.sub.2 --OR, R is an alkyl group having 1 to 4 carbon atoms), methylol type (X=-- _CH.sub.2 --OH), They can be roughly classified into imino types (X=-H). From the viewpoint of reactivity, it is preferable to use a full ether type or a methylol type, more preferably a full ether type. Most preferably used. The higher the hexamethoxymethylmelamine content of the melamine-based compound, the higher the reactivity and the higher the modulus of elasticity of the release layer.

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, still more preferably 400 or more and 800 or less. When the weight average molecular weight is 1000 or less, the cross-linking reaction proceeds easily, a film having a higher cross-linking density can be formed, and the release layer can be easily released and has a low charge amount, which is preferable. A weight-average molecular weight of 250 or more is preferable because the crosslink density does not become excessively large and curling does not deteriorate. In addition, the weight average molecular weight in this specification is the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.

The fact that the weight average molecular weight of the melamine compound is 250 to 1000 means that the melamine compound used in the present invention contains a large amount of mononuclear molecules. A mononuclear body has more cross-linking points and is more reactive than a polynuclear body formed by condensing two or more melamine derivatives. Therefore, a release layer having a high cross-linking density and excellent releasability can be obtained. The higher the mononuclear content, the more preferable, and it is most preferable to use a melamine-based compound consisting only of mononuclear.

The weight average molecular weight can also be represented by the weight average degree of polymerization. The weight average degree of polymerization of the melamine-based compound to be used is preferably 1.7 or less, more preferably 1.5 or less, even more preferably 1.3 or less, and the smaller the degree, the more suitable it can be used. . When the weight average degree of polymerization is 1.7 or less, the content of the mononuclear substance contained in the melamine-based compound increases, so that the release layer has excellent reactivity, excellent peelability, and is difficult to be charged. It is preferable because it can be done. In addition, the weight average degree of polymerization in this specification is the value calculated based on the weight average molecular weight calculated|required by standard polystyrene conversion by a gel permeation chromatography.

A melamine-based compound may be mixed with an imino group (--NH ₂ --)-containing compound or a polynuclear compound during its synthesis process. Even if these melamine derivatives are mixed, if the weight-average molecular weight (that is, weight-average degree of polymerization) of the melamine-based compound is within the above range, the reactivity is excellent and each can be preferably used.

The release layer in the present invention preferably contains 80% by mass or more and 99.9% by mass or less of the melamine compound relative to the solid content of the release layer-forming composition, more preferably 90% by mass or more. It is 99.9% by mass or less, more preferably 95% by mass or more and 99.9% by mass or less. When the melamine-based compound is contained in an amount of 80% by mass or more, the release layer can obtain a high cross-linking density due to self-crosslinking of the melamine-based compound, and the release layer has a high elastic modulus, which is preferable. At this time, the solid content of the release layer-forming composition is substantially the sum of the solid content of the melamine-based compound and the release agent, since a considerable portion of the solvent and acid catalyst evaporates during the drying process. It is safe to assume.

It is preferable to add an acid catalyst to the release layer in the present invention in order to promote the cross-linking reaction of the melamine-based compound. preferable. As the acid catalyst to be used, it is preferable to use a sulfonic acid catalyst.

As the sulfonic acid catalyst, for example, p-toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, trifluoromethanesulfonic acid and the like can be preferably used. From the viewpoint of compatibility, p-toluenesulfonic acid can be particularly preferably used.

Commercially available sulfonic acid catalysts can also be used in the present invention. Examples of commercially available products include Dryer (registered trademark) 900 (p-toluenesulfonic acid, manufactured by Hitachi Chemical Co., Ltd.), NACURE (registered trademark) DNNDSA series (dinonylnaphthalenedisulfonic acid, manufactured by Kusumoto Chemicals Co., Ltd.), DNNSA series ( Dinonylnaphthalene (mono)sulfonic acid, manufactured by Kusumoto Chemicals Co., Ltd.), DDBSA series (dodecylbenzenesulfonic acid, manufactured by Kusumoto Chemicals Co., Ltd.), p-TSA series (p-toluenesulfonic acid, manufactured by Kusumoto Chemicals Co., Ltd.), and the like. be done.

A sulfonic acid-based catalyst has higher acidity and superior reactivity as compared with other acid catalysts such as carboxylic acid-based catalysts, so that the release layer can be processed at a lower temperature. Therefore, it is possible to suppress deterioration of film flatness due to heat during processing and deterioration of winding appearance, which is preferable.

The amount of acid catalyst to be added is preferably 0.1 to 10% by mass based on 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. A content of 0.1% by mass or more is preferable because the curing reaction proceeds easily. On the other hand, when the content is 10% by mass or less, the acid catalyst is not likely to migrate to the ceramic green sheet to be molded, which is preferable because there is no possibility of having an adverse effect.

As the release agent (additive that improves the releasability of the release layer) used in the release layer in the present invention, general ones can be used without particular limitation, but carboxyl group, hydroxyl group, amino group, thiol It is preferable to use polyorganosiloxanes having functional groups, such as groups, that are capable of reacting with melamine compounds. 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 releasability and antistatic properties. Among polyorganosiloxane structures, those having a polydimethylsiloxane structure (abbreviated as PDMS) can be preferably used.

By containing carboxyl groups in the release agent polyorganosiloxane, the release agent does not show a strong interaction with the melamine compound during the drying process, making it easier to orient on the surface of the release layer, resulting in good releasability. can get. Therefore, it is preferable to use a polyorganosiloxane containing a carboxyl group, because even if the amount of the release agent added is small, the releasability can be satisfied. In addition, it is preferable because it becomes easier to orient on the surface of the release layer, thereby improving the slipperiness of the surface of the release layer and making it difficult to be charged.

A carboxyl group may be introduced at one terminal of the polyorganosiloxane, or may be at both terminals or in a side chain. Also, the position to be introduced may be one or plural.

Carboxyl group-modified polyorganosiloxane may be one in which carboxyl groups are directly bonded to silicon atoms of polyorganosiloxane, but those in which carboxyl groups are bonded to polyorganosiloxane via alkyl groups or aryl groups There may be. However, polyorganosiloxanes in which carboxyl groups are bonded via organic groups having repeating structures such as polyethers, polyesters, and polyurethanes are not very preferable.

The functional group to be introduced into the release agent polyorganosiloxane may have a functional group other than the carboxyl group in one molecule, but only the carboxyl group is preferred. Including a functional group other than a carboxyl group is not preferable because the intermolecular interaction with the melamine-based compound increases more than necessary and orientation to the surface of the release layer may become difficult.

Polyorganosiloxanes modified with hydroxyl groups that show strong interaction with melamine-based compounds react rapidly with melamine-based compounds during the drying process, so it is difficult to align on the surface of the release layer and exhibit releasability. There is Therefore, it is necessary to increase the amount of addition in order to provide sufficient releasability, but in that case, the elastic modulus of the release layer may decrease and the release force may increase. Further, when the amount of polyorganosiloxane added is increased, the coatability may be deteriorated when molding the ceramic green sheet, 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, polyorganosiloxane containing carboxyl groups tends to segregate on the release layer surface, which is preferable from the viewpoint of releasability and charge amount.

As described above, the carboxyl group-containing polyorganosiloxane is more preferably carboxyl group-containing polydimethylsiloxane. As polydimethylsiloxane containing a carboxyl group, X22-3701E (side chain carboxyl-modified polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.), X22-3710 (single-end carboxyl-modified polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.), X22 -162C (both terminal carboxyl-modified polydimethylsiloxane, manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-750 (both terminal carboxyl-modified polydimethylsiloxane, Toray Dow Corning Co., Ltd.), BY16-880 (side chain carboxyl-modified polydimethylsiloxane, Toray manufactured by Dow Corning), Magnasoft 800L (polydimethylsiloxane modified with carboxyl at both ends, manufactured by Momentive), and the like can be used.

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. Examples of acrylic resins in which polydimethylsiloxane is introduced into the side chain of the acrylic main chain containing a carboxyl group include Saimac (registered trademark) US-350, US-352, and US-380 (manufactured by Toagosei Co., Ltd.). can be used. Moreover, it may be an acrylic resin 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. As an acrylic resin in which polydimethylsiloxane is introduced into the side chain of the acrylic main chain containing a carboxyl group and a hydroxyl group in one molecule, Saimac (registered trademark) US-450, US-480 (manufactured by Toagosei Co., Ltd.) ) 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 based on the solid content of the composition for forming a release layer. It is more preferably 0.1% by mass or more and 3% by mass or less, and still more preferably 0.1% by mass or more and 1% by mass or less. When the amount is 0.05% by mass or more, not only is the releasability improved, but the release layer becomes more slippery, making it difficult to be charged, which is preferable. On the other hand, when it is 5% by mass or less, the elastic modulus of the release layer as a whole is not excessively lowered, which is preferable. In addition, when the content is 5% by mass or less, it is preferable from the viewpoint that there is no possibility that the coatability during molding of the ceramic green sheet is deteriorated. At this time, the solid content of the release layer-forming composition is substantially the sum of the solid content of the melamine-based compound and the release agent, since a considerable portion of the solvent and acid catalyst evaporates during the drying process. It is safe to assume.

The release layer in the present invention may contain particles having a particle size of 1 μm or less, but from the viewpoint of pinhole generation, it is preferable not to contain particles that form protrusions.

Other additives 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 preferred that the release layer does not contain an antistatic agent. A release layer containing no antistatic agent is preferable because the compatibility with the release agent and the melamine-based compound is deteriorated, and there is no possibility that the smoothness of the release layer is impaired due to the formation of aggregates. Moreover, it is preferable because the release layer can be formed more economically.

(Other characteristics)
In the present invention, the thickness of the release layer may be set according to the purpose of use, and is not particularly limited. Well, more preferably 0.05 to 0.8 μm, still more preferably 0.1 to 0.6 μm, and more preferably 0.1 to 0.4 μm. It is preferable that the thickness of the release layer is 0.01 μm or more, because the release performance can be obtained. Further, when the thickness is 1.0 μm or less, the curing time can be shortened, the flatness of the release film can be maintained, and the thickness unevenness of the ceramic green sheet can be suppressed, which is preferable. In addition, it is preferable that the release layer has a smaller thickness because it becomes more difficult to charge.

The release layer surface of the release film of the present invention is desirably flat in order not to cause defects in the ceramic green sheet coated and molded thereon, and the area surface average roughness (Sa) is 7 nm or less and the maximum The protrusion height (P) is preferably 100 nm or less. More preferably, the average surface roughness of the region is 5 nm or less and the maximum projection height is 80 nm or less.
For example, the maximum protrusion height (P) may be 45 nm or less.
If the surface roughness of the region 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 sheets are formed, and the yield is good, which is preferable. It can be said that the smaller the region surface average roughness (Sa) is, the more preferable it is, but it may be 0.1 nm or more, or 0.3 nm or more. It can be said that the smaller the maximum projection height (P) is, the more preferable it is, but the maximum projection height (P) may be 1 nm or more, or 3 nm or more.

The release film of the present invention preferably uses a base film having a surface layer A that is highly flattened. The mold layer surface can be smoothed. Therefore, even with a release layer using a highly reactive melamine-based compound, curling can be suppressed. In addition, since the amount of solvent and resin to be used can be reduced, it is environmentally friendly, and a release film for molding an ultra-thin ceramic green sheet can be produced at a low cost.

The release film of the present invention preferably has a peel 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. A peeling force of 0.5 mN/mm or more is preferable because the peeling force is not too light and there is no possibility that the ceramic green sheet will lift during transportation. When the peel force is 2.0 mN/mm or less, the ceramic green sheet is not likely to be damaged during peeling, which is preferable. For example, even when the required thickness of the ceramic green sheet is an ultra-thin product of 0.2 to 1.0 μm, the release film of the present invention can release the ceramic green sheet satisfactorily.

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 superimposed, for example, 0.25 or less and less than 0.25. is more preferred. If the coefficient of static friction is less than 0.30, the adhesive force between the release layer and the surface layer B is reduced, so that the film is tightly wound when stored in a roll and is electrified due to vibration during transportation. can be suppressed, which is preferable. The smaller the coefficient of static friction, the more preferable it is so that charging can be suppressed.

The release film of the present invention preferably has a curl of 3 mm or less, more preferably 1 mm or less after heating at 80° C. for 5 minutes without tension. Of course, it is also preferable not to curl at all. A thickness of 3 mm or less is preferable because curling can be minimized and printing accuracy can be improved when the ceramic green sheet is molded and the electrodes are printed.

In the present invention, the method for forming the release layer is not particularly limited. is removed by drying, followed by heat drying and heat curing. At this time, the drying temperature during solvent drying and heat curing is 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 preferred. The heating time is preferably 30 seconds or less, more preferably 20 seconds or less. When the temperature is 180° C. or lower, the planarity of the film is maintained, and the possibility of causing unevenness in the thickness of the ceramic green sheet is small, which is preferable. When the temperature is 140° C. or lower, the film can be processed without impairing the flatness of the film, and the possibility of causing unevenness in the thickness of the ceramic green sheet is further reduced, which is particularly preferred. If the temperature is lower than 100° C., the curing reaction of melamine does not proceed sufficiently and the elastic modulus of the release layer is lowered, which is not preferable.

In the present invention, the coating liquid for coating 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. By adding 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. As for the amount to be added, it is preferable to add about 10 to 80% by mass based on the entire coating liquid.

As a method for applying the coating liquid, any known coating method can be applied, 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 method, a die coating method, a spray coating method, and an air knife. A conventionally known method such as a coating method can be used.

(ceramic green sheet and ceramic capacitor)
Generally, a multilayer ceramic capacitor has a rectangular parallelepiped ceramic body. 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 surface of the ceramic body. A first external electrode is provided on the first end surface. The first internal electrode is electrically connected to the first external electrode at the first end surface. The second internal electrode is exposed on the second end face of the ceramic body. A second external electrode is provided on the second end surface. The second internal electrode is electrically connected to the second external electrode at the second end surface.

The release film for producing ceramic green sheets of the present invention is used for producing such a laminated ceramic capacitor. For example, it is manufactured as follows. First, using the release film of the present invention as a carrier film, a ceramic slurry for forming a ceramic body is applied and dried. As for the thickness of the ceramic green sheet, an ultra-thin product with a thickness of 0.2 to 1.0 μm is required. A conductive layer for forming the first or second internal electrode is printed on the coated and dried ceramic green sheet. Ceramic green sheets, ceramic green sheets printed with conductive layers for forming first internal electrodes, and ceramic green sheets printed with conductive layers for forming second internal electrodes are appropriately laminated and pressed. Thus, a mother laminate is obtained. The mother laminate is divided into a plurality of pieces to produce raw ceramic bodies. A ceramic body is obtained by firing a raw ceramic body. After that, the multilayer ceramic capacitor can be completed by forming the first and second external electrodes.

EXAMPLES The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. The characteristic values used in the present invention were evaluated using the following methods.

(Surface roughness)
These are values measured under the following conditions using a non-contact surface profile measurement system (VertScan R550H-M100). The area surface average roughness (Sa) was the average value of 5 measurements, and the maximum protrusion height (P) was measured 7 times, and the maximum value of the 5 measurements excluding the maximum and minimum values was used.
(Measurement condition)
・Measurement mode: WAVE mode ・Objective lens: 10x ・0.5×Tube lens ・Measurement area: 936 μm×702 μm
(analysis conditions)
・Surface correction: Quaternary correction ・Interpolation processing: Complete interpolation

(Evaluation of ceramic slurry coatability)
A slurry composition I consisting of the following materials was stirred and mixed for 10 minutes, and dispersed for 10 minutes with zirconia beads having a diameter of 0.5 mm using a bead mill to obtain a primary dispersion. After that, a slurry composition II consisting of the following materials was added to the primary dispersion at a ratio of (slurry composition I): (slurry composition II) = 3.4: 1.0, and a bead mill was used to prepare a slurry having a diameter of 0. Secondary dispersion was carried out for 10 minutes with 0.5 mm zirconia beads to obtain a ceramic slurry.
(Slurry composition I)
Toluene 22.3 parts by mass Ethanol 18.3 parts by mass Barium titanate (average particle diameter 100 nm) 57.5 parts by mass Homogenol L-18 (manufactured by Kao Corporation) 1.9 parts by mass (slurry composition II)
Toluene 39.6 parts by mass Ethanol 39.6 parts by mass Dioctyl phthalate 3.3 parts by mass Polyvinyl butyral (Eslec BM-S manufactured by Sekisui Chemical Co., Ltd.) 16.3 parts by mass
1-Ethyl-3-methylimidazolium ethylsulfate 0.5 parts by mass Then, 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 µm, and the temperature was 60°C. After drying for 1 minute, the coatability was evaluated according to the following criteria.
◯: Coating was completed on the entire surface without cissing or the like.
x: Sheet defects such as repelling are observed.

(Evaluation of pinholes in ceramic green sheets)
A ceramic green sheet having a thickness of 1 μm was formed on the release surface of the release film in the same manner as in the evaluation of the ceramic slurry coatability. Next, the release film was peeled off from the molded release film with the ceramic green sheet to obtain a ceramic green sheet. In the central region of the obtained ceramic green sheet in the film width direction, light was applied from the opposite side of the ceramic slurry-coated surface in a range of 25 cm ² , and the occurrence of pinholes that can be seen through light transmission was observed. judged visually.
○: No pinholes △: Almost no pinholes ×: Many pinholes

(Peelability evaluation of ceramic green sheet)
A slurry composition I consisting of the following materials was stirred and mixed for 10 minutes, and dispersed for 10 minutes with zirconia beads having a diameter of 0.5 mm using a bead mill to obtain a primary dispersion. After that, a slurry composition II consisting of the following materials was added to the primary dispersion at a ratio of (slurry composition I): (slurry composition II) = 3.4: 1.0, and a bead mill was used to prepare a slurry having a diameter of 0. Secondary dispersion was carried out for 10 minutes with 0.5 mm zirconia beads to obtain a ceramic slurry.
(Slurry composition I)
Toluene 22.3 parts by mass Ethanol 18.3 parts by mass Barium titanate (average particle diameter 100 nm) 57.5 parts by mass Homogenol L-18 (manufactured by Kao Corporation) 1.9 parts by mass (slurry composition II)
Toluene 39.6 parts by mass Ethanol 39.6 parts by mass Dioctyl phthalate 3.3 parts by mass Polyvinyl butyral (Eslec BM-S manufactured by Sekisui Chemical Co., Ltd.) 16.3 parts by mass
1-ethyl-3-methylimidazolium ethyl sulfate 0.5 parts by mass

Then, the dried slurry was applied to the release surface of the release film sample using an applicator so that the thickness of the slurry after drying was 1.0 μm, and dried at 60° C. for 1 minute to form a ceramic green sheet on the release film. bottom. After the release film with the resulting ceramic green sheet was statically eliminated using a static eliminator (manufactured by Keyence Corporation, SJ-F020), a peel tester (manufactured by Kyowa Interface Science Co., Ltd., VPA-3, load cell load 0.1N) was used. It was peeled at a peeling angle of 90 degrees, a peeling temperature of 25°C, and a peeling speed of 10 m/min. As for the peeling direction, a double-sided adhesive tape (manufactured by Nitto Denko Co., Ltd., No. 535A) was attached to the SUS plate attached to the peel tester, and the ceramic green sheet side was adhered to the double-sided tape on the release film. was fixed and peeled off by pulling the release film side. Among the obtained measured values, the average value of the peel force at the peel distance of 20 mm to 70 mm was calculated, and the value was defined as the peel force. The measurement was carried out a total of 5 times, and the average value of the peel strength was used for evaluation. Judgment was made according to the following criteria from the numerical value of the obtained peel strength.
◎: 0.5 mN / mm or more, 1.5 mN / mm or less ○: greater than 1.5 mN / mm, 2.0 mN / mm or less ×: less than 0.5 mN / mm, greater than 2.0 mN / mm

(Curl evaluation of release film)
A release film sample was cut into a size of 10 cm×10 cm, and heat-treated in a hot air oven at 80° C. for 5 minutes without applying tension to the release film. After that, it was taken out of the oven and cooled to room temperature, and then the release film sample was placed on a glass plate so that the release surface faced up, and the heights of the portions floating above the glass plate at the four corners were measured. The average value of the floating amounts measured at the four corners was taken as the curl amount. Curl property was evaluated according to the following criteria.
⊚: Curl of 1 mm or less, almost no curl O: Curl of more than 1 mm and 3 mm or less, slightly curled.
x: The curl was larger than 3 mm, and the curl was observed.

(Method for measuring weight average degree of polymerization)
Analysis Conditions 16 mg of sample was weighed and dissolved in 8 ml of chloroform. After filtration through a 0.2 μm membrane filter, GPC analysis of the resulting sample solution was performed under the following conditions.
Equipment: TOSOH HLC-8320GPC
Column: K-G + K-802 (exclusion limit molecular weight 5 × 10 ³ ) + K-801 (exclusion limit molecular weight 1.5 × 10 ³ ) (Shodex),
Solvent: 100% chloroform
Flow rate: 1.0ml/min
Concentration: 0.2%
Injection volume: 50 μL
Temperature: 40℃
Detector: RI

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) of the PStQuick series was used as polystyrene. Among the polystyrenes added to PStQuick C (TOSOH), polystyrene Mws of 2110000, 427000 and 37900, which greatly exceed the exclusion limit of the column, were excluded from the preparation of the calibration curve.

(charge amount)
Two samples for evaluation were prepared by cutting the release film into 10 cm×10 cm. Two samples for evaluation are neutralized using a static eliminator (manufactured by Keyence Corporation, SJ-F020), and after confirming that the voltage is 0 kV, the release layer and the surface layer B are separated with the release layer facing upward. made contact. The two contacting samples were sandwiched between medicine-wrapped papers, a load of 10.2 kg (pressure of 10 kPa) was applied thereon, and the sample was held at 50° C. for 48 hours. After 48 hours, the temperature was returned to room temperature (25°C), and then the two evaluation samples that had been in contact were peeled off, and the charge amount of the release layer that was in contact with the surface layer B was measured using a digital electrostatic potential meter. (KSD-1000, manufactured by Kasuga Denki Co., Ltd.). The charge amount measured at this time was evaluated according to the following criteria.
◎: Absolute value of charge amount is less than 3 kV ○: Absolute value of charge amount is 3 kV or more and 5 kV or less ×: Absolute value of charge amount is more than 5 kV

(Static friction coefficient)
A sample film was prepared by cutting an area of 8 cm×5 cm from the release film roll. This was fixed to the bottom surface of a metal cuboid weighing 4.4 kg and having a bottom surface size of 6 cm x 5 cm so that the surface layer B appeared on the surface. At this time, the 5 cm width direction of the sample film was aligned with the 5 cm width direction of the metal rectangular parallelepiped, one longitudinal side of the sample film was bent, and fixed to the side surface of the metal rectangular parallelepiped with an adhesive tape.

Next, a sample film having an area of 20 cm x 10 cm was cut from the same release film roll, and the longitudinal ends were fixed on a flat metal plate with an adhesive tape so that the surface of the release layer appeared. The measurement surface of the rectangular parallelepiped metal to which the sample film was adhered was placed on this so as to be in contact therewith, 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 coefficient of static friction (μs). The measurement was performed using a Tensilon universal testing machine RTG-1210 manufactured by A&D.

(Preparation of polyethylene terephthalate pellets (PET (I)))
As the esterification reactor, a continuous esterification reactor comprising a three-stage complete mixing tank having a stirrer, a partial condenser, a raw material inlet and a product outlet was used. TPA (terephthalic acid) was adjusted to 2 tons/hour, EG (ethylene glycol) was adjusted to 2 mol per 1 mol of TPA, and antimony trioxide was adjusted to give an amount of Sb atoms of 160 ppm relative to the produced PET. It was continuously supplied to the first esterification reactor of the reaction apparatus and reacted at 255° C. for an average residence time of 4 hours under normal pressure. Next, 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 into the second esterification reaction can. 8 mass % of EG is supplied to the produced PET, and further, an EG solution containing magnesium acetate tetrahydrate in an amount such that the Mg atom is 65 ppm relative to the produced PET, and an EG solution containing 40 ppm of P atom relative to the produced PET. An EG solution containing TMPA (trimethyl phosphate) in an amount corresponding to the above was added and reacted at 260° C. under normal pressure for an average residence time of 1 hour. Next, the reaction product in the second esterification reactor was continuously taken out of the system and supplied to the third esterification reactor, and was subjected to 39 MPa (400 kg/cm ² ) using a high-pressure disperser (manufactured by Nippon Seiki Co., Ltd.). 0.2% by mass of porous colloidal silica having an average particle size of 0.9 μm, which has been subjected to dispersion treatment for an average number of 5 passes at a pressure of , and 1% by mass of ammonium salt of polyacrylic acid per calcium carbonate. While adding 0.4% by mass of synthetic calcium carbonate with a diameter of 0.6 μm as a 10% EG slurry, the mixture was reacted at normal pressure at 260° C. for an average residence time of 0.5 hours. The esterification reaction product produced in the third esterification reaction vessel was continuously supplied to a three-stage continuous polycondensation reactor for polycondensation to sinter stainless steel fibers having a 95% cut diameter of 20 μm. After filtration with a filter, ultrafiltration was performed, the product was extruded into water, and after cooling, it was cut into chips to obtain PET chips having an intrinsic viscosity of 0.60 dl/g (hereinafter abbreviated as PET (I)). . The lubricant content in the PET chip was 0.6% by mass.

(Preparation of polyethylene terephthalate pellets (PET (II)))
On the other hand, in the production of the PET(I) chip, a PET chip containing no particles of calcium carbonate, silica, etc. and having an intrinsic viscosity of 0.62 dl/g was obtained (hereinafter abbreviated as PET(II)).

(Production of laminated film X1)
After drying these PET chips, they were melted at 285° C. and melted at 290° C. by a separate melt extruder extruder to filter sintered stainless steel fibers with a 95% cut diameter of 15 μm and Two-stage filtration of sintered stainless steel particles of 15 μm is performed, and they are combined in the feed block to form PET (I) on the surface layer B (anti-releasing surface side layer) and PET (II) on the surface. Laminated so as to form layer A (releasing surface side layer), extruded (cast) into a sheet at a speed of 45 m / min, electrostatically adhered on a casting drum at 30 ° C. by an electrostatic adhesion method, cooled, An unstretched polyethylene terephthalate sheet having an intrinsic viscosity of 0.59 dl/g was obtained. The layer ratio was adjusted so that PET (I)/(II)=60% by mass/40% by mass by calculating the discharge amount of each extruder. Then, the unstretched sheet was heated with an infrared heater and then stretched 3.5 times in the machine direction at a roll temperature of 80° C. due to the speed difference between the rolls. After that, it was led to a tenter and stretched 4.2 times in the transverse direction at 140°C. It was then heat treated at 210° C. in a heat setting zone. After that, a 2.3% relaxation treatment was applied in the transverse direction at 170° C. to obtain a biaxially stretched polyethylene terephthalate film X1 having a thickness of 31 μm. The Sa of the surface layer A of the obtained film X1 was 1 nm, and the Sa of the surface layer B was 28 nm.

(Production of laminated film X2)
As the laminated film X2, E5101 (Toyobo Ester (registered trademark) film, manufactured by Toyobo Co., Ltd.) having a thickness of 25 μm was used. E5101 has a structure in which surface layer A and surface layer B contain particles. 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.

(Production of laminated film X3)
As a film material polymer, PET resin pellets (PETII) having an intrinsic viscosity (solvent: phenol/tetrachloroethane = 60/40) of 0.62 dl/g and containing substantially no inorganic particles were prepared under a reduced pressure of 133 Pa. and dried at 135° C. for 6 hours. After that, it was supplied to an extruder, melt-extruded into a sheet at about 280° C., and rapidly cooled and solidified on a rotating cooling metal roll whose surface temperature was maintained at 20° C. to obtain an unstretched PET sheet.

This unstretched PET sheet was heated to 100° C. by a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction by a roll group with a peripheral speed difference to obtain a uniaxially stretched PET film.

Next, after coating one side of the PET film with a smooth coating liquid having the composition shown below with a bar coater, it was dried at 80° C. for 15 seconds. The coating amount after the final stretching and drying was adjusted to 0.1 μm. Subsequently, the film was stretched 4.0 times in the width direction at 150°C with a tenter, heated at 230°C for 0.5 seconds while fixing the length of the film in the width direction, and further heated at 230°C for 10 seconds 3. % in the width direction to obtain a laminated film X3 with a thickness of 31 μm. Laminated film X3 has a structure in which the surface layer A does not substantially contain inorganic particles, and the surface opposite to the surface layer A has an easy-slip coating layer. 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 slippery coating liquid)
Water 41.86 parts by mass Isopropyl alcohol 35.00 parts by mass Acrylic polyol resin (solid concentration 20% by mass) 16.57 parts by mass Oxazoline-based cross-linking agent (solids concentration 25% by mass) 5.68 parts by mass Colloidal silica 0.5 parts by mass 59 parts by mass (manufactured by Nissan Chemical Industries, trade name MP2040, average particle size 200 nm, solid content concentration 40% by mass)
Fluorinated surfactant (solid content concentration 10% by mass) 0.30 parts by mass

(Production of the acrylic polyol resin)
77 parts by mass of methyl methacrylate (MMA), 100 parts by mass of hydroxyethyl methacrylate (HEMA), and 33 parts by mass of methacrylic acid (MAA) were added to a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen blowing tube. and 490 parts by mass of isopropyl alcohol (IPA) were charged, and the temperature inside the flask was raised to 80° C. while stirring. Stirring was performed for 3 hours while maintaining the inside of the flask at 80° C., and then 0.5 parts by mass of 2,2-azobis-2-methyl-N-2-hydroxyethylpropionamide was added to the flask. After purging with nitrogen while raising the temperature in the flask to 120° C., the mixture was stirred at 120° C. for 2 hours.
Subsequently, a pressure reduction operation of 1.5 kPa was performed at 120° C. to remove unreacted raw materials and solvent to obtain an acrylic polyol. The inside of the flask was returned to atmospheric pressure and cooled to room temperature, and 840 parts by mass of an IPA aqueous solution (water content: 50% by mass) was added and mixed. After that, using a dropping funnel while stirring, triethylamine is added, the acrylic polyol is neutralized until the pH of the solution is in the range of 5.5 to 7.5, and the solid content concentration is 20% by mass. got

(Production of the above oxazoline-based cross-linking agent)
A flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer was charged with 460.6 parts of isopropyl alcohol and heated to 80° C. while nitrogen gas was slowly passed through. A previously prepared monomer mixture consisting of 126 parts of methyl methacrylate, 210 parts of 2-isopropenyl-2-oxazoline and 84 parts of methoxypolyethylene glycol acrylate, and 2,2′-azobis as a polymerization initiator were added thereto. (2-Methylbutyronitrile) ("ABN-E" manufactured by Nippon Hydrazine Kogyo Co., Ltd.) 21 parts of an initiator solution and 189 parts of isopropyl alcohol are dropped from a dropping funnel over 2 hours to react, and dropwise. After completion, the reaction was continued for 5 hours. Nitrogen gas was continuously flowed during the reaction to keep the temperature in the flask at 80±1°C. Thereafter, the reaction solution was cooled to obtain a resin having an oxazoline group with a solid concentration of 25%. The obtained resin having oxazoline groups had an oxazoline group content of 4.3 mmol/g and a number average molecular weight of 20,000 as measured by GPC (gel permeation chromatography).

(Example 1)
A coating liquid was prepared by mixing a release layer-forming material having the following composition (described in terms of the solid content; the same applies hereinafter) in a mixed solvent of methyl ethyl ketone, toluene and isopropyl alcohol. This coating solution was applied onto the surface layer A of the laminated film X1 using reverse gravure so that the thickness of the release layer after drying was 0.5 μm, and dried at 130° C. for 15 seconds to form an ultra-thin film. A release film for the production of layered ceramic green sheets was obtained. The resulting release film was evaluated for the charge amount of the release layer, slipperiness, surface roughness, ceramic sheet peelability, ceramic sheet coatability, curling, and pinholes, 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: Nicalac MW-30M, weight average degree of polymerization 1.3, main component is hexamethoxymethyl melamine)
Release agent 0.3 parts by mass (single-end carboxyl-modified PDMS, manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X22-3710, alkyl group interposed between dimethylsiloxane and carboxyl group)
p-toluenesulfonic acid 2.0 parts by mass

(Examples 2 and 3)
A release film for producing an ultra-thin ceramic green sheet was obtained in the same manner as in Example 1, except that the contents of the melamine-based compound and the one-end carboxyl-modified PDMS were changed to the amounts shown in Table 1.

(Example 4)
Ultra-thin in the same manner as in Example 1 except that the release agent was changed to carboxyl-modified PDMS at both ends (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X22-162C, an alkyl group interposed between the dimethylsiloxane and the carboxyl group). A release film for the production of layered ceramic green sheets was obtained.

(Example 5)
The content of the melamine compound was 99.9 parts by mass, and the mold release agent was carboxyl-modified PDMS (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X22-162C, an alkyl group interposed between the dimethylsiloxane and the carboxyl group). A release film for producing an ultra-thin ceramic green sheet was obtained in the same manner as in Example 1, except that the content was changed to 1 part by mass.

(Example 6)
Ultrathin in the same manner as in Example 1 except that the release agent was changed to a side chain carboxyl-modified PDMS (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: X22-3701E, an alkyl group interposed between the dimethylsiloxane and the carboxyl group). A release film for the production of layered ceramic green sheets was obtained.

(Example 7)
A release film for producing an ultra-thin ceramic green sheet was obtained in the same manner as in Example 1, except that the release agent was changed to a COOH-modified copolymerized acrylic silicone (manufactured by Toagosei Co., Ltd., trade name: Cymac US-352). rice field.

(Example 8)
Example 1 except that the melamine-based compound was changed to a full-ether type methylated melamine (manufactured by Sanwa Chemical Co., Ltd., trade name: Nicalac MW-30, weight average polymerization degree 1.5, main component is hexamethoxymethyl melamine). A release film for producing an ultra-thin ceramic green sheet was obtained in the same manner as in .

( Reference example 9)
Example 1 except that the melamine-based compound was changed to a full-ether type methylated melamine (manufactured by Sanwa Chemical, trade name: Nicalac MW-390, weight average polymerization degree 1.0, main component is hexamethoxymethyl melamine). A release film for producing an ultra-thin ceramic green sheet was obtained in the same manner. Also in Tables 1A and 1C, "Example 9" should be read as "Reference Example 9".

(Example 10)
The melamine compound (MW-30M) of Example 1 was recrystallized in isopropanol, except that it was changed to a full-ether methylated melamine (weight average degree of polymerization: 1.1, main component: hexamethoxymethylmelamine). A release film for producing an ultra-thin ceramic green sheet was obtained in the same manner as in Example 1.

(Examples 11 and 12)
A release film for producing an ultra-thin ceramic green sheet was obtained in the same manner as in Example 1, except that the thickness of the release layer was changed to the thickness shown in Table 1.

(Example 13)
A release film for producing an ultra-thin ceramic green sheet was obtained in the same manner as in Example 1, except that the surface layer A of the laminate film X2 was coated.

(Example 14)
A release film for producing an ultra-thin ceramic green sheet was obtained in the same manner as in Example 1, except that the surface layer A of the laminated film X3 was coated.

(Example 15)
A 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 PDMS modified with one terminal hydroxyl group was used as the release agent. The resulting release film had a charge amount of 3.5 kV, a static friction coefficient of 0.28, and a floating amount of 0.7, and had good ceramic sheet coatability. In addition, the obtained release film showed a peeling force comparable to that of the release film obtained in Example 7, and almost no pinholes were generated.

(Example 16)
A release film for producing an ultra-thin 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 release agent. A release film for producing an ultra-thin ceramic green sheet was obtained in the same manner as in Example 1 under the conditions shown in Table 1B. The obtained release film had a charge amount of 3.9 kV, a static friction coefficient of 0.26, and a floating amount of 0.7, and had good ceramic sheet coatability. In addition, the obtained release film showed a peeling force comparable to that of the release film obtained in Example 7, and almost no pinholes were generated.

(Comparative example 1)
The melamine compound is an imino type melamine resin (manufactured by Sanwa Chemical Co., Ltd., trade name: Nikalac MX-730, weight average polymerization degree 2.4) 99.5 parts by mass, and the release agent is polyether-modified hydroxyl group-containing PDMS (Big Chemie Co., Ltd. BYK-377 manufactured by Japan Co., Ltd.) was changed to 0.5 parts by mass, and the film thickness was changed to 1.0 μm. A release film for

(Comparative example 2)
An ultra-thin ceramic green sheet was prepared in the same manner as in Example 1, except that the melamine compound was changed to an imino-type melamine resin (manufactured by Sanwa Chemical Co., Ltd., trade name: Nikalac MX-730, weight average degree of polymerization: 2.4). A production release film was obtained.

(Comparative Example 3)
A release film for producing an ultra-thin ceramic green sheet was obtained in the same manner as in Example 1, except that the contents of the melamine-based compound and the one-end carboxyl-modified PDMS were changed to the amounts shown in Table 1.

(Comparative Example 4)
An ultra-thin ceramic green sheet was prepared in the same manner as in Example 1, except that the melamine compound was changed to a methylol-type melamine resin (manufactured by Sanwa Chemical Co., Ltd., trade name: Nikalac MS-11, weight average degree of polymerization: 1.8). A production release film was obtained.

(Comparative Example 5)
An ultra-thin layer ceramic was produced in the same manner as in Example 1, except that the melamine-based compound was changed to an imino-methylol-type melamine resin (manufactured by Sanwa Chemical Co., Ltd., trade name: Nikalac MS-001, weight average polymerization degree 5.7). A release film for green sheet production was obtained.

The charge amounts of the release films obtained in the comparative examples were all outside the range of the present invention. For this reason, minute environmental foreign matter during the process tends to adhere to the release film.

According to the present invention, the surface of the release layer is highly smooth, and the ceramic green sheet can be peeled uniformly with a low force. The ultra-thin layer ceramic green sheets described below can be manufactured without practically causing defects caused by foreign matter.

Claims (9)

When a polyester film is used as a base material, a layer forming one surface of the base material is a surface layer A, and a layer forming the other surface is a surface layer B, the surface layer A A release film in which a release layer is directly laminated,
The release layer and the surface layer B are brought into contact with each other and held under an atmosphere of 50° C. and a pressure of 10 kPa for 48 hours. ±5 kV or less,
An antistatic layer is not provided on the surfaces of the surface layer A and the surface layer B, and the surface layer A and the surface layer B do not contain an antistatic agent,
The release layer is obtained by curing a release layer-forming composition.
The release layer-forming composition contains polyorganosiloxane having a carboxyl group as a release agent,
The amount of the release agent used is 0.05-5% by mass in the release layer
The release layer-forming composition contains a melamine compound,
The weight average degree of polymerization of the melamine compound is more than 1.0 and 1.7 or less,
The melamine-based compound includes a full-ether type melamine resin,
Release film for manufacturing ceramic green sheets. 2. The release film for producing a ceramic green sheet according to claim 1, wherein the static friction coefficient μs when the release layer and the surface layer B are superimposed is less than 0.30. 2. The release film for manufacturing a ceramic green sheet according to claim 1 , wherein said ceramic green sheet has a thickness of 0.2 μm to 1.0 μm . The release layer-forming composition does not contain an antistatic agent ,
The release film for producing a ceramic green sheet according to claim 1 , wherein the content of the melamine-based compound in the release layer is 80% by mass or more relative to the solid content of the release layer- forming composition. The release film for producing a ceramic green sheet according to claim 1, wherein the melamine compound has a weight average molecular weight of 400 or more and 1000 or less . 2. The release film for producing a ceramic green sheet according to claim 1, wherein the surface layer A contains substantially no inorganic particles. 2. The surface layer B according to claim 1, wherein the surface layer B contains particles, at least part of the particles are silica particles and/or calcium carbonate particles, and the total content of the particles relative to the mass of the surface layer B is 5000 to 15000 ppm. Release film for manufacturing ceramic green sheets. 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 claims 1 to 7, wherein the molded ceramic green sheet has a thickness of 0.2 μm to 1 μm. A method for producing a ceramic green sheet having a thickness of 0 μm. A method for manufacturing a ceramic capacitor employing the method for manufacturing a ceramic green sheet according to claim 8.