KR102342605B1 - Mold release film for ceramic green sheet production - Google Patents

Abstract

The present invention provides a release film for manufacturing a ceramic green sheet that has high smoothness by suppressing deterioration of surface roughness due to aggregation during drying of the release layer, and excellent releasability by adjusting the amount of silicone-based components on the surface of the release layer will do
The present invention uses a polyester film as a substrate, the substrate has a surface layer A substantially free of particles on at least one side, and at least one side of the surface layer A directly or another layer on the surface of the surface A release film in which a release layer is laminated via It is a release film for manufacturing a ceramic green sheet having a maximum protrusion height (P) of 50 nm or less on the surface of the layer and an average area roughness (Sa) of 1.5 nm or less.

Description

Release film for manufacturing ceramic green sheet {MOLD RELEASE FILM FOR CERAMIC GREEN SHEET PRODUCTION}

The present invention relates to a release film for manufacturing a ceramic green sheet, and more particularly, an ultra-thin ceramic capable of manufacturing a product that suppresses the occurrence of process defects due to pinholes and thickness non-uniformity during manufacturing of an ultra-thin ceramic green sheet It relates to a release film for manufacturing a green sheet.

In recent years, with the miniaturization and increase in capacity of multilayer multilayer ceramic capacitors (abbreviated MLCCs), thinning of the ceramic green sheet is required. In the multilayer multilayer ceramic capacitor, a ceramic green sheet is formed by coating a slurry containing a binder resin and a ceramic component such as barium titanate on a release film, and drying the resulting ceramic green sheet. After printing an electrode, It is manufactured by peeling from a release film, laminating|stacking and pressing a ceramic green sheet, degreasing and baking, and apply|coating an external electrode.

In order to make the MLCC smaller and larger in capacity, it is necessary to thin the ceramic green sheet, and the film thickness has become a thin film of 1.0 µm or less and further 0.6 µm or less, and further thinning is progressing. However, when the ceramic green sheet is thinned, there is a problem that defects such as pinholes and cracks are likely to occur due to extremely minute protrusions on the release film or force at the time of peeling from the release film.

In order to solve these problems, as a release film used for molding a ceramic green sheet, a film in which a release layer is provided on a polyester film and the surface of the release layer is highly smoothed has been proposed. In patent document 1, providing a smoothing layer on the surface of a polyester film, and providing a mold release layer on the smoothing layer after that is disclosed. Moreover, it is disclosed by patent document 2 to form the release layer which consists of (meth)acrylic acid ester and a silicone type component with the film thickness of 0.3 micrometer or more. According to description of patent document 1 and patent document 2, it is disclosed that the arithmetic mean roughness Ra of the mold release layer surface can be 8 nm or less, and the maximum processus|protrusion height Rp can be made into 50 nm or less.

However, according to the technique described in Patent Documents 1 and 2, since the thickness of the resin layer (release layer and smoothing layer) laminated on the polyester film is thick, curing takes time and the amount of the organic solvent to be used increases. There were problems such as a large environmental load. Moreover, since the film thickness of a release layer was thick, the curl etc. of the obtained release film may also become a subject. Moreover, in the technique described in these documents, the quantity of the silicone type component contained in a mold release layer was large, the elastic modulus of the surface of a mold release layer became low, and there existed a possibility that peeling became unstable.

Moreover, as a release layer of the release film for ceramic green sheet shaping|molding, the following proposals are also made|formed. In patent document 3, the non-silicone type|system|group mold release layer which does not contain silicone in a mold release layer is proposed. In patent document 4, the film which used the silicone resin as the mold release layer is proposed. However, if it is a non-silicon type release layer like the technique described in patent document 3, however, the peeling force at the time of peeling a ceramic green sheet becomes large, and there exists a subject of receiving damage in the thinned ceramic green sheet. In addition, in the release layer of a silicone resin as described in Patent Document 4, the peeling force at the time of peeling the ceramic green sheet is small, but since the glass transition temperature of the silicone resin is generally room temperature or less, the elastic modulus is low, and the peeling force is low. Since the release layer deformed at the time, there was a problem that the peeling force became unstable.

Moreover, in patent document 5, the release layer containing an alkyd resin, an amino resin, and a modified silicone resin is proposed. Moreover, in patent document 6, the mold release layer containing a melamine resin and polyorganosiloxane is proposed. It has been proposed to increase the elastic modulus of the release layer and make both deformability and releasability compatible by mainly containing a crosslinked product such as a melamine resin as a binder of the release layer and adding a silicone resin as a release component.

However, as described in Patent Documents 5 and 6, in the case of a release layer containing a binder resin and a silicone-based resin, the solubility of the binder resin and the silicone-based resin in an organic solvent and the surface tension of the solution are greatly different. Compatibility worsened, and each resin aggregated and became a processus|protrusion, and there existed a subject which worsened the surface roughness of the surface of a mold release layer. When a ceramic green sheet having a thickness of 1.0 µm or less and further 0.6 µm or less is molded, pinholes or the like are generated even with such a slight deterioration of the surface roughness, and the defect rate of the obtained multilayer ceramic capacitor is deteriorated. Smoothness was required.

Japanese Patent Laid-Open No. 2014-177093 International Publication No. 2013/145864 Japanese Patent Laid-Open No. 2010-144046 Japanese Patent Laid-Open No. 2012-207126 Japanese Patent Laid-Open No. 9-239913 Japanese Patent Laid-Open No. 2017-7226

In the present invention, in view of the above situation, as a release layer of a release film for manufacturing a ceramic green sheet, even if it is a release layer formed by curing a composition containing at least a binder component and a silicone-based release agent, the surface roughness due to aggregation of the component during drying An object of the present invention is to provide a release film for manufacturing a ceramic green sheet excellent in releasability by controlling the deterioration of the surface and having high smoothness and by adjusting the amount of the silicone-based component on the surface of the release layer.

That is, this invention consists of the following structures.

1. A polyester film as a substrate, the substrate having a surface layer A substantially free of particles on at least one side, and directly or another layer on the surface of the surface layer A of at least one side A release film in which a release layer is laminated therebetween, wherein the release layer is formed by curing a composition containing a binder component and a silicone-based release agent, and the Si element ratio on the surface of the release layer is 2.0at% or more and 10.0at% or less, and the release layer A release film for manufacturing a ceramic green sheet having a surface maximum protrusion height (P) of 50 nm or less and an area average roughness (Sa) of 1.5 nm or less.

2. The release film for manufacturing a ceramic green sheet according to 1 above, wherein the silicone-based release agent is a silicone-based resin having a polyether moiety or a carboxyl group.

3. The release film for manufacturing a ceramic green sheet according to the first or second above, wherein the silicone-based release agent-derived component is contained in the release layer by 1 to 15 mg/m 2 .

4. The release film for manufacturing a ceramic green sheet according to any one of Items 1 to 3, wherein the binder component contains a resin having a long-chain alkyl group and/or a silicon skeleton.

5. A method for manufacturing a ceramic green sheet in which a ceramic green sheet is formed using the release film for manufacturing a ceramic green sheet according to any one of the above 1 to 4, wherein the molded ceramic green sheet has a thickness of 0.2 μm to 1.0 μm. A method of manufacturing a ceramic green sheet having

6. A method for manufacturing a ceramic capacitor employing the method for manufacturing a ceramic green sheet according to the fifth aspect.

According to the present invention, even a release layer comprising at least a binder component and a silicone-based release agent has high smoothness by suppressing deterioration of surface roughness due to aggregation of the component during drying, and the amount of the silicone-based component on the surface of the release layer is adjusted This makes it possible to provide a release film for manufacturing a ceramic green sheet that has good peelability and can reduce defects such as pinholes even in the production of an ultra-thin ceramic green sheet having a film thickness of 0.2 to 1.0 μm with excellent peelability.

The present inventors, in order to solve the above problems, by carefully examining and optimizing the drying conditions after the application of the release layer and the content of the silicone compound in the release layer, a polyester film having a surface layer A substantially free of particles on at least one side A release film formed by laminating a release layer directly or through another layer on at least one surface layer A of A release film for manufacturing ceramic green sheets having a (P) of 50 nm or less, an area average roughness (Sa) of 1.5 nm or less, and an Si element ratio of the outermost surface of the release layer of 2.0 at% or more and 10.0 at% or less, has a film thickness of 0.2 to 1.0 It was found that, when the ultra-thin ceramic green sheet of ㎛ was formed, the peelability was excellent and defects such as pinholes were reduced. EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

(polyester film)

In the present invention, the polyester constituting the polyester film used as the base material is not particularly limited, and as a base material for a release film, a film obtained by forming a film of polyester generally used in general can be used. Preferably, an aromatic dichromate It is preferable that it is a crystalline linear saturated polyester comprising a base acid component and a diol component, for example, polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, polytrimethylene terephthalate, or Copolymers mainly composed of the constituent components of these resins are more suitable, and among them, a polyester film formed from polyethylene terephthalate is particularly suitable. In polyethylene terephthalate, 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 small amounts, but from the viewpoint of cost, terephthalic acid and ethylene glycol alone. Moreover, you may add well-known additives, for example, antioxidant, a light stabilizer, a ultraviolet absorber, a crystallizer, etc. within the range which does not impair the effect of the film of this invention. It is preferable that a polyester film is a biaxially-oriented polyester film from reasons, such as high bidirectional elastic modulus.

0.50-0.70 dl/g is preferable and, as for the intrinsic viscosity of the said polyethylene terephthalate film, 0.52-0.62 dl/g is more preferable. When the intrinsic viscosity is 0.50 dl/g or more, it is preferable because breakage does not occur much in the stretching step. Conversely, when it is 0.70 dl/g or less, it is preferable because cutability is good when cutting to a predetermined product width, and dimensional defects do not occur. Moreover, it is preferable to fully vacuum-dry a raw material pellet.

The manufacturing method of the polyester film in this invention is not specifically limited, The method generally used conventionally can be used. For example, the polyester is melted with an extruder, extruded into a film form, and cooled with a rotary cooling drum to obtain an unstretched film, and can be obtained by biaxially stretching the unstretched film. . The biaxially oriented film is a method of sequentially biaxially stretching a longitudinal or transverse uniaxially oriented film in the transverse or longitudinal direction, or a method of simultaneously biaxially stretching an unstretched film in the longitudinal and transverse directions. can be obtained with

In this invention, it is preferable to make the extending|stretching temperature at the time of extending|stretching a polyester film more than the secondary transition point (Tg) of polyester. It is preferable to extend|stretch by 1 to 8 times, especially 2 to 6 times in each direction longitudinally and horizontally.

It is preferable that the said polyester film is 12-50 micrometers in thickness, More preferably, they are 15-38 micrometers, More preferably, they are 19 micrometers - 33 micrometers. If the thickness of the film is 12 μm or more, it is preferable because there is no risk of deformation by heat during film production, processing of a release layer, or molding of a ceramic green sheet. On the other hand, when the thickness of the film is 50 µm or less, the amount of the film to be discarded after use does not become extremely large, which is preferable in order to reduce the environmental load.

Although the said biaxially-oriented polyester film base material may be a single layer or a multilayer of two or more layers may be sufficient, it is preferable to have the surface layer A which does not contain a particle|grain substantially on at least single side|surface. In the case of a laminated polyester film having a multilayer structure of two or more layers, it is preferable to have a surface layer B that can contain particles or the like on the opposite surface of the surface layer A substantially free of particles. As for the laminated structure, when 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 other deep layers are layer C, the layer structure in the thickness direction is the release layer/A A laminated structure, such as /B or a release layer /A/C/B, is mentioned. Naturally, the layer C may have a multiple layer structure. Moreover, particle|grains may not be included in the surface layer B. In that case, it is preferable to provide a coating layer containing particles and a binder on the surface layer B in order to impart the sliding properties for winding the film in roll shape.

The polyester film base material in this invention WHEREIN: It is preferable that the surface layer A which forms the surface which apply|coats a mold release layer does not contain particle|grains substantially. At this time, it is preferable that the area|region surface average roughness Sa of the surface layer A is 7 nm or less. When Sa is 7 nm or less, it is preferable that pinholes or the like do not easily occur during molding of the ultra-thin ceramic green sheet to be laminated. Although it can be said that it is so preferable that the area|region surface average roughness Sa of the surface layer A is small, 0.1 nm or more may be sufficient. Here, when an anchor coat layer or the like described later is provided on the surface layer A, it is preferable that the coating layer contains substantially no particles, and the area surface average roughness (Sa) after lamination of the coating layer satisfies the above range. it is preferable In the present invention, "substantially free of particles" means, for example, in the case of inorganic particles, 50 ppm or less, preferably 10 ppm or less, most preferably detection when the inorganic element is quantified by fluorescence X-ray analysis. Content used below the limit is meant. This is because, even if particles are not actively added to the film, foreign matter-derived contaminants, raw material resins, or dirt adhering to lines and equipment in the production process of the film may be peeled off and mixed into the film.

The polyester film base material in this invention WHEREIN: It is preferable that the surface layer B which forms the surface opposite to the surface to which a mold release layer is apply|coated contains particle|grains from a viewpoint of the slipperiness|lubricacy of a film, and air removal easiness, especially, It is preferred to use silica particles and/or calcium carbonate particles. It is preferable to contain 5000-15000 ppm of particle|grain content in the total of particle|grains in the surface layer B. At this time, it is preferable that the area|region surface average roughness Sa of the film of the surface layer B is the range of 1-40 nm. More preferably, it is the range of 5-35 nm. When the total of silica particles and/or calcium carbonate particles is 5000 ppm or more and Sa is 1 nm or more, when the film is rolled up in roll shape, air can be uniformly released, so that the wound state is good and the flatness is good. As a result, it becomes suitable for the manufacture 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 less likely to occur and coarse protrusions do not occur, so ultra-thin ceramic green It is preferable because the quality is stable during sheet production.

As the particles contained in the surface layer B, inactive inorganic particles and/or heat-resistant organic particles other than silica and/or calcium carbonate can be used. It is more preferable to use silica particles and/or calcium carbonate particles from the viewpoints of transparency and cost, but other inorganic particles that can be used include alumina-silica composite oxide particles and hydroxyapatite particles. Moreover, crosslinked polyacrylic particle|grains, crosslinked polystyrene particle|grains, benzoguanamine type particle|grains, etc. are mentioned as heat resistant organic particle|grains. Further, 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.

0.1 micrometer or more and 2.0 micrometers or less are preferable and, as for the average particle diameter of the particle|grains added to the said surface layer B, 0.5 micrometer or more and 1.0 micrometer or less are especially preferable. When the average particle diameter of the particles is 0.1 µm or more, the slip property of the release film is good, and it is preferable. Moreover, if the average particle diameter is 2.0 µm or less, there is no fear of pinholes being generated in the ceramic green sheet due to the coarse particles on the surface of the release layer, which is preferable.

You may make the said surface layer B contain two or more types of particle|grains from which a material differs. Moreover, you may contain the particle|grains of the same type and different in average particle diameter.

When particle|grains are not included in the surface layer B, it is preferable to give lubricity by the coating layer containing particle|grains on the surface layer B. Although this coating layer is not specifically limited, It is preferable to provide by so-called in-line coat applied during film forming of a polyester film. When the surface layer B does not contain particles and has a coating layer containing particles on the surface layer B, the surface of the coating layer is the region surface for the same reason as the region surface average roughness Sa of the surface layer B described above. It is preferable that the average roughness Sa is in the range of 1 to 40 nm. More preferably, it is the range of 5-35 nm.

It is preferable not to use a recycled raw material or the like in the surface layer A, which is a layer on the side where the release layer is provided, in order to prevent mixing of particles such as lubricants from the viewpoint of reducing pinholes.

It is preferable that the thickness ratio of the surface layer A which is a layer by the side which provides the said mold release layer are 20% or more and 50% or less of the total thickness of a base film. If it is 20 % or more, it is difficult to receive the influence of the particle|grains contained in the surface layer B etc. from the inside of a film, and it is easy for the area|region surface average roughness Sa to satisfy the said range, and it is preferable. If it is 50% or less of the thickness of all the layers of a base film, the usage-rate of the reproduction|regeneration raw material in the surface layer B can be increased, an environmental load becomes small, and it is preferable.

Moreover, 50-90 mass % of film scrap or plastic bottle recycling raw material can be used for layers other than the said surface layer A (surface layer B or the above-mentioned intermediate|middle layer C) from an economical viewpoint. Also in this case, it is preferable that the type, amount, particle size, and area average roughness (Sa) of the lubricant contained in the surface layer B satisfy the above ranges.

In addition, in order to improve the adhesion of a release layer applied later, or to prevent electrification, etc., a coating layer may be provided on the surface of the surface layer A and/or the surface layer B before or after stretching in the film forming process or after uniaxial stretching. , corona treatment, etc. may be performed. When providing a coating layer on the surface layer A, it is preferable that the said coating layer does not contain particle|grains substantially.

(release layer)

It is preferable that the composition containing at least a binder component and a silicone type mold release agent hardens|cures the release layer in this invention. In the range which does not impair the effect of this invention, other components can be added besides the said resin and a compound.

(binder component)

The binder component included in the composition for forming a release layer of the present invention is not particularly limited, but a crosslinkable component is crosslinked in order to increase the crosslinking density of the release layer and improve durability and solvent resistance of the release layer it is preferable Therefore, it is preferable that resin which has a reactive functional group and a crosslinking agent react with a binder component. Moreover, it is also preferable to carry out self-crosslinking independently of either a reactive functional group or a crosslinking agent. However, in the present invention, the binder component does not exclude the embodiment comprising only a resin or a crosslinking agent having a reactive functional group.

Although it does not specifically limit as resin which has a reactive functional group, A polyester-type resin, poly(meth)acrylic-type resin, a polyurethane-type resin, polyolefin resin, etc. can be used suitably. It is preferable in these resins to have at least 1 type or more selected from a carboxyl group, a hydroxyl group, an epoxy, an amino group, etc. as a reactive functional group.

It is preferable that resin which has a reactive functional group has a long-chain alkyl group and/or silicone skeleton in a part of resin skeleton. By having a low-surface free energy site such as a long-chain alkyl group and/or a silicone skeleton in a part of the resin skeleton, compatibility between the silicone-based release agent and the binder component, which will be described later, increases, making it difficult to cause agglomeration during drying, so it is preferable because smoothness is improved. do.

Specific examples of the reactive functional group-containing resin having a long-chain alkyl group in the resin skeleton include an alkyd resin or (meth)acrylic resin having a long-chain alkyl group in the side chain. As the long-chain alkyl group to be used, a straight-chain alkyl group having 6 to 20 carbon atoms is suitable. By having the above-mentioned carbon number, the surface free energy of resin obtained can be reduced, and since compatibility with a silicone type mold release agent improves, it is preferable.

In the case of an alkyd resin having a long-chain alkyl group in the side chain, an acid having a long-chain alkyl group as described above (eg, octylic acid or stearic acid, etc.) is mixed with a polybasic acid such as phthalic acid, and a polyhydric alcohol component (pentaerythritol, diethylene glycol, etc.) It can be obtained by mixing with a dehydration condensation reaction.

It is preferable to obtain the (meth)acrylic resin which has a long-chain alkyl group in a side chain by copolymerizing two or more types of (meth)acryl monomers. As the monomer to be copolymerized, it is preferable to include a monomer having a long-chain alkyl group (eg, lauryl (meth)acrylate, stearyl (meth)acrylate, isodecyl (meth)acrylate, etc.), and a reactive functional group moiety As such, it is preferable to include a monomer having a hydroxyl group (eg, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, etc.). In addition to the above, other bases such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexanediol dimethacrylate and butanediol diacrylate (旣知) may also contain a monomer.

It is preferable that content of the monomer which has a long-chain alkyl group which comprises the obtained acrylic resin is 1 mol% or more and 50 mol% or less with respect to all the monomers which comprise an acrylic resin. If it is 1 mol% or more, since there is an effect of lowering|hanging surface free energy, it is preferable. If it is 50 mol% or less, since the monomer having a reactive functional group becomes relatively high, the crosslinking density of the resin becomes high, so it is preferable.

Specific examples of the reactive functional group-containing resin having a silicone skeleton in the resin skeleton include an alkyd resin or an acrylic resin having a polydimethylsiloxane skeleton in the side chain. Specific examples of commercially available products include Cymac (registered trademark) US350, US352 (manufactured by Toagosei, reactive functional group: carboxyl group), Cymac (registered trademark) US270 (manufactured by Toagosei, reactive functional group: hydroxyl group), etc. have.

(crosslinking agent)

It is also preferable to contain a crosslinking agent in a binder component. Although it does not specifically limit as a crosslinking agent, The crosslinking agent of a melamine type, an isocyanate type, a carbodiimide type, an oxazoline type, an epoxy type, etc. can be used, You may use one type or two or more types in combination. Particularly preferably, a crosslinking agent that reacts with the reactive functional group introduced into the binder component is preferred.

As a crosslinking agent used for this invention, a melamine type compound is preferable from a reactive viewpoint. By using a melamine-type compound, even if the application amount after curing of the release layer is a thin film such as 0.2 g/m 2 or less, it can be cured quickly and the crosslinking density is increased, so it is preferable.

As the melamine-based compound used in the present invention, a general compound can be used and is not particularly limited, but it is obtained by condensing melamine and formaldehyde, and a triazine ring, and a methylol group and/or an alkoxymethyl group in one molecule, respectively It is preferable to have more than one. Specifically, a compound obtained by condensing a methylol melamine derivative obtained by condensing melamine and formaldehyde with methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol or the like as a lower alcohol is subjected to a dehydration condensation reaction to etherify the compound or the like. Examples of the methylolated melamine derivative include monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, and hexamethylol melamine. It does not matter whether one type is used or two or more types are used.

As the melamine-based compound, since the crosslinking density of the binder component can be increased, it is preferable to use hexamethylol melamine or hexamethoxymethylol melamine having many crosslinking points in one molecule. In the case of using an ether compound subjected to a dehydration condensation reaction using alcohol for the methylol melamine derivative, hexamethoxymethylmethylol melamine obtained by dehydration condensation with methyl alcohol is particularly preferable from the viewpoint of reactivity.

It is preferable that the quantity of the crosslinking agent contained in the binder component in this invention is 15 mass % or more with respect to resin which has a reactive functional group, More preferably, it is 30 mass % or more, More preferably, it is 50 mass %. Moreover, when a crosslinking agent self-condenses and can form a resin film, a binder component may be comprised only with a crosslinking agent. By including 15 mass % or more of a crosslinking agent, since the crosslinking density of a mold release layer can be raised and solvent resistance and an elastic modulus can be improved, it is preferable.

(catalyst)

In order to harden a crosslinking agent, you may contain a catalyst in the composition for mold release layer formation in this invention. When using a melamine-type compound, it is preferable to use an acid catalyst, Although it does not specifically limit, A carboxylic acid type, metal salt type, phosphoric acid ester type, and a sulfonic acid type can be used suitably. In addition, a block-type catalyst in which an acid moiety is blocked can also be used. In particular, para-toluenesulfonic acid can be suitably used from the viewpoint of reactivity. When using an isocyanate type compound, a general thing can be used and an organotin, an amine compound, a trialkyl phosphine compound, etc. can be used suitably.

It is preferable that content of a catalyst is 0.1-40 mass % with respect to the crosslinking agent contained in the composition for mold release layer formation. More preferably, it is 0.5-30 mass %. More preferably, it is 0.5-20 mass %. If it is 0.1 mass % or more, hardening reaction advances easily, and it is preferable. On the other hand, if it is 40 mass % or less, there is no possibility that an acid catalyst will migrate to the ceramic green sheet to shape|mold, and it is preferable at the point which does not have a possibility of exerting a bad influence.

(Silicone-based release agent)

Although it will not specifically limit if it is a compound which has a silicone structure in a molecule|numerator and the effect of this invention can be acquired as a silicone type release agent used for a release layer in this invention, Polyorganosiloxane etc. can be used suitably. Among polyorganosiloxanes, polydimethylsiloxane (abbreviation, PDMS) can be suitably used, and it is also preferable to have a functional group in a part of polydimethylsiloxane. Having a functional group is preferable because intermolecular interactions such as hydrogen bonding with the binder resin are more likely to be expressed, making it difficult to transfer to a ceramic green sheet.

Although it does not specifically limit as a functional group introduce|transduced into polydimethylsiloxane, A reactive functional group or a non-reactive functional group may be sufficient. Moreover, the functional group may be introduce|transduced into the single terminal of polydimethylsiloxane, and it does not matter whether it is both terminals or a side chain. In addition, the number of positions to be introduced may be one, or it may be plural.

An amino group, an epoxy group, a hydroxyl group, a mercapto group, a carboxyl group, a methacryl group, an acryl group etc. are mentioned as a reactive functional group introduce|transduced into polydimethylsiloxane. As the non-reactive functional group, a polyether group, an aralkyl group, a fluoroalkyl group, a long-chain alkyl group, an ester group, an amide group, a phenyl group and the like can be used. Although not limited by theory, it is preferable to have an epoxy group, a carboxyl group, a polyether group, a methacryl group, an acryl group, and an ester group among the above.

It is more preferable that the functional group introduce|transduced into polydimethylsiloxane does not react with a binder component. For example, polydimethylsiloxane modified with a hydroxyl group that reacts with melamine resin reacts with melamine in the drying process, so it is difficult to align on the surface of the release layer. There are difficult cases. Therefore, it is necessary to increase the addition amount in order to have sufficient releasability, but in that case, the elastic modulus of a release layer may fall and there exists a possibility that the deformation|transformation of a release layer may occur easily.

As the functional group to be introduced into the polydimethylsiloxane, for the above reasons, the functional group does not react with the binder resin, is easily oriented on the surface of the release layer, and has little transferability to the ceramic green sheet. In particular, a polyether group or an ester group is preferable. and a polyether group is particularly preferable. A carboxyl group is mentioned as a functional group with which the ratio of Si element on the surface of a mold release layer comparatively increases even if it reacts with binder resin.

It is preferable that the molecular weight of the silicone type mold release agent used in this invention is 40000 or less. More preferably, it is 30000 or less. It is preferable that a silicone type mold release agent segregates easily that molecular weight is 40000 or less on the surface of a mold release layer, and peelability is good.

It is preferable that content of the component derived from a silicone type mold release agent contained in the mold release layer after hardening in this invention is 1 mg/m<2> or more and 15 mg/m<2> or less. 1 mg/m 2 or more and 10 mg/m 2 or less are more preferable. When it is 1 mg/m 2 or more, the silicon component can be sufficiently precipitated on the outermost layer of the release layer, and the releasability of the ceramic green sheet is stable, so it is preferable. When it is 15 mg/m 2 or less, since the release layer contains few silicone components with a relatively low elastic modulus, the elastic modulus of the release layer does not become too low and the releasability of the ceramic sheet is stable. Here, if the silicone-based release agent exists in the same structure without changing the chemical structure even in the release layer after curing, the chemical structure is changed by causing a chemical reaction between the binder component and the like. there is also Therefore, the mass of the substance derived from the silicone-based release agent in the composition before curing and existing per unit area of the release layer after curing is described as the content of the silicone-based mold release agent-derived component. The content of the silicone-based mold release agent-derived component can be calculated and calculated from the ratio (mass %) of the silicone-based mold release agent in the solid content of the coating solution containing the composition and the application amount of the mold release layer solid content after curing (g/m 2 ).

Although the release layer in the present invention may contain particles having a particle size of 1 µm or less, it is preferable not to contain particles or the like that form protrusions from the viewpoint of suppressing pinholes in the ceramic green sheet.

You may add additives, such as a close_contact|adherence improving agent and an antistatic agent, etc. to the mold release layer in this invention, as long as it is a range which does not impair the effect of this invention. Moreover, in order to improve adhesiveness with a base material, it is also preferable to perform pretreatment, such as anchor coat, corona treatment, plasma treatment, atmospheric pressure plasma treatment, on the surface of a polyester film before installing a mold release coating layer.

Although the application amount of the release layer after hardening in this invention is not specifically limited, It is preferable that it is 1.0 g/m<2> or less. More preferably, it is 0.01-0.5 g/m<2>, More preferably, it is 0.02-0.20 g/m<2>, More preferably, it is 0.02-0.09 g/m<2>. It is easy to obtain peeling performance that the application amount of a mold release layer is 0.01 g/m<2> or more, and it is preferable. If it is 0.2 g/m 2 or less, since the curing time of the release layer can be shortened, the planarity of the release film is maintained, and thus the thickness unevenness of the ceramic green sheet can be suppressed, which is preferable. In addition, if it is 0.2 g/m 2 or less, the curl of the obtained film is also reduced, so that the molding precision is improved at the time of forming the ceramic green sheet, so it is preferable.

It is preferable that the surface free energy of the surface of the release layer of the release film of this invention is 18 mJ/m<2> or more and 35 mJ/m<2> or less. More preferably, they are 20 mJ/m<2> or more and 30 mJ/m<2> or less, More preferably, they are 21 mJ/m<2> or more and 28 mJ/m<2> or less. If it is 18 mJ/m 2 or more, cissing is unlikely to occur when the ceramic slurry is coated, so that it can be coated uniformly, which is preferable. Moreover, if it is 35 mJ/m<2> or less, there is no possibility that the releasability of a ceramic green sheet will fall, and it is preferable. By setting it as the said range, there is no sheathing at the time of coating, and the release film excellent in releasability can be provided.

The release film of the present invention preferably has a peeling force of 0.5 mN/m m 2 or more and 3 mN/m m 2 or less when peeling the ceramic green sheet. More preferably, they are 0.8 mN/mm<2> or more and 2.5 mN/mm<2> or less. More preferably, it is 1.0 mN/mm<2> or more and 1.8 mN/mm<2> or less. If the peeling force is 0.5 mN/mm 2 or more, the peeling force is not too light and there is no fear of floating the ceramic green sheet during conveyance, which is preferable. If the peeling force is 3 mN/mm 2 or less, there is no fear that the ceramic green sheet may be damaged during peeling, so it is preferable.

It is preferable that the release film of this invention has few curls. It is preferable that the curl after heating at 100 degreeC for 15 minutes without applying tension|tensile_strength to a film specifically, is 2 mm or less, More preferably, it is 1 mm or less. Of course, it is also preferable not to curl at all. By setting it to 2 mm or less, when forming a ceramic green sheet and printing an electrode, there are few curls, and since printing precision can be improved, it is preferable.

It is preferable that the silicone type mold release agent-derived component contained in a mold release layer fully precipitates on the release layer surface of the release film of this invention. As a parameter|index which shows the precipitation amount of the component derived from a silicone type mold release agent, the ratio of the Si element on the surface of a mold release layer can be used. The Si element ratio on the surface of the mold release layer can be evaluated by ESCA capable of measuring only the surface of the mold release layer. In addition, let the ratio of Si element in this invention be the ratio (at%) of Si in 5 elements C, S, Si, O, and N as shown in the following formula.

Si element ratio (at%) = {Si/(C+O+N+S+Si)} x 100 ... ceremony

It is preferable that the Si element ratio of the outermost surface of the mold release layer of the release film of this invention is 2.0 at% or more. More preferably, it is 2.5 at% or more, it is more preferable in it being 3.0 at% or more, and 3.5 at% or more is still more preferable. If it is 2.0 at% or more, the silicone-based release agent can sufficiently coat the surface of the release layer, so that the peeling force is stable during peeling of the ceramic green sheet of a thin film, so it is preferable. 10 at% or less is preferable, as for the upper limit of the Si element ratio, 9 at% or less is more preferable, 8 at% or less is still more preferable. If it is 10 at% or less, since the elastic modulus of the surface of a mold release layer does not become low and peeling is stable, it is preferable.

In order to achieve the Si element ratio of the outermost surface of the release layer of the release film of the present invention, the content of the silicone-based release agent-derived component contained in the release layer after curing as described above and the passage time of the initial drying step after the release layer coating to be described later are optimized. it is preferable

The surface of the release layer of the release film of the present invention is preferably flat in order not to cause defects in the ceramic green sheet to be coated and molded thereon, and preferably has an average area surface roughness (Sa) of 1.5 nm or less, more preferably Preferably it is 1.2 nm or less, and 1.0 nm or less is still more preferable. Moreover, it is preferable that the maximum processus|protrusion height P on the surface of a mold release layer is 50 nm or less, 40 nm or less is more preferable, 30 nm or less is still more preferable. When the area surface average roughness Sa is 1.5 nm or less and the maximum protrusion height P is 50 nm or less, defects such as pinholes do not occur when forming the ceramic green sheet, and the yield is good, which is preferable. Although it can be said that the area|region surface average roughness Sa is so preferable that it is small, 0.1 nm or more may be sufficient and 0.3 nm or more may be sufficient as it. Although it can be said that it is so preferable that the maximum processus|protrusion height P is also small, 1 nm or more may be sufficient, and 3 nm or more may be sufficient as it.

Since the release film of the present invention uses a highly flattened base film, it is preferable that the application amount of the release layer is 0.2 g/m 2 or less, and furthermore, even if it is thinner than 0.09 g/m 2, the surface of the release layer can be smoothed Therefore, it is possible to reduce the amount of solvent and resin to be used, which is environmentally friendly, and a release film for forming an ultra-thin ceramic green sheet can be prepared at low cost.

In order to set the maximum protrusion height (P) on the surface of the release layer of the release film of the present invention to 50 nm or less and the area average roughness (Sa) to 1.5 nm or less, the coating liquid of the release layer is coated and dried until the silicone-based release agent or binder component It is desirable to suppress aggregation of Therefore, as described in the manufacturing method mentioned later, the target ultra-high-smooth mold release layer surface can be obtained by implementing time from after coating to drying under fixed conditions.

(Manufacturing method of release film)

The method for producing the release film of the present invention is not particularly limited, but at least a coating step in which a binder component and a silicone-based release agent are dissolved or dispersed in a solvent is laminated on at least one side of the polyester film of the base material by applying or the like; After that, it is preferable to use a method in which the release layer is laminated through an initial drying process of mainly removing the solvent and the like and a heat curing process of mainly curing the binder resin. It is preferable that the surface on the side which provides a mold release layer of a polyester film is the surface layer A which does not contain particle|grains substantially, and another coating layer may exist between the surface layer A and a mold release layer.

(application process)

Although it does not specifically limit as a solvent which melt|dissolves or disperse|distributes the binder resin and a silicone type mold release agent, It is preferable to use an organic solvent. Since the surface tension of the coating liquid can be lowered by using an organic solvent, it is difficult to generate a see-through after application|coating, and since the smoothness of the surface of a release layer can be maintained high, it is preferable.

It does not specifically limit as an organic solvent used for the manufacturing method of the release film of this invention, An existing thing can be used. Examples of the solvent usually include aromatic hydrocarbons such as benzene, toluene and xylene, fatty acid hydrocarbons such as cyclohexane, n-hexane and n-heptane, halogenated hydrocarbons such as perchlorethylene, ethyl acetate, and methyl ethyl ketone; methyl isobutyl ketone; and the like. Considering the applicability in the case of application to the surface of the base film, although not limited, a mixed solvent of toluene and methyl ethyl ketone is practically preferable.

In this invention, although it does not specifically limit in the coating liquid used for application|coating for mold release layer formation, It is preferable that two or more types of organic solvents with different boiling points are included. It is preferable that the boiling point of at least 1 type of organic solvent is 100 degreeC or more. By adding the solvent with a boiling point of 100 degreeC or more, bumpiness at the time of drying can be prevented, a coating film can be leveled, and the smoothness of the coating-film surface after drying can be improved. It is preferable to add about 10-50 mass % with respect to the whole coating liquid as the addition amount. Toluene, xylene, octane, cyclohexanone, methyl isobutyl ketone, n-propyl acetate, etc. are mentioned as an example of a solvent with a boiling point of 100 degreeC or more.

In this invention, although the surface tension (20 degreeC) of the coating liquid at the time of apply|coating the coating liquid for mold release layer formation is not specifically limited, It is preferable that it is 30 mN/m or less. By making surface tension as mentioned above, the wettability after coating can improve and the unevenness|corrugation of the coating-film surface after drying can be reduced. In order to lower the surface tension of the coating liquid, it is preferable to use a low surface tension organic solvent for forming the coating liquid. It is preferable that the surface tension (20 degreeC) of at least 1 type of organic solvent is 26 mN/m or less, More preferably, it is 23 mN/m or less. By including an organic solvent having a surface tension (20° C.) of 26 mN/m or less, it is preferable to reduce appearance defects such as seething during application. As the addition amount, it is preferable to add 20 mass % or more with respect to the whole coating liquid.

As for the solid content concentration of the mold release agent contained in a coating liquid, 0.1 mass % or more and 10 mass % or less are preferable, More preferably, they are 0.2 mass % or more and 8 mass % or less. Since drying after application|coating is quick by making solid content concentration into 0.1 mass % or more, aggregation etc. of the component in a mold release agent do not occur easily, and it is preferable. On the other hand, since the viscosity of a coating liquid is low and leveling property is favorable as solid content concentration is 10 mass % or less, planarity after coating can be improved, and it is preferable. 1 mPa*s or more and 100 mPa*s or less are preferable from the point of a coating external appearance, and, as for the viscosity of a coating liquid, 2 mPa*s or more and 10 mPa*s or less are more preferable. It is preferable to adjust a solid content concentration, an organic solvent, etc. so that it may become this range.

In this invention, it is preferable to filter the coating liquid for mold release layer formation before application|coating. The filtration method is not particularly limited and an existing method can be used, but it is preferable to use a surface type, depth type, or adsorption type cartridge filter. The use of a cartridge-type filter is preferable because it can be used when continuously feeding the coating liquid from the tank to the coating part, and thus it can be efficiently filtered with good productivity. As the filtration accuracy of the filter, it is preferable to use a filter that removes 99% or more of a 1 μm-sized thing, and more preferably a filter capable of filtering 99% or more of a 0.5 μm-sized thing. By using the one having the above filtration accuracy, foreign substances mixed in the mold release agent can be removed, and the foreign substances adhering to the mold release layer of the mold release film for ceramic green sheet molding of the present invention can be significantly reduced. Therefore, defects of the ceramic green sheet molded using the release film of the present invention are reduced, and the defect rate of the ceramic capacitor can also be reduced.

As the coating method of the coating solution, 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, a die coating method, and a spray coating method Conventionally known methods, such as the method and the air knife coating method, can be used.

It is preferable that the coating liquid film thickness (Wet amount) at the time of application|coating is 1 g/m<2> or more and 10 g/m<2> or less. If it is 1 g/m 2 or more, it is preferable because the coating is stable, so it is difficult to show defects such as seething or streaks. Moreover, if it is 10 g/m<2> or less, drying is quick and it is difficult for the component contained in a mold release layer to aggregate, and it is preferable.

(drying process)

As a method of apply|coating a coating liquid on a base film and drying, although well-known hot air drying, heat drying by an infrared heater, etc. are mentioned, Hot air drying with a quick drying rate is preferable. The drying furnace can be divided into a constant-rate drying process (hereinafter, referred to as an initial drying process) in the initial stage of drying and a process (hereinafter, referred to as a heat-hardening process) in which reduced-rate drying and curing of the resin proceed. Although the initial stage drying process and the heat-hardening process may be continuous or discontinuous, it is not cared about, but the continuous one has good productivity and is preferable. It is preferable to distinguish each process by dividing the zone of a drying furnace. As long as the number of zones in each process is one or more, it does not matter how many.

In the manufacturing method of the release film of this invention, it is preferable to put into a drying furnace within 1.5 second after application|coating, More preferably, it is within 1.0 second, and less than 0.8 second is still more preferable. Since it can be dried before aggregation of the components contained in the release layer occurs by putting it in a drying furnace within 1.5 seconds after application and starting drying, it is preferable because deterioration of the smoothness of the surface of the release layer due to aggregation can be prevented. It is preferable that the time from application|coating to putting in a drying furnace is short, although a minimum is not provided in particular, It may be 0.05 second or more, and 0.1 second or more may be sufficient as it.

The initial drying process is not specifically limited, An existing drying furnace can be used. As for the drying furnace method, it does not matter whether it is a roll support method or a floating method, but the roll support method is preferable because it has a wider range for adjusting the air volume during drying, so the air volume can be adjusted according to the type of release layer. do.

The temperature of the initial drying step is preferably 60°C or higher and 140°C or lower, more preferably 70°C or higher and 130°C or lower, and still more preferably 80°C or higher and 120°C or lower. By setting it as 60 degreeC or more and 140 degrees C or less, since the amount of organic solvent contained in the mold release layer after application|coating can be dried effectively without planarity defect by heat, it is preferable.

As time to pass through an initial stage drying process, it is preferable that they are 1.0 second or more and 3.0 second or less, 1.0 second or more and 2.5 second or less are more preferable, 1.2 second or more and 2.5 second or less are still more preferable. If it is 1.0 second or more, since the organic solvent contained in the mold release layer after application|coating can fully be dried, it is preferable. Moreover, since the silicone type mold release agent-derived component contained in a mold release layer can be effectively precipitated on the mold release layer surface by setting it as 1.0 second or more, it is preferable. Moreover, if it is 3.0 second or less, aggregation of the component in a mold release layer does not occur easily, and it is preferable. By adjusting the solid content concentration, organic solvent species, and the like of the coating solution so that it can be dried in the above-mentioned time, deterioration of smoothness due to aggregation can be suppressed even when a coating solution that tends to agglomerate is used.

It is preferable that the amount of the organic solvent contained in the mold release layer after passing through an initial stage drying process is 5 mass % or less, More preferably, it is 2 mass % or less. When the amount of the organic solvent is 5 mass% or less, even if heated in the heating step, deterioration in appearance due to Dolby or the like can be prevented, which is preferable. Although the amount of organic solvent in a mold release layer can sample the film after an initial stage drying process and can measure it by gas chromatography, thermogravimetric analysis, etc., the method of guessing using simulation of drying can also be taken. The one obtained from the simulation is preferable because it can measure without stopping the process. The simulation is not particularly limited, but existing simulation software can be used.

(heat curing process)

It is preferable that the release film of the present invention undergoes a heat curing process after the initial drying process. A heat-hardening process is not specifically limited, An existing drying furnace can be used. About the system of a drying furnace, either a roll support system or a floating system may be sufficient. Although the heat-hardening process may be a process continuous with an initial stage drying process, or a discontinuous process may be sufficient as it, It is preferable that it is a continuous process from a viewpoint of productivity.

The temperature of the heat curing step is preferably 80°C or higher and 180°C or lower, more preferably 90°C or higher and 160°C or lower, and most preferably 90°C or higher and 140°C or lower. When the temperature is 180° C. or less, the flatness of the film is maintained, and the risk of causing uneven thickness of the ceramic green sheet is small, which is preferable. If it is 140 degrees C or less, processing can be performed without impairing the planarity of a film, and since the fear of raising the thickness non-uniformity of a ceramic green sheet further falls, it is especially preferable. If it is 80 degreeC or more, since hardening advances sufficiently in the case of a thermosetting resin, it is preferable.

2 seconds or more and 30 seconds or less are preferable, and, as for time to pass a heat-hardening process, 2 second or more and 20 seconds or less are still more preferable. If the passage time is 2 seconds or more, curing of the thermosetting resin proceeds, which is preferable. Moreover, if it is 30 seconds or less, the flatness of the film by a heat|fever does not fall, but it is preferable.

In the last of a heat-hardening process, it is preferable to make hot-air temperature or less than the glass transition temperature of a base film, and to make room temperature of a base film into a glass transition temperature or less in a flat state. When the room temperature of a base film leaves a drying furnace with a glass transition temperature or more, when it contacts a roll surface, slipping becomes unsatisfactory, and not only a flaw etc. generate|occur|produce, but a curl etc. may generate|occur|produce.

It is preferable to wind up the release film of this invention in roll shape after heat-hardening process passage. It is preferable to take 2 second or more, and, as for the time until winding-up in roll shape after heat-hardening process pass, 3 second or more is more preferable. If it is 2 seconds or more, since the release film whose temperature rose by the heat-hardening process is cooled and wound up on a roll, there is no fear of damaging planarity, and it is preferable.

In the release film of the present invention and its manufacturing method, various treatments may be performed between the heat curing step and winding up to roll shape, aging treatment, antistatic treatment, corona treatment, plasma treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, etc. can be done

(Ceramic Green Sheet and Ceramic Capacitor)

In general, 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 face. The first internal electrode is electrically connected to the first external electrode in the first end face. The second internal electrode is exposed on the second end surface 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 in 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. For example, it is manufactured as follows. First, the release film of the present invention is used as a carrier film, and a ceramic slurry for constituting a ceramic body is applied and dried. A conductive layer for constituting the first or second internal electrode is printed on the coated and dried ceramic green sheet. A mother laminate is obtained by appropriately laminating and pressing a ceramic green sheet, a ceramic green sheet printed with a conductive layer for constituting the first internal electrode, and a ceramic green sheet printed with a conductive layer for constituting the second internal electrode. . By dividing the mother laminate into a plurality of parts, a raw (raw) ceramic body is produced. A ceramic body is obtained by firing the green ceramic body. Thereafter, the multilayer ceramic capacitor can be completed by forming the first and second external electrodes.

Example

Hereinafter, the present invention will be described in more detail using Examples, but the present invention is not limited by these Examples in any way. The characteristic values used in the present invention were evaluated using the following method.

(area surface average roughness (Sa), maximum asperity height (P))

It is a value measured under the following conditions using the non-contact surface shape measurement system (The Ryoka Systems company make, VertScan R550H-M100). For the area surface average roughness Sa, the average value of 5 measurements was adopted, and the maximum projection height P was measured 7 times, and the maximum value of 5 times excluding the maximum value and the minimum value was used.

(Measuring conditions)

・Measurement mode: WAVE mode

·Objective lens: 10x

·0.5×Tube lens

・Measurement area 936㎛ × 702㎛

(analysis conditions)

・Face correction: 4th correction

Interpolation processing: full interpolation

·Filter treatment: Gaussian cutoff value 50㎛

(Amount of release layer applied)

The application amount of the release layer after hardening of the release film of this invention was measured using the gravimetric method. The release film was sampled to a size of 15 cm × 15 cm, and after static elimination using an electric eliminator, the weight was measured using a precision balance (AUW120D manufactured by Shimadzu Corporation). The release layer of the measured release film was wiped off using methyl ethyl ketone, and after drying at 80°C for 1 minute with a hot air dryer, the mass was measured again using a precision balance. The release layer application amount (g/m 2 ) was calculated by dividing the difference in the film weight after wiping off by the film area (15 cm x 15 cm) from the film weight before wiping off the release layer. In addition, the measurement was performed 5 times using the film sampled from another location, and the average value of 3 times except the maximum value and the minimum value was used.

(Ratio of Si element on the outermost surface of the release layer)

The ratio of Si element on the outermost surface of the release layer of the release film of the present invention was measured by ESCA. As the device, K-Alpha ⁺ (manufactured by Thermo Fisher Scientific) was used. The details of the measurement conditions were shown below. Using this apparatus, a narrow scan was performed on five elements of C, O, N, S, and Si on the surface of the mold release layer, and the Si element ratio (at%) was calculated from this by the following formula. In the present invention, the Si element ratio is defined as the ratio (at%) of Si among the five elements C, O, N, S, and Si.)

Si element ratio (at%) = {Si/(C+O+N+S+Si)} x 100 ... ceremony

In addition, during the analysis, the removal of the background was performed by the Shirley method. In addition, the surface Si element ratio was made into the average value of the measurement result of three or more places.

·Measuring conditions

Excitation X-ray: Monochromated Al Ka-ray

X-ray output: 12 kV, 6mA

Photoelectron escape angle: 90°

Spot size: 400 mm f (accurate)

Pass Energy: 50 eV

Step: 0.1eV

(surface free energy)

Water (1.8 μL of droplet) and diiodo on the release surface of the release film using a contact angle meter (manufactured by Kyowa Kaimen Chemical Co., Ltd.: fully automatic contact angle meter DM-701) under the conditions of 25° C. and 50% RH. Droplets of methane (a droplet amount of 0.9 µL) and ethylene glycol (a droplet amount of 0.9 µL) were prepared, and the contact angle was measured. The contact angle employ|adopted the contact angle 10 second after dripping each liquid to the release film. Calculate the contact angle data of water, diiodomethane, and ethylene glycol obtained by the above method using the "Kitazaki-Hata" theory to obtain the dispersion component γsd, the polar component γsp, and the hydrogen bonding component γsh of the surface free energy of the release film, What summed up each component was made into surface free energy gamma s. This calculation was performed using the calculation software in this contact angle meter software (FAMAS).

(surface tension of the coating liquid)

The surface tension of the coating solution was measured by Wilhelmy method using a surface tensiometer (manufactured by Kyowa Kaimen Chemical Co., Ltd.: high-function surface tensiometer DY-500) under 20°C conditions and using a platinum plate. It measured three times and employ|adopted the average value.

(Viscosity of coating solution)

The viscosity of the coating liquid was measured under 20 degreeC conditions using the rotary viscometer (Toki Sangyo Co., Ltd. make: TVB-15M). When measuring a low-viscosity liquid of 10 mPa·s or less, the measurement was performed using an optional low-viscosity adapter. The measurement was performed three times and the average value was employ|adopted.

(Evaluation of coating properties of ceramic slurry)

The composition comprising the following materials was stirred and mixed, and dispersed for 60 minutes with zirconia beads having a diameter of 0.5 mm using a bead mill to obtain a ceramic slurry.

Toluene 76.3 parts by mass

Ethanol 76.3 parts by mass

Barium titanate (HPBT-1 manufactured by Fuji Titan Corporation) 35.0 parts by mass

3.5 parts by mass of polyvinyl butyral (Sekisui Chemical Co., Ltd. S-Rec (registered trademark) BM-S)

DOP (dioctyl phthalate) 1.8 parts by mass

Next, using an applicator to the release surface of the obtained release film sample, it coated so that the slurry after drying might be set to 1 micrometer, and after drying at 90 degreeC for 1 minute, the following references|standards evaluated coatability.

○: It is coated on the entire surface without seething or the like.

(triangle|delta): Although there exists a little shedding at the coating edge part, it is coated on almost the whole surface.

x: There are many searings, and it is not coated.

(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 coatability of the ceramic slurry.

Next, the obtained release film sample was coated with an applicator so that the dried slurry had a thickness of 1 μm, dried at 90° C. for 1 minute, and then the release film was peeled off to obtain a ceramic green sheet.

In the central region in the film width direction of the obtained ceramic green sheet, light was irradiated from the opposite side of the coated surface of the ceramic slurry in a range of 25 cm 2 , the state of occurrence of pinholes through which light was transmitted was observed, and the visual judgment was made based on the following criteria.

○: No occurrence of pinholes

△: almost no occurrence of pinholes

×: There are many occurrences of pinholes

(Evaluation of peelability of ceramic green sheet)

The composition comprising the following materials was stirred and mixed, and dispersed for 60 minutes with zirconia beads having a diameter of 0.5 mm using a bead mill to obtain a ceramic slurry.

Toluene 38.3 parts by mass

Ethanol 38.3 parts by mass

Barium titanate (HPBT-1 manufactured by Fuji Titan) 64.8 parts by mass

6.5 parts by mass of polyvinyl butyral (S-Rec (registered trademark) BM-S manufactured by Sekisui Chemical Co., Ltd.)

DOP (dioctyl phthalate) 3.3 parts by mass

Then, the obtained release film sample was coated with an applicator so that the dried slurry had a thickness of 10 μm, dried at 90° C. for 1 minute, and a ceramic green sheet was molded on the release film. After the obtained release film with a ceramic green sheet was neutralized using a static electricity eliminator (manufactured by Keyence Corporation, SJ-F020), it was peeled off with a width of 30 mm, a peeling angle of 90 degrees, and a peeling rate of 10 m/min. The stress applied at the time of peeling was measured and it was set as peeling force.

(Evaluation of peeling stability of ceramic green sheet)

It carried out similarly to the peelability evaluation of the above-mentioned ceramic green sheet, and evaluated the peelability 10 times. The following reference|standard evaluated the nonuniformity of 10 times of peeling force, and it was set as evaluation of peeling stability.

○: The difference between the maximum value and the minimum value when measured 10 times was smaller than 0.5 mN/m m 2 .

(triangle|delta): The difference of the maximum value and minimum value when measured 10 times was 0.5 mN/mm<2> or more and less than 1.0N/mm<2>.

x: The difference between the maximum value and the minimum value when it measured 10 times was 1.0 mN/mm<2> or more.

(Evaluation of curl of release film)

The release film sample was cut to a size of 10 cm × 10 cm, and heat treatment was performed at 100° C. for 15 minutes in a hot air oven so that no tension was applied to the release film. Then, after taking out from oven and cooling to room temperature, the mold release film sample was put on the glass plate so that a mold release surface might become up, and the height of the part floating from a glass plate was measured. At this time, the height of the largest floating part from the glass plate was made into a measurement value. Curl|Karl property was evaluated on the following reference|standard.

(circle): Curl|Karl is 1 mm or less, and it is hardly curled.

(triangle|delta): The curl was larger than 1 mm, and it was 2 mm or less, and curl was seen a little.

x: The curl was larger than 2 mm.

(Preparation of polyethylene terephthalate pellets (PET(I)))

As the esterification reaction apparatus, a continuous esterification reaction apparatus consisting of a three-stage complete mixing tank having a stirring device, a dust separator, a raw material inlet and a product outlet was used. TPA (terephthalic acid) is 2 tons/hour, EG (ethylene glycol) is 2 moles per 1 mole of TPA, and antimony trioxide is used in an amount such that the Sb atom is 160 ppm with respect to the produced PET, and the slurry is subjected to an esterification reaction apparatus was continuously supplied to the first esterification reaction tube of Next, the reaction product in the first esterification tube is continuously taken out of the system and supplied to the second esterification tube, and is distilled off from the first esterification tube in the second esterification tube. 8 mass % of EG to be produced is supplied with respect to the produced PET, and an EG solution containing magnesium acetate tetrahydrate in an amount such that the Mg atom is 65 ppm with respect to the produced PET, and P with respect to the produced PET. An EG solution containing TMPA (trimethyl phosphate) in an amount of 40 ppm valency was added, and the reaction was carried out at 260° C. with an average residence time of 1 hour at normal pressure. Next, the reaction product of the second esterification reaction tube is continuously taken out of the system and supplied to the third esterification reaction tube, and is averaged at a pressure of 39 MPa (400 kg/cm 2 ) using a high-pressure disperser (manufactured by Nippon Seiki Co., Ltd.) 0.2 mass% of porous colloidal silica having an average particle diameter of 0.9 μm, subjected to dispersion treatment in 5 passes of treatment, and 0.4 mass% of synthetic calcium carbonate having an average particle diameter of 0.6 μm, obtained by adhering 1 mass% of ammonium salt of polyacrylic acid per calcium carbonate , were reacted at 260°C for an average residence time of 0.5 hours at normal pressure while adding as a 10% EG slurry, respectively. The esterification reaction product produced in the third esterification reaction tube is continuously supplied to a three-stage continuous polycondensation reaction apparatus for polycondensation, and is filtered with a filter obtained by sintering stainless steel fibers with a 95% cut diameter of 20 µm. After performing ultrafiltration, extruding in water, and cutting into chips after cooling 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 mass%.

(Preparation of polyethylene terephthalate pellets (PET(II)))

On the other hand, in the production of the PET chip, a PET chip having an intrinsic viscosity of 0.62 dl/g containing no particles such as calcium carbonate or silica was obtained (hereinafter abbreviated as PET(II)).

(Preparation of polyethylene terephthalate pellets (PET(III)))

PET(I) was similar to PET(I) except that the type and content of the particles were changed to 0.75% by mass of synthetic calcium carbonate having an average particle diameter of 0.9 μm in which 1 mass% of ammonium salt of polyacrylic acid was adhered per calcium carbonate. A chip was obtained (hereinafter abbreviated as PET(III)). The lubricant content in the PET chip was 0.75 mass%.

(Preparation of laminated film X1)

After drying these PET chips, they are melted at 285°C, melted at 290°C by a separate melt extruder, and a filter obtained by sintering stainless steel fibers having a 95% cut diameter of 15 μm, and a 95% cut diameter of 15 μm Two-stage filtration of a filter in which stainless steel particles are sintered is performed, merged in the feed block, PET(I) is applied to the surface layer B (anti-release side layer), and PET(II) is applied to the surface layer A (release side layer). ), extruded (cast) into a sheet at a speed of 45 m/min, and electrostatically adhered and cooled on a casting drum at 30° C. by an electrostatic adhesion method, and unstretched polyethylene having an intrinsic viscosity of 0.59 dl/g A terephthalate sheet was obtained. The layer ratio was adjusted so that it might become PET(I)/PET(II)=60%/40% by the discharge amount calculation of each extruder. Next, after heating this unstretched sheet|seat with an infrared heater, it extended|stretched 3.5 times longitudinally by the speed difference between rolls at the roll temperature of 80 degreeC. Then, it guide|induced with the tenter, and it extended|stretched 4.2 times in the transverse direction at 140 degreeC. Next, in the heat setting zone, it heat-processed at 210 degreeC. Thereafter, a 2.3% relaxation treatment was performed in the transverse direction at 170°C to obtain a biaxially stretched polyethylene terephthalate film X1 having a thickness of 31 µm. Sa of the surface layer A of the obtained film X1 was 2 nm, and Sa of the surface layer B was 28 nm.

(Preparation of laminated film X2)

The thickness was adjusted by changing the speed at the time of casting, without changing the layer structure and extending|stretching conditions similar to laminated|multilayer film X1, and the biaxially stretched polyethylene terephthalate film X2 of a thickness of 25 micrometers was obtained. Sa of the surface layer A of the obtained film X2 was 3 nm, and Sa of the surface layer B was 29 nm.

(Laminated Film X3)

As laminated|multilayer film X3, A4100 (Cosmo Shine (trademark), the Toyobo company make) with a thickness of 25 micrometers was used. A4100 has a structure in which a coating layer containing particles is provided by in-line coating on the surface layer B side without substantially containing particles in the film. Sa of the surface layer A of laminated|multilayer film X3 was 1 nm, and Sa of the surface layer B was 2 nm.

(Laminated Film X4)

As laminated|multilayer film X4, 25 micrometers in thickness E5101 (Toyobo Ester (trademark) film, the Toyobo company make) was used. E5101 has a structure containing particles in the surface layers A and B of the film. Sa of the surface layer A of laminated|multilayer film X4 was 24 nm, and Sa of the surface layer B was 24 nm.

(Preparation of laminated film X5)

PET(III) was laminated so as to become surface layer B (semi-release side layer) and PET(II) became surface layer A (release side layer), and the layer ratio was calculated by calculating the discharge amount of each extruder, PET(III)/(II) = 80 A 31-micrometer-thick biaxially stretched polyethylene terephthalate film X5 was obtained by the method similar to laminated|multilayer film X1 except having set it as %/20%. Sa of the surface layer A of the obtained film X5 was 2 nm, and Sa of the surface layer B was 30 nm.

(Resin solution A) Long-chain alkyl group-containing acrylic polyol

20 mol% of stearyl (meth)acrylate, 40 mol% of hydroxyethyl (meth)acrylate, and 40 mol% of methyl (meth)acrylate are mixed and diluted with toluene so that the solid content concentration is 40% by mass. , 0.5 mol% of azobisisobutyronitrile was added and copolymerized under a nitrogen stream to obtain a resin solution A. The weight average molecular weight of the obtained polymer at this time was 30000.

(Example 1)

After passing the coating solution 1 having the following composition on the surface layer A of the laminated film X1 through a filter capable of removing 99% or more of foreign substances of 0.5 μm or more, the coating film thickness (wet amount) was 5 g/m 2 using reverse gravure. It adjusted so that it might enter the initial stage drying furnace in 0.5 second after coating as much as possible. After 2 second drying at 100 degreeC in an initial stage drying furnace, it was made to enter the heat-hardening process continuously, and it heated at 130 degreeC for 7 second. After the heat curing step, 8 seconds later, it was wound up into a roll to obtain a release film for producing an ultra-thin ceramic green sheet. Table 1 shows the results of measuring the film thickness, surface roughness, surface free energy, curl, etc. of the obtained release film. Moreover, when the ceramic slurry was coated on the obtained release film and coatability, peelability, and a pinhole were evaluated, favorable evaluation result was obtained.

(Coating solution 1) Solid content 1.0 mass %, surface tension: 27 mN/m, viscosity 5 mPa*s

57.93 parts by mass of methyl ethyl ketone

40.00 parts by mass of toluene

1.75 parts by mass of resin solution A (long-chain alkyl group-containing acrylic polyol, solid content: 40%)

0.25 parts by mass of crosslinking agent (hexamethoxymethylol melamine, solid content 100%)

0.05 parts by mass of silicone mold release agent (polyether-modified polydimethylsiloxane, TSF4446, solid content 100%, manufactured by Momentive)

Acid catalyst (paratoluenesulfonic acid) 0.02 parts by mass

(Examples 2 to 4, Comparative Examples 1 and 7)

A release film for producing an ultra-thin ceramic green sheet was prepared in the same manner as in Example 1, except that the composition of the coating solution 1 was changed to have the ratio shown in Table 1. When the obtained release film was evaluated, good results were obtained with good peeling force for the Example containing the silicone-based release agent, but in Comparative Example 1 without the silicone-based release agent, the peeling force was increased, so that the ceramic green sheet was peeled from the release film. It brought the result which became easy to produce faults, such as a pinhole, at the time. Moreover, there was little amount of a silicone type mold release agent, and the peeling uniformity in surface worsened also in Comparative Example 7 with a low Si element ratio on the surface of a mold release layer.

(Examples 5-7, Comparative Example 2)

As for the resin ratio of coating solution 1, the solid content was changed as described in Table 2, and the release film for producing an ultra-thin ceramic green sheet was prepared in the same manner as in Example 1 except that the application amount (solid content) of the release layer was changed.

When the obtained release film was evaluated, there was no curl for the Example in which the application amount of the release layer was 0.2 g / m 2 or less and there was no curl, but in Comparative Example 2 where the application amount of the release layer was 0.75 g / m 2 , the curl was greatly deteriorated. . Moreover, in Comparative Example 2, the content of the silicone-based mold release agent contained in the mold release layer was large, and the ratio of the Si element on the outermost surface of the mold release layer was increased, and the peeling stability tended to deteriorate.

(Example 8)

Except having changed the coating liquid 1 into the coating liquid 8, it carried out similarly to Example 1, and created the release film for ultra-thin ceramic green sheet manufacture.

(Paint 8)

57.35 parts by mass of methyl ethyl ketone

40.00 parts by mass of toluene

Cymac (registered trademark) US270 2.33 parts by mass (silicone group-containing acrylic polyol, manufactured by Toagosei Co., Ltd., solid content 30%)

0.25 parts by mass of crosslinking agent

(Hexamethoxymethylol melamine, solid content 100%)

0.05 parts by mass of silicone mold release agent (polyether-modified polydimethylsiloxane, TSF4446, solid content 100%, manufactured by Momentive)

Acid catalyst (paratoluenesulfonic acid) 0.02 parts by mass

(Example 9)

Except having changed the coating liquid 1 to the coating liquid 9, it carried out similarly to Example 1, and created the release film for ultra-thin ceramic green sheet manufacture.

(Paint 9)

58.03 parts by mass of methyl ethyl ketone

40.00 parts by mass of toluene

Tespine 305 1.90 parts by mass (a long-chain alkyl group-containing amino alkyd resin, manufactured by Hitachi Chemical Co., Ltd., solid content 50%)

0.05 parts by mass of silicone mold release agent (polyether-modified polydimethylsiloxane, TSF4446, solid content 100%, manufactured by Momentive)

Acid catalyst (paratoluenesulfonic acid) 0.02 parts by mass

(Example 10)

Except having changed the coating liquid 1 to the coating liquid 10, it carried out similarly to Example 1, and created the release film for ultra-thin ceramic green sheet manufacture.

(Paint 10)

57.55 parts by mass of methyl ethyl ketone

40.00 parts by mass of toluene

Tespine 322 2.38 parts by mass (a long-chain alkyl group-containing aminoacrylic resin, manufactured by Hitachi Chemical Co., Ltd., solid content 40%)

0.05 parts by mass of silicone mold release agent (polyether-modified polydimethylsiloxane, TSF4446, solid content 100%, manufactured by Momentive)

Acid catalyst (paratoluenesulfonic acid) 0.02 parts by mass

(Example 11)

A release film for producing ultra-thin ceramic green sheets was prepared in the same manner as in Example 1, except that Coating Solution 11 in which the resin solution A of Coating 1 was changed to 6AN-5000 (acrylic resin not containing a long-chain alkyl group) was used.

(Paint 11)

57.93 parts by mass of methyl ethyl ketone

40.00 parts by mass of toluene

6AN-5000 1.75 parts by mass (acrylic polyol, manufactured by Daisei Fine Chemicals, solid content 40%)

0.25 parts by mass of crosslinking agent (hexamethoxymethylol melamine, solid content 100%)

0.05 parts by mass of silicone mold release agent (polyether-modified polydimethylsiloxane, TSF4446, solid content 100%, manufactured by Momentive)

Acid catalyst (paratoluenesulfonic acid) 0.02 parts by mass

(Example 12)

Except having changed the coating solution 1 to the coating solution 12, it carried out similarly to Example 1, and created the release film for ultra-thin ceramic green sheet manufacture.

(Paint 12)

58.95 parts by mass of methyl ethyl ketone

40.00 parts by mass of toluene

Hexamethoxymethylol melamine 0.95 mass part (solid content 100%)

0.05 parts by mass of silicone mold release agent (polyether-modified polydimethylsiloxane, TSF4446, solid content 100%, manufactured by Momentive Performance Materials)

Acid catalyst (paratoluenesulfonic acid) 0.05 parts by mass

As in Examples 8 to 12, good results were obtained even when the binder component was changed. Even if the resin containing a long-chain alkyl group or a silicone skeleton in the binder component was processed under the same conditions, the surface protrusions tended to be lower.

(Example 13)

Except having changed the coating liquid 1 into the coating liquid 13, it carried out similarly to Example 1, and created the release film for ultra-thin ceramic green sheet manufacture.

(Paint 13)

57.78 parts by mass of methyl ethyl ketone

40.00 parts by mass of toluene

1.75 parts by mass of resin solution A (long-chain alkyl group-containing acrylic polyol, solid content 40%)

0.25 mass parts of crosslinking agent (hexamethoxymethylol melamine, solid content 100%)

0.08 parts by mass of silicone mold release agent (polyester-modified polydimethylsiloxane, BYK-310, solid content 25%, manufactured by Big Chemie Japan)

Acid catalyst (paratoluenesulfonic acid) 0.02 parts by mass

(Example 14)

Except having changed the coating liquid 1 into the coating liquid 14, it carried out similarly to Example 1, and created the release film for ultra-thin ceramic green sheet manufacture.

(Paint 14)

57.93 parts by mass of methyl ethyl ketone

40.00 parts by mass of toluene

1.75 parts by mass of resin solution A (long-chain alkyl group-containing acrylic polyol, solid content 40%)

0.25 mass parts of crosslinking agent (hexamethoxymethylol melamine, solid content 100%)

0.02 parts by mass of silicone mold release agent (carboxyl-modified polydimethylsiloxane, X22-3710, solid content 100%, manufactured by Shin-Etsu Chemical Co., Ltd.)

Acid catalyst (paratoluenesulfonic acid) 0.02 parts by mass

(Example 15)

Except having changed the coating liquid 1 to the coating liquid 15, it carried out similarly to Example 1, and created the release film for ultra-thin ceramic green sheet manufacture.

(Paint 15)

57.78 parts by mass of methyl ethyl ketone

40.00 parts by mass of toluene

1.75 parts by mass of resin solution A (long-chain alkyl group-containing acrylic polyol, solid content 40%)

0.25 mass parts of crosslinking agent (hexamethoxymethylol melamine, solid content 100%)

0.08 parts by mass of silicone-based mold release agent (polydimethylsiloxane containing polyester-modified hydroxyl groups, BYK-370, solid content 25%, manufactured by Big Chemie Japan)

Acid catalyst (paratoluenesulfonic acid) 0.02 parts by mass

In Examples 13 to 15, in which the type of silicone-based release agent was changed, good evaluation results were obtained in any of them, but the one that did not contain a hydroxyl group that reacts with the crosslinking agent (melamine in this example) was the best release layer under the same conditions. There was a tendency for the peelability to be improved because the ratio of the Si element on the surface was high.

(Examples 16 to 18, Comparative Example 3)

Except having changed the base film of Example 1 into the base film of Table 1, it carried out similarly to Example 1, and created the release film for ultra-thin ceramic green sheet manufacture.

When the obtained release film was evaluated, in Examples 1 to 15 and 16 to 18 using X1, X2, X3, and X5 containing no particles in the surface layer A of the base film, Sa and P on the surface of the release layer were low and pinhole evaluation In Comparative Example 3, where X4 containing particles was used in the surface layer A of the base film, and the application amount of the release layer was relatively small, compared to the good Comparative Example 3, both Sa and P on the surface of the release layer were high, and pinhole evaluation was deteriorated. was the result.

(Examples 19 to 22, Comparative Examples 4 and 5)

The manufacturing conditions of Example 1 were carried out in the same manner as in Example 1, except that the time from application to entering the initial drying furnace, or the temperature and passage time of the initial drying furnace were changed to the conditions shown in Table 2. The release film for green sheet manufacture was created.

(Comparative Example 6)

Except having changed the manufacturing conditions of Example 11 to the conditions shown in Table 1, it carried out similarly to Example 11, and created the release film for ultra-thin ceramic green sheet manufacture.

(Comparative Example 8)

A release film for producing an ultra-thin ceramic green sheet was prepared in the same manner as in Comparative Example 4 except that the content of the silicone-based release agent was changed to the one described in Table 1.

As a result of evaluating the obtained film, in Examples in which the time from application to entering the initial drying furnace was 1.5 seconds or less and the passing time to the initial drying furnace was 1.0 seconds or more and 3.0 seconds or less, the surface roughness (Sa) of the surface of the release layer was While the maximum protrusion height (P) was low and pinhole evaluation was good, in the comparative example outside the above conditions, aggregation of the release layer was seen, and the surface roughness (Sa) and maximum protrusion height (P) of the release layer were high. . Moreover, in Comparative Examples 4 and 8, in which the passage time of the initial drying step was shortened, there was little precipitation of the silicone-based mold release agent on the surface of the release layer, and the ratio of the Si element on the outermost surface of the release layer tended to be low. In particular, in Comparative Example 8, the ratio of the Si element on the outermost surface of the release layer was lowered, resulting in deterioration of peel stability.

[Table 1]

[Table 2]

[Table 3]

According to the present invention, as a release layer of a release film for manufacturing a ceramic green sheet, a composition comprising at least a binder component and a silicone-based release agent is cured, thereby suppressing deterioration of surface roughness due to agglomeration of the component during drying. It has become possible to provide a release film which has smoothness and is excellent in peelability. According to the present invention, even in the production of an ultra-thin ceramic green sheet having a film thickness of 0.2 to 1.0 mu m, the peelability is good, and defects such as pinholes in the ceramic green sheet can be reduced.

Claims (8)

A release film using a polyester film as a base material and having a release layer laminated directly on the surface of the base material,
The release layer is made by curing a composition containing a binder component and a silicone-based release agent,
Si element ratio on the surface of the release layer is 2.0 at% or more and 10.0 at% or less,
A release film for manufacturing a ceramic green sheet having a maximum protrusion height (P) of 50 nm or less and an average area roughness (Sa) of 1.5 nm or less on the surface of the release layer. The method of claim 1,
The release film for manufacturing a ceramic green sheet, wherein the silicone-based release agent is a silicone-based resin having a polyether group, a carboxyl group, or an ester group that does not react with the binder component. The method of claim 1,
A release film for manufacturing a ceramic green sheet having a curl of 2 mm or less, measured under the condition that the release film was heated at 100° C. for 15 minutes. The method of claim 1,
A release film for manufacturing a ceramic green sheet, wherein the silicone-based release agent is a silicone-based resin having a polyether moiety or a carboxyl group. The method of claim 1,
A release film for manufacturing a ceramic green sheet in which a silicone-based release agent-derived component is contained in the release layer in an amount of 1 to 15 mg/m2. The method of claim 1,
A release film for manufacturing a ceramic green sheet, wherein the binder component includes a resin having a long-chain alkyl group and/or a silicon skeleton. A method of manufacturing a ceramic green sheet by molding a ceramic green sheet using the release film for manufacturing a ceramic green sheet according to any one of claims 1 to 6, wherein the formed ceramic green sheet has a thickness of 0.2 μm to 1.0 μm. A method of manufacturing a ceramic green sheet having A method for manufacturing a ceramic capacitor employing the method for manufacturing a ceramic green sheet according to claim 7.