Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B28—WORKING CEMENT, CLAY, OR STONE
  • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
  • B28B1/00—Producing shaped prefabricated articles from the material
  • B28B1/30—Producing shaped prefabricated articles from the material by applying the material on to a core or other moulding surface to form a layer thereon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/06—Interconnection of layers permitting easy separation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
  • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/02—2 layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/538—Roughness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2386/00—Specific polymers obtained by polycondensation or polyaddition not provided for in a single one of index codes B32B2363/00 - B32B2383/00

Definitions

• the present invention relates to a release film for molding a resin sheet, and more particularly to a release film used when molding an ultrathin layer resin sheet.
• a release film having a polyester film as a base material and a release layer laminated on the polyester film has been used as a process film for molding a resin sheet such as an adhesive sheet, a cover film, a polymer film, and an optical lens.
• a resin sheet such as an adhesive sheet, a cover film, a polymer film, and an optical lens.
• the release film is also used as a process film for molding a ceramic green sheet, which is required to have high smoothness, such as a laminated ceramic capacitor and a ceramic substrate.
• a ceramic green sheet is molded by applying a slurry containing a ceramic component such as barium titanate and a binder resin onto a release film and drying it.
• a laminated ceramic capacitor is manufactured by laminating, pressing, firing, and applying an external electrode to a ceramic green sheet obtained by printing an electrode on a molded ceramic green sheet and peeling it from a release film.
• the peelability when peeling the ceramic green sheet from the release film becomes more important. If the peeling force is large and non-uniform, the ceramic green sheet is damaged in the peeling process, sheet defects, uneven thickness, etc. occur, and there is a problem that problems such as pinholes and sheet cracks occur. Therefore, it is also required to peel off the ceramic green sheet with a lower and uniform force. That is, in order to produce an ultrathin layer resin sheet, particularly a ceramic green sheet, without defects, a release film having extremely high smoothness and excellent peelability is required.
• Patent Document 1 proposes a release film having a release layer using a radical curable resin as a main component.
• Patent Document 2 proposes a release film having a structure in which a smoothing layer and a release layer are laminated.
• Patent Document 3 proposes a release film having a release layer using a cationically curable epoxy resin as a main component.
• Patent Document 4 proposes a release film having a release layer using a cationically cured polydimethylsiloxane as a main component.
• Patent No. 5492352 JP-A-2015-164762 International Publication No. 2018/07937 JP-A-2016-079349A
• the release film of Patent Document 1 has a problem that the smoothness of the release layer is insufficient because the release layer is provided on the base film having insufficient smoothness. Furthermore, as a result of diligent studies, the present inventors have found that the radically curable resin has poor curing due to oxygen inhibition, resulting in poor solvent resistance on the surface of the release layer, and when molding a ceramic green sheet or printing an internal electrode. It has been found that there is a problem that the release layer is eroded by the organic solvent sometimes used and the peelability is deteriorated. In the invention of Patent Document 2, a thermosetting melamine resin is used for the smoothing coating layer and the release coating layer, and high heat is required to accelerate the curing reaction.
• the flatness of the release film may be impaired by the heat during processing.
• multiple processes of the smoothing coating layer and the release coating layer are required, not only foreign matter may be mixed into the release film, but also the release layer may be scratched, so that the mold is molded on the release layer. Foreign matter and scratches may be transferred to the ceramic green sheet, causing problems.
• Patent Documents 3 and 4 propose release layers using a cationically curable resin in order to improve curing defects caused by oxygen inhibition and flat surface defects caused by processing heat.
• the release film of Patent Document 3 has a problem that the smoothness of the surface of the release layer is poor because the smoothness of the base film is poor.
• the release agent component disclosed in Patent Document 3 has poor reactivity, poor solvent resistance, and has a problem in peelability.
• the release film of Patent Document 4 has a release layer using a liquid cation-curable polydimethylsiloxane resin as a main component, unevenness of the base film, oligomers existing on the surface of the base film, and the like are present. There was a risk that the resin would aggregate on the protrusions, causing problems with flatness. In addition, the crosslink density of the release layer was low, and there was a problem in peelability.
• the present invention has been made against the background of the problems of the prior art. That is, it is possible to provide a mold release film having a mold release layer having particularly excellent smoothness and peelability, and further, a mold release film capable of molding an ultra-thin layer resin sheet, particularly an ultra-thin layer ceramic green sheet without defects.
• the purpose is to provide a film.
• the present invention has the following configuration.
• the polyester film has a surface layer A that does not substantially contain inorganic particles.
• the release layer is provided on the surface layer A, and the release layer is provided.
• the release layer is a layer on which the release layer forming composition is cured.
• the release layer forming composition contains a cationically cured polydimethylsiloxane (a) and contains.
• the region surface roughness (Sa) of the release layer is 2 nm or less, and the area surface roughness (Sa) is 2 nm or less.
• the number of protrusions having a height of 10 nm or more existing on the surface of the release layer is 200 pieces / mm 2 or less.
• the maximum protrusion height (Sp) of the release layer is 20 nm or less, the number of protrusions having a height of 5 nm or more and less than 10 nm existing on the surface of the release layer, and the number of protrusions of 10 nm or more.
• the cationically cured polydimethylsiloxane (a) has at least one functional group selected from a vinyl ether group, an oxetanyl group, an epoxy group, and an alicyclic epoxy group.
• the content of the cationically cured polydimethylsiloxane (a) contained in the release layer is 90 mg / m 2 or less.
• the release layer forming composition further contains a cationically curable compound (b-1) having no silicone skeleton.
• the cationically cured compound (b-1) has two or more alicyclic epoxy groups in the molecule, and the total mass of the cationically cured polydimethylsiloxane (a) and the cationically cured compound (b-1) is 100.
• the content of the cation-curable compound (b-1) is 80% by mass or more with respect to the part.
• the release layer forming composition further contains a cyclic siloxane compound (b-2) having an alicyclic epoxy group.
• the cyclic siloxane compound (b-2) has two or more alicyclic epoxy groups in the molecule, and has a total of 100 parts by mass of the cationically cured polydimethylsiloxane (a) and the cyclic siloxane compound (b-2).
• the content of the cyclic siloxane compound (b-2) is 80% by mass or more.
• the release layer forming composition contains an organic solvent having an SP value ( ⁇ ) of 14 or more and 17 or less, and the release layer forming composition has an SP value ( ⁇ ) of 14 or more and 17 or less.
• the organic solvent of the above is contained in an amount of 10% by mass or more with respect to 100 parts by mass of the total weight of the release layer forming composition.
• a release film for producing a resin sheet containing an inorganic compound is provided.
• the resin sheet containing an inorganic compound is a ceramic green sheet.
• a release film for molding a resin sheet having a thickness of 0.2 ⁇ m or more and 1.0 ⁇ m or less is provided.
• the release film for molding a resin sheet of the present invention can enhance the smoothness and peelability of the release layer, and can further suppress the occurrence of defects in the ultrathin layer resin sheet, particularly the ceramic green sheet. ..
• the present invention comprises a polyester film as a base material and a release film for molding a resin sheet having a release layer.
• the polyester film has a surface layer A that is substantially free of inorganic particles. It has a release layer on the surface layer A and has a mold release layer.
• the release layer is a layer on which the release layer forming composition is cured.
• the release layer forming composition contains a cationically cured polydimethylsiloxane (a) and contains.
• the region surface roughness (Sa) of the release layer is 2 nm or less, This is a release film for molding a resin sheet, in which the number of protrusions having a height of 10 nm or more and 200 pieces / mm 2 or less existing on the surface of the release layer is 200 pieces / mm 2.
• the present invention having such a structure is excellent in smoothness and peelability of the release layer, for example, it is possible to provide a uniform thickness without defects for a resin sheet having a thickness of 0.2 ⁇ m to 1.0 ⁇ m or less. , Pinholes and other defects can be suppressed.
• the invention of the present application can exert the following effects.
• the release layer is provided on the base film having sufficient smoothness, the smoothness of the release layer can be ensured.
• the present invention can suppress curing defects due to oxygen inhibition in the release layer, and can achieve high cross-linking of the release layer. INDUSTRIAL APPLICABILITY
• the present invention exhibiting such an effect can improve, for example, the solvent resistance of the surface of the release layer.
• the release layer forming composition can be suppressed from agglomerating by going through the coating step and the drying step according to the present invention, and the mold release having extremely high smoothness can be suppressed. A release film with layers can be obtained.
• a release layer forming composition containing a predetermined amount of cationically curable polydimethylsiloxane (a) is applied to the surface layer A which does not substantially contain the inorganic particles of the base film. Then, by curing, a release layer having extremely high smoothness can be obtained. Further, by controlling the content of the cationically cured polydimethylsiloxane (a) in the release layer to a predetermined amount or less, it is derived from a very small foreign substance or oligomer present in the base film during processing of the release layer. It is possible to suppress the aggregation of cationically cured polydimethylsiloxane (a) to the microprojections.
• the component (a) aggregates with respect to the fine protrusions caused by the raw fabric. It can be prevented.
• a mold release body such as a ceramic green sheet can be obtained.
• a release layer having excellent smoothness, hardness, peelability, and stain resistance to the release layer can be obtained.
• the cationically cured polydimethylsiloxane (a) is less likely to aggregate during the drying of the organic solvent contained in the release layer forming composition, and the release layer having excellent smoothness can be obtained. Details will be described later.
• the present invention provides, in another embodiment, a method for producing a release film for molding a resin sheet, which comprises the following steps.
• the surface layer A is a layer that does not substantially contain inorganic particles.
• the release layer forming composition comprises a cationically cured polydimethylsiloxane (a).
• Coating process A drying step of heating and drying a polyester film coated with a release layer forming composition. The heat drying has a first drying step and then a second drying step.
• the drying step T1 in the first drying step is higher than the drying temperature T2 in the second drying step;
• a photocuring step of irradiating with active energy rays to cure the release layer forming composition.
• a release layer having high smoothness can be formed, for example, coating of a release layer forming composition. Controlling the amount, organic solvent composition, drying time, drying temperature and the like can be mentioned.
• aggregation of the cationically curable polydimethylsiloxane (a) contained in the release layer forming composition can be suppressed, and a release layer having excellent smoothness can be obtained. Can be done. Details will be described later.
• the polyester constituting the polyester film used as the base material of the present invention is not particularly limited, and a film-molded polyester usually generally used as a base material for a release film can be used.
• a film-molded polyester usually generally used as a base material for a release film
• it is a crystalline linear saturated polyester composed of an aromatic dibasic acid component and a diol component, for example, polyethylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, polytrimethylene terephthalate or these.
• a copolymer containing the constituent components of the resin as a main component is more preferable, and a polyester film formed from polyethylene terephthalate is particularly suitable.
• the repeating unit of ethylene terephthalate is preferably 90 mol% or more, more preferably 95 mol% or more, and other dicarboxylic acid components and diol components may be copolymerized in a small amount, but from the viewpoint of cost. , Preferably made only from terephthalic acid and ethylene glycol. Further, known additives such as antioxidants, light stabilizers, ultraviolet absorbers, crystallization agents and the like may be added as long as the effects of the film of the present invention are not impaired.
• the polyester film is preferably a biaxially oriented polyester film because of its high bidirectional elastic modulus and the like.
• the intrinsic viscosity of the polyester film is preferably 0.50 to 0.70 dl / g, more preferably 0.52 to 0.62 dl / g.
• the intrinsic viscosity is 0.50 dl / g or more, it is preferable because many breaks do not occur in the stretching step. On the contrary, when it is 0.70 dl / g or less, it is preferable because the cutability when cutting to a predetermined product width is good and dimensional defects do not occur. Further, it is preferable that the raw material pellets are sufficiently vacuum dried.
• the term "polyester film” simply means a polyester film having a surface layer A (laminated).
• the polyester film has a surface layer A that does not substantially contain inorganic particles, and has the release layer on the surface layer A.
• a polyester film having a surface layer B (laminated) may be simply referred to as a "polyester film”.
• the method for producing a polyester film in the present invention is not particularly limited, and a method generally used in the past can be used.
• the polyester can be obtained by melting the polyester with an extruder, extruding it into a film, cooling it with a rotary cooling drum to obtain an unstretched film, and stretching the unstretched film.
• the stretching is preferably biaxial stretching because of its mechanical properties and the like.
• the biaxially stretched film can be obtained by a method of sequentially biaxially stretching a uniaxially stretched film in a vertical or horizontal direction in a horizontal or vertical direction, or a method of simultaneously biaxially stretching an unstretched film in the vertical and horizontal directions. I can.
• the stretching temperature at the time of stretching the polyester film is preferably set to be equal to or higher than the secondary transition point (Tg) of the polyester. It is preferable to stretch 1 to 8 times, particularly 2 to 6 times in each of the vertical and horizontal directions.
• the thickness of the polyester film is preferably 12 to 50 ⁇ m, more preferably 15 to 38 ⁇ m, and even more preferably 19 ⁇ m to 33 ⁇ m.
• the thickness of the film is 12 ⁇ m or more, it is preferable because there is no possibility of deformation due to heat during film production, a process of processing a release layer, and molding of a ceramic green sheet or the like.
• the thickness of the film is 50 ⁇ m or less, the amount of the film discarded after use does not become extremely large, which is preferable in reducing the environmental load.
• the polyester film may be a single layer or a multilayer of two or more layers.
• the polyester film has a surface layer A that is substantially free of inorganic particles.
• it may be a single layer of the surface layer A or a multilayer structure having the surface layer A and another layer, for example, the surface layer B described later.
• it is preferable to have a surface layer B capable of containing particles or the like on the opposite surface of the surface layer A which does not substantially contain inorganic particles.
• the layer structure in the thickness direction is the release layer /
• the layer structure in the thickness direction is the release layer /
• the layer C may have a plurality of layer configurations.
• the surface layer B may not contain particles. In that case, it is preferable to provide a coat layer containing particles and a binder on the surface layer B in order to impart slipperiness for winding the film into a roll.
• the surface layer A located on the surface to which the release layer is applied does not substantially contain inorganic particles.
• the surface layer A since the surface layer A does not substantially contain inorganic particles, the following region surface average roughness can be exhibited.
• the region surface average roughness (Sa) of the surface layer A is the region surface average roughness (Sa) on the surface on which the release layer is arranged, and the region surface average on the surface on which the release layer is arranged.
• the roughness (Sa) is 7 nm or less.
• the release layer laminated on the surface layer A can also exhibit high smoothness, and pinholes and the like can be formed during molding of the ultrathin ceramic green sheet laminated on the release layer. Is unlikely to occur. Furthermore, when the release layer is formed, it is possible to suppress the aggregation of the release layer component on the protrusions on the surface layer A, and it is possible to prevent deterioration of the smoothness of the release layer surface.
• the region surface average roughness (Sa) of the surface layer A is 0.1 nm or more and 7 nm or less, for example, 0.5 nm or more and 5 nm or less, and 0.5 nm or more and 4 nm or less.
• the smoothness of the release layer can be improved, and the generation of pinholes and the like can be suppressed during the molding of the ultrathin layer ceramic green sheet to be laminated.
• the release layer when the release layer is formed, it is possible to suppress the aggregation of the release layer component on the protrusions on the surface layer A, and it is possible to prevent deterioration of the smoothness of the release layer surface.
• substantially free of inorganic particles means a content of 50 ppm or less, preferably 10 ppm or less, and most preferably detection limit or less when the inorganic element is quantified by fluorescent X-ray analysis. .. This is because even if inorganic particles are not actively added to the film, contamination components derived from foreign substances and stains attached to the raw material resin or the line or device in the film manufacturing process may be mixed in the film. Is.
• the surface layer B may be provided on the opposite surface to the surface on which the release layer is arranged.
• the surface layer B preferably contains particles.
• the film is excellent in slipperiness and air release, and can have excellent transportability and winding property.
• the total amount of particles contained in the surface layer B is 1000 to 15000 ppm.
• the region surface average roughness (Sa) of the film of the surface layer B is, for example, 1 nm or more and 40 nm or less. More preferably, it is 5 nm or more and 35 nm or less.
• the total amount of silica particles and / or calcium carbonate particles is 1000 ppm or more and Sa is 1 nm or more, air can be uniformly released when the film is rolled up into a roll shape, and the rolled shape is good and the flatness is good. Can be done.
• these characteristics for example, when manufacturing an ultrathin layer resin sheet having a thickness of 0.2 ⁇ m or more and 1.0 ⁇ m or less, for example, a ceramic green sheet, wrinkles and misalignment of the wound ceramic green sheet are prevented. It is possible to provide a release film having excellent transportability, winding property, and storage property.
• the total amount of silica particles and / or calcium carbonate particles is 15,000 ppm or less and Sa is 40 nm or less, aggregation of particles that also function as a lubricant is unlikely to occur, and coarse protrusions (for example, protrusions having a height of 1 ⁇ m or more) are formed. Therefore, when manufacturing an ultra-thin layer resin sheet, for example, a ceramic green sheet, it is possible to suppress the generation of pinholes due to winding, for example, and it is possible to provide a resin sheet with stable quality.
• inert inorganic particles and / or heat-resistant organic particles other than silica and / or calcium carbonate can be used. From the viewpoint of transparency and cost, it is more preferable to use silica particles and / or calcium carbonate particles.
• examples of other inorganic particles that can be used include alumina-silica composite oxide particles and hydroxyapatite particles.
• examples of the heat-resistant organic particles include crosslinked polyacrylic particles, crosslinked polystyrene particles, and benzoguanamine particles.
• silica particles porous colloidal silica is preferable.
• calcium carbonate particles When calcium carbonate particles are used, light calcium carbonate surface-treated with a polyacrylic acid-based high-molecular compound is preferable from the viewpoint of preventing the particles from falling off.
• the average particle size of the particles added to the surface layer B is preferably 0.1 ⁇ m or more and 2.0 ⁇ m or less, and particularly preferably 0.5 ⁇ m or more and 1.0 ⁇ m or less.
• the average particle size of the particles is 0.1 ⁇ m or more, the slipperiness of the release film is good, which is preferable.
• the average particle size is 2.0 ⁇ m or less, the deformation of the surface layer A can be suppressed, and the uneven thickness of the ceramic green sheet and the occurrence of pinholes can be suppressed.
• the surface layer B may contain two or more types of particles made of different materials. Further, particles of the same type having different average particle sizes may be contained. Further, two or more kinds of different particles may have different average particle diameters within the above range. By including two different types of particles, the unevenness formed on the surface layer B can be highly controlled, and the smoothness of slipperiness can be achieved at the same time, which is preferable.
• the surface layer A which is the layer on which the release layer is provided, in order to prevent the mixing of particles or impurities.
• the thickness ratio of the surface layer A which is the layer on which the release layer is provided, is preferably 20% or more and 50% or less of the total thickness of the base film. When it is 20% or more, it is not easily affected by the particles contained in the surface layer B or the like from the inside of the film, and the region surface average roughness Sa can satisfy the above range, which is preferable. When it is 50% or less of the thickness of all the layers of the base film, the ratio of the recycled raw materials used in the surface layer B and the above-mentioned intermediate layer C by coextrusion can be increased, and the environmental load is reduced, which is preferable.
• the layers other than the surface layer A surface layer B or the above-mentioned intermediate layer C. Even in this case, it is preferable that the type and amount of the lubricant contained in the surface layer B, the particle size, and the region surface average roughness (Sa) satisfy the above ranges.
• the film is applied to the surface of the surface layer A and / or the surface layer B before or after stretching in the film forming process.
• a coat layer may be provided, and corona treatment or the like may be applied.
• the coat layer is provided on the surface layer A, it is preferable that the coat layer contains substantially no particles.
• the release layer is laminated on the surface layer A.
• the release layer is a layer obtained by curing the release layer forming composition, and the release layer and the release layer forming composition contain at least a cationically cured polydimethylsiloxane (a), and the release layer is released.
• the region surface roughness (Sa) of the layer is 2 nm or less,
• the number of protrusions with a height of 10 nm or more existing on the surface of the release layer is 200 / mm 2 or less.
• the release layer has such characteristics, it is possible to suppress the generation of pinholes in an ultra-thin resin sheet that requires high smoothness, for example, a ceramic green sheet, and it is possible to form a resin sheet having a uniform film thickness. .. More specifically, the present invention can suppress poor curing due to oxygen inhibition in the release layer, and can achieve high cross-linking of the release layer. INDUSTRIAL APPLICABILITY The present invention exhibiting such an effect can improve, for example, the solvent resistance of the surface of the release layer. By improving the solvent resistance of the release layer surface, it is possible to prevent the release layer from being eroded by the organic solvent used when molding the ceramic green sheet and printing the internal electrodes, and it is possible to have high peelability. can.
• high heat of 130 ° C. or higher is not required to accelerate the curing reaction. Therefore, it is possible to prevent the flatness of the release film from being impaired by the heat during processing. In addition, it is possible to suppress the mixing of foreign matter into the release film for molding the resin sheet and the occurrence of scratches on the release layer, and the generation of sheet damage due to the transfer of foreign matter and scratches to the mold release body such as the ceramic green sheet. Can be suppressed.
• the region surface average roughness (Sa) of the release layer is 2 nm or less. Further, the number of protrusions having a height of 10 nm or more existing on the surface of the release layer is 200 pieces / mm 2 or less.
• the surface of the release layer of the release film has predetermined conditions of the region surface average roughness (Sa) and the number of protrusions of 10 nm or more so as not to cause defects in the ceramic sheet coated and molded on the release layer surface.
• the region surface roughness (Sa) is 2 nm or less and the number of protrusions having a height of 10 nm or more is 200 pieces / mm 2 or less, there is no defect such as pinholes in the ceramic sheet when molding the ceramic sheet, and the yield is achieved. Is good and preferable. More preferably, the region surface roughness (Sa) is 1.7 nm or less, for example, 1.6 nm or less, and may be 1.5 nm or less. In one embodiment, the region surface roughness (Sa) is 1.3 nm or less. Further, the region surface roughness (Sa) may be 0.1 nm or more, and may be 0.2 nm or more.
• the number of protrusions having a height of 10 nm or more is 180 pieces / mm 2 or less, for example, 170 pieces / mm 2 or less, and 160 pieces / mm 2 or less. In one embodiment, the number of protrusions having a height of 10 nm or more may be 120 pieces / mm 2 or less, or 100 pieces / mm 2 or less. The number of protrusions having a height of 10 nm or more may be 1 piece / mm 2 or more, and may be, for example, 10 pieces / mm 2 or more.
• the ceramic sheet does not have defects such as pinholes and can have excellent mold releasability in a well-balanced manner.
• the region surface roughness (Sa) is 1.0 nm or less, and the number of protrusions having a height of 10 nm or more is 100 / mm 2 or less.
• the release layer having the region surface average roughness (Sa) and the number of protrusions according to the present invention can exhibit extremely excellent smoothness.
• the maximum protrusion height (Sp) of the release layer is 20 nm or less. When the maximum protrusion height is in such a range, defects in the ceramic sheet can be further suppressed. More preferably, the maximum protrusion height (Sp) is 15 nm or less, and even more preferably 10 nm or less. In one embodiment, the total number of protrusions having a height of 5 nm or more and less than 10 nm on the surface of the release layer and the number of protrusions having a height of 10 nm or more is 1500 pieces / mm 2 or less.
• the total number of protrusions having a height of 5 nm or more and less than 10 nm and the number of protrusions having a height of 10 nm or more on the release layer is 1500 pieces / mm 2 or less, defects in the ceramic sheet can be further suppressed and high smoothness is achieved. It is possible to obtain a release layer having the above, which is preferable. More preferably, the total number of protrusions having a height of 5 nm or more and less than 10 nm and the number of protrusions having a height of 10 nm or more is 1000 pieces / mm 2 or less, and for example, 500 pieces / mm 2 or less.
• the release layer according to the release film for molding a resin sheet of the present invention is a layer obtained by curing the release layer forming composition, and the release layer forming composition contains at least a cationically cured polydimethylsiloxane (a). include. Since the cationically cured polydimethylsiloxane (a) proceeds with the crosslinking reaction by the cationic curing reaction, it is a release layer having excellent solvent resistance without causing curing failure due to oxygen inhibition. Therefore, the release layer is not likely to be eroded by the organic solvent used during molding of the ceramic green sheet, printing of the internal electrode, and the like, and a release layer having excellent peelability can be obtained.
• the cationically cured polydimethylsiloxane (a) is preferably contained in the release layer at 90 mg / m 2 or less, for example, 60 mg / m 2 or less, 50 mg / m 2 or less, and 40 mg / m 2 or less. It is more preferably present, and more preferably 30 mg / m 2 or less.
• the amount of the cationically cured polydimethylsiloxane (a) may be 20 mg / m 2 or less.
• the content of the cationically cured polydimethylsiloxane (a) in the release layer is 50 mg / m 2 or less, the polydimethylsiloxane (a) aggregates during the step of forming the release layer, for example, the drying step. This can be suppressed, and there is no possibility that a large number of protrusions outside the scope of the present invention will occur, and the effect of the present invention can be achieved.
• the release layer and the release layer forming composition may contain components other than the cationically cured polydimethylsiloxane (a).
• polydimethylsiloxane (a) can be segregated on the surface of the release layer during processing of the release layer, and it is contained.
• the amount is 50 mg / m 2 or less, it is difficult to aggregate and a release layer having high smoothness can be formed.
• the release layer forming composition contains a cationically cured polydimethylsiloxane (a). Further, in the release layer in which the release layer forming composition is cured, a compound (cured product) derived from the cationically cured polydimethylsiloxane (a) is present. In the present specification, the compound derived from (a) present in the release layer may also be simply referred to as cationically cured polydimethylsiloxane (a).
• the cationically curable polydimethylsiloxane (a) refers to a polydimethylsiloxane having a cationically curable functional group.
• the cationically curable functional group is a reactive functional group exhibiting cationic curability, and specific examples thereof include a vinyl ether group, an oxetanyl group, an epoxy group, and an alicyclic epoxy group. Among them, it is preferable to have at least one functional group selected from an oxetanyl group, an epoxy group and an alicyclic epoxy group from the viewpoint of reactivity, and an alicyclic epoxy group is most preferable. Having such a functional group is preferable because a crosslinked structure is formed by a cationic curing reaction, and the release layer has excellent solvent resistance and excellent peelability.
• the number of cationically curable functional groups contained in the cationically curable polydimethylsiloxane (a) may be one or more. For example, having two or more cationically curable functional groups is preferable because the cationic curing reaction is more likely to proceed and the release layer has a high crosslink density.
• the introduction position of the cationically curable functional group is not particularly limited, and it is generally possessed at the side chain or the end of polydimethylsiloxane.
• the structure of the polydimethylsiloxane may be a linear structure or a branched structure, and can be used without any problem even if it has a functional group other than the cationically curable functional group.
• cation-curable polydimethylsiloxane (a) a commercially available product can be preferably used.
• Siricollies registered trademark
• the weight average molecular weight of the cationically cured polydimethylsiloxane (a) is preferably 1000 to 500,000, more preferably 5000 to 100,000.
• the weight average molecular weight is 1000 or more, the cationic curing reaction easily proceeds and the peelability is excellent, which is preferable.
• it is 500,000 or less the viscosity does not become too high, the coatability is excellent, and the release layer has high flatness, which is preferable.
• the release layer forming composition of the present invention may contain other resins in addition to the cationically cured polydimethylsiloxane (a). In this case, the film thickness of the release layer can be reduced.
• the release layer since the release layer is provided on the surface layer A of the base film that does not substantially contain inorganic particles, the release layer has extremely high smoothness even if the thickness of the release layer is thin. be able to. Further, since the release layer has a thin film thickness, the curing reaction easily proceeds, processing can be performed at a higher speed, and the release layer can be economically obtained.
• the film thickness is further thin, there is no possibility that the base film, extremely small foreign substances existing in the mold release processing process, etc. are taken into the mold release layer. Therefore, there is no possibility that protrusions due to foreign substances are generated on the surface of the release layer, and the release layer having a smooth surface as described above can be obtained.
• the film thickness of the release layer is preferably 0.001 ⁇ m or more and less than 0.050 ⁇ m.
• it is 0.001 ⁇ m or more, it is preferable because it is excellent in releasability.
• it is less than 0.050 ⁇ m aggregation of the release layer forming composition can be prevented, and a smooth release layer is preferable.
• the composition when the main component is the cationically cured polydimethylsiloxane (a), the composition is a cationically cured polydimethylsiloxane (a) with respect to 100 parts by mass of the resin solid content of the release layer. It contains 50 parts by mass or more, for example, more than 50 parts by mass, preferably 70 parts by mass or more, for example, 80 parts by mass or more, and in one embodiment, 90 parts by mass or more. Further, it may be an embodiment in which the cationically cured polydimethylsiloxane (a) is substantially contained in the entire resin solid content of the release layer.
• the release layer forming composition of the present invention may contain a cationically curable resin (b) in addition to the cationically curable polydimethylsiloxane (a).
• (b) is a resin different from (a), and the resin (b) does not have a polydimethylsiloxane structure. Specifically, it is roughly classified into two types: a cationically curable compound (b-1) having no silicone skeleton and a cyclic siloxane compound (b-2) having an alicyclic epoxy group.
• the release layer forming composition further contains a cationically curable compound (b-1) having no silicone skeleton, in addition to the cationically curable polydimethylsiloxane (a).
• a cationically curable compound (b-1) having no silicone skeleton include polymers and monomers having two or more cationically curable functional groups in the molecule and not having a silicone skeleton.
• a resin having two or more epoxy groups or an alicyclic epoxy group is preferable, and it is more preferable to have two or more alicyclic epoxy groups.
• the number of alicyclic epoxy groups may be 6 or less.
• the crosslinking reaction proceeds by the cationic curing reaction, and the release layer has excellent solvent resistance. Further, since the cross-linking reaction proceeds with the polydimethylsiloxane (a) contained in the release layer at the same time, it is preferable because it is excellent in peelability and the transfer of the polydimethylsiloxane (a) to the ceramic green sheet is suppressed.
• the release layer forming composition contains both a cationically curable resin (b-1) having no silicone skeleton and polydimethylsiloxane (a), so that a release layer having high smoothness can be obtained. realizable.
• a release layer containing the compound (b-1) it is possible to fill fine irregularities, extremely minute foreign substances, protrusions derived from oligomers, etc. existing in the base film, and the release layer is ultra-smooth. Become.
• the curing reaction proceeds by ultraviolet rays, the release layer has high smoothness.
• (b-1) and (a) are uniformly leveled and the flatness is improved. It can be inferred that the curing proceeds after the height is increased, and a release layer having high smoothness can be obtained. Further, in the present invention, the polydimethylsiloxane (a) contained at the same time segregates on the surface of the release layer in the drying step, so that a release layer having excellent peelability can be obtained.
• the cationically curable compound (b-1) having no silicone skeleton is preferably a low molecular weight monomer.
• the number average molecular weight is preferably 200 or more and less than 5000, more preferably 200 or more and less than 2500, and further preferably 200 or more and less than 1000.
• the number average molecular weight is 200 or more, the boiling point does not decrease, and the cationically curable compound (b-1) does not volatilize in the drying step of the release layer forming composition during the release layer processing, which is preferable.
• it is less than 5000 the crosslink density of the release layer is increased and the solvent resistance is excellent, which is preferable.
• it since it can exist in a fluid state during the drying step, it is preferable because it has excellent leveling property and becomes an ultra-smooth release layer.
• cationically curable compound (b-1) having no silicone skeleton a commercially available compound can be preferably used.
• examples of compounds having an alicyclic epoxy group include Daicel's Celoxide 2021P, Celoxide 2081, Epolide GT401, EHPE3150, Shikoku Chemicals' HiREM-1, ENEOS's THI-DE, DE-102, and DE. -103 etc. can be mentioned.
• resins having epoxy groups are DIC's EPICLON® 830, 840, 850, 1051-75M, N-665, N-670, N-690, N-673-80M, N-690- Examples include 75M, Denacol (registered trademark) EX-611, EX-313, and EX-321 manufactured by Nagase Chemtech.
• the content of the cationically cured compound (b-1) having no silicone skeleton is 100 parts by mass in total of the cationically cured polydimethylsiloxane (a) and the cationically cured compound (b-1) in the release layer. It is preferably 80% by mass or more, more preferably 85% by mass or more, and further preferably 90% by mass or more. It is preferable to set the content of the cationically curable compound (b-1) to 80% by mass or more and use it as the main component in the release layer because the release layer has a high crosslink density and excellent peelability.
• the content of the cationically cured polydimethylsiloxane (a) contained in the release layer can be reduced, and the composition derived from polydimethylsiloxane (a) can be suppressed from aggregating on the surface of the release layer in the drying step. It is preferable because there is no risk of deterioration of flatness.
• the cationically curable type The compound (b-1) is preferably 99.9% by mass or less.
• a compound (cured product) derived from the cationically curable compound (b-1) having no silicone skeleton is present in the release layer on which the release layer forming composition is cured.
• the compound derived from (b-1) present in the release layer may be simply described as a cationically curable compound (b-1) having no silicone skeleton.
• the release layer forming composition contains a cationically cured polydimethylsiloxane (a) and a cationically cured compound (b-1), the release layer has a high crosslink density, excellent solvent resistance, and excellent peeling power. It is preferable because it is a release layer to have. Further, when the cationically curable compound (b-1) is contained, the film thickness of the release layer can be increased while keeping the content of the cationically curable polydimethylsiloxane (a) within a predetermined range. preferable. By increasing the film thickness of the release layer, scratches and extremely minute irregularities existing in the base film can be filled, and as described above, a smooth release layer can be obtained, which is preferable.
• the thickness of the release layer may be 0.05 ⁇ m or more and 1.0 ⁇ m or less. It is more preferably 0.1 ⁇ m or more and 0.5 ⁇ m or less. When it is 0.05 ⁇ m or more, it is preferable because it becomes a smooth release layer. When it is 1.0 ⁇ m or less, a release film having excellent flatness can be obtained without curling, which is preferable.
• the release layer forming composition may further contain a cyclic siloxane compound (b-2) having an alicyclic epoxy group.
• a cyclic siloxane compound (b-2) having an alicyclic epoxy group include those represented by the following structural formula (Chemical formula 1) (in Chemical formula 1, R2 is an alkyl having 1 to 4 carbon atoms. Based on).
• the cationically curable compound (b-2) having a cyclic siloxane skeleton has at least two or more alicyclic epoxy groups. When two or more alicyclic epoxy groups are present, the cationic curing reaction proceeds and a release layer having a high crosslink density is obtained, which is preferable.
• the cyclic siloxane compound (b-2) having an alicyclic epoxy group because it becomes an ultra-smooth release layer for the same reason as when the cationically curable compound (b-1) is used. That is, it is possible to fill fine irregularities, extremely fine foreign substances, protrusions derived from oligomers, etc. existing in the base film.
• the compound (b-2) and polydimethylsiloxane (a) are uniformly leveled in the drying step of the release layer forming composition during the release layer processing, and the flatness is improved. Since curing proceeds after that, an ultra-smooth release layer can be obtained. Further, in the present invention, since the polydimethylsiloxane (a) contained at the same time segregates on the surface of the release layer in the drying step, a release layer having excellent peelability can be obtained.
• the cyclic siloxane compound (b-2) having an alicyclic epoxy group has good compatibility with the cationically cured polydimethylsiloxane (a), it is appropriately mixed in the release layer and the cross-linking reaction proceeds with each other. Therefore, it is preferable because it is a release layer having excellent solvent resistance and excellent peelability. Further, since the cyclic siloxane compound (b-2) has a cyclic siloxane structure, it has a rigid molecular skeleton, and the film hardness when cured is increased, which is preferable. By increasing the film hardness, the release layer is less likely to be deformed when the resin sheet, for example, the ceramic green sheet is peeled off, and good peelability can be exhibited. Further, it is preferable that the release layer is less likely to be scratched and that the scratches on the release layer are not transferred to the resin sheet, for example, the ceramic green sheet, causing a problem.
• the release layer forming composition contains the cyclic siloxane compound (b-2) because the adhesion of the release layer to the base film is improved.
• the adhesion of the release layer is improved, the generation of scratches in the transport process can be suppressed, and the release layer is not likely to be transferred when the resin sheet is peeled off, which is preferable.
• the cyclic siloxane compound (b-2) has two or more alicyclic epoxy groups in the molecule.
• the crosslinking reaction proceeds by the cationic curing reaction, and the release layer has excellent solvent resistance.
• the cross-linking reaction proceeds with the polydimethylsiloxane (a) contained in the release layer at the same time, it is preferable because it is excellent in peelability and the transfer of the polydimethylsiloxane (a) to the ceramic green sheet is suppressed.
• the cyclic siloxane compound (b-2) has 6 or less alicyclic epoxy groups in the molecule.
• cyclic siloxane compound (b-2) having an alicyclic epoxy group a commercially available one can be used.
• X-40-2670 and X-40-2678 manufactured by Shin-Etsu Chemical Co., Ltd. can be mentioned.
• the content of the cyclic siloxane compound (b-2) is 80% by mass or more based on 100 parts by mass of the total of the cationically cured polydimethylsiloxane (a) and the cyclic siloxane compound (b-2) in the release layer. It is more preferably 85% by mass or more, and even more preferably 90% by mass or more. It is preferable to set the content of the cyclic siloxane compound (b-2) to 80% by mass or more and use it as the main component in the release layer because the release layer has a high crosslink density and excellent peelability.
• the content of the cationically cured polydimethylsiloxane (a) contained in the release layer can be reduced, and in the present invention, the cationically cured polydimethylsiloxane (a) aggregates on the surface of the release layer in the drying step. It is preferable because it can suppress the problem and the flatness is not deteriorated.
• the cyclic siloxane compound ( b-2) is preferably 99.9% by mass or less.
• a compound (cured product) derived from the cyclic siloxane compound (b-2) is present in the release layer on which the release layer forming composition is cured.
• the compound derived from the cyclic siloxane compound (b-2) present in the release layer may also be simply referred to as the cyclic siloxane compound (b-2).
• the thickness of the release layer shall be 0.05 ⁇ m or more and 1.0 ⁇ m or less. Is preferable, and it is more preferably 0.1 ⁇ m or more and 0.5 ⁇ m or less. When it is 0.05 ⁇ m or more, it is preferable because it becomes a smooth release layer. When it is 1.0 ⁇ m or less, a release film having excellent flatness can be obtained without curling, which is preferable.
• the release layer may contain both the cationically curable resin (b-1) and the cyclic siloxane compound (b-2), and these cationically curable resins (b-1) and the cyclic siloxane compound (b-).
• the total amount of 2) is 80% by mass with respect to 100 parts by mass of the total of the cationically cured polydimethylsiloxane (a), the cationically cured compound (b-1) and the cyclic siloxane compound (b-2) in the release layer. It can be 99.9% by mass or less.
• the release layer forming composition contains the acid generator (c).
• a compound derived from the acid generator (c) may be present in the release layer.
• the compound derived from the acid generator (c) present in the release layer may also be simply described as the acid generator (c).
• the acid generator is not particularly limited and a general one is used, but by using a photoacid generator that generates an acid under ultraviolet irradiation, the amount of heat during processing can be suppressed and the flatness is excellent. It is preferable because it becomes a release layer.
• a salt composed of onium ions and non-nucleophilic anions from the viewpoint of reactivity.
• an organic metal complex typified by an iron allene complex or a carbocation salt typified by tropylium may be used, or phenols substituted with an anthracene derivative or an electron-withdrawing group, for example, pentafluorophenol may be used. ..
• the salt composed of the onium ion and the non-nucleophilic anion is used as a photoacid generator
• iodonium, sulfonium, and ammonium can be used as the onium ion.
• organic group of the onium ion triaryl, diaryl (monoalkyl), monoaryl (dialkyl), or trialkyl may be used, and benzophenone, 9-fluorene may be introduced, or other organic groups may be used. good.
• non-nucleophilic anion hexafluorophosphorate, hexafluoroantimonate, hexafluoroborate, and tetra (pentafluorophenyl) borate are preferably used. Further, a tetra (pentafluorophenyl) gallium ion or an anion in which some of the fluorine anions are replaced with a perfluoroalkyl group or an organic group may be used, or other anion components may be used.
• the amount of the photoacid generator added is 100 parts by mass in total of the cationically cured polydimethylsiloxane (a), the cationically cured compound (b-1) and / or the cyclic siloxane compound (b-2) in the release layer. It is 0.1 to 10% by mass, more preferably 0.5 to 8% by mass. More preferably, it is 1 to 5% by mass. When it is 0.1% by mass or more, the amount of generated acid is insufficient and there is no possibility of insufficient curing, which is preferable. Further, when the content is 10% by mass or less, the amount of generated acid becomes appropriate, and the amount of acid transferred to the ceramic green sheet to be molded can be suppressed, which is preferable.
• a total of 100 parts by mass of the cationically cured polydimethylsiloxane (a) and the cationically cured compound (b-1) and / or the cyclic siloxane compound (b-2) in the release layer is a cationically cured type. It means the total value of the solid content of the polydimethylsiloxane (a) and the solid content of the cationically curable resin (b).
• the weight of the cationically cured polydimethylsiloxane (a) corresponds to 100 parts by mass of the resin solid content in the release layer.
• the release layer forming composition contains an organic solvent having an SP value ( ⁇ ) of 14 or more and 17 or less, and the release layer forming composition has an SP value ( ⁇ ) of 14 or more and 17 or less. Is contained in an amount of 10% by mass or more with respect to 100 parts by mass of the total weight of the release layer forming composition.
• An organic solvent having an SP value ( ⁇ ) of 14 to 17 exhibits excellent solubility in a cationically cured polydimethylsiloxane (a). Therefore, in the drying step after the coating step, even if the organic solvent is dried and the concentration of (a) in the release layer forming composition is increased, the state of being uniformly dissolved can be maintained, and the leveling can be performed cleanly without agglomeration.
• the cationically cured polydimethylsiloxane (a) can be maintained in a dissolved state for a long time during drying, so that it may aggregate during drying and the smoothness may deteriorate. It is preferable because there is no such thing. Details of the organic solvent having an SP value ( ⁇ ) of 14 or more and 17 or less will be described later.
• an adhesion improver an additive such as an antistatic agent, or the like may be added to the release layer as long as the effect of the present invention is not impaired. Further, in order to improve the adhesion to the substrate, it is also preferable to perform pretreatment such as anchor coating, corona treatment, plasma treatment, and atmospheric pressure plasma treatment on the surface of the polyester film before providing the release coating layer.
• the release film obtained by the present invention preferably has a peeling force of 0.01 mN / mm or more and 2.0 mN / mm or less when peeling the ceramic green sheet. More preferably, it is 0.05 mN / mm or more and 1.0 mN / mm or less.
• the peeling force is 0.01 mN / mm or more, there is no possibility that the ceramic green sheet will be lifted during transportation, which is preferable.
• the peeling force is 2.0 mN / mm or less, the ceramic green sheet is not likely to be damaged at the time of peeling, which is preferable.
• the thickness of the release layer is 1.0 ⁇ m or less, 0.5 ⁇ m or less, and further 0.3 ⁇ m or less. Even if there is, the surface of the release layer can be smoothed. Therefore, the amount of solvent and resin used can be reduced, which is environmentally friendly, and a release film for molding an ultra-thin ceramic green sheet can be produced at low cost.
• the present invention provides, in another embodiment, a method for producing a release film for molding a resin sheet, which comprises the following steps.
• the surface layer A is a layer that does not substantially contain inorganic particles.
• the release layer forming composition comprises a cationically cured polydimethylsiloxane (a).
• Coating process A drying step of heating and drying the polyester film coated with the release layer forming composition. The heat drying has a first drying step and then a second drying step.
• the drying step T1 in the first drying step is higher than the drying temperature T2 in the second drying step;
• a photocuring step of irradiating with active energy rays to cure the release layer forming composition.
• the production method of the present invention by strengthening the first drying condition (by strengthening the drying), aggregation of the resin constituting the release layer can be prevented, and a release layer having high smoothness can be obtained.
• the first drying step has predetermined conditions, and in one embodiment, a release layer having high smoothness can be obtained by using a specific solvent.
• a release layer forming composition containing at least a cationically cured polydimethylsiloxane (a) is placed on a surface layer A which does not substantially contain inorganic particles of a polyester film. It has a coating step of coating, a drying step of heating and drying the film after coating, for example, using a drying furnace, and a photocuring step of curing the film using active energy rays after heating and drying. In particular, it is preferable to adopt a method in which the coating step, the drying step, and the photocuring step are performed in this order.
• a release layer having high smoothness can be realized by devising the manufacturing conditions in the coating process. Specifically, by containing an organic solvent having an SP value ( ⁇ ) of 14 to 17 in the release layer forming composition, aggregation of the cationically cured polydimethylsiloxane (a) can be suppressed, which is excellent. A release layer can be obtained.
• the SP value ( ⁇ ) can be used to predict the solubility of the substance, and the organic solvent having the SP value ( ⁇ ) of 14 to 17 shows excellent solubility in the cationically cured polydimethylsiloxane (a). ..
• the content of the organic solvent having an SP value ( ⁇ ) of 14 to 17 contained in the release layer forming composition is preferably 10% by mass or more, preferably 10% by mass or more, based on 100 parts by mass of the release layer forming composition. It is preferably mass% or more.
• the content is 10% by mass or more, the cationically cured polydimethylsiloxane (a) can be maintained in a dissolved state for a long time during drying, so that there is no risk of aggregation during drying and deterioration of smoothness, which is preferable.
• the content of the organic solvent having an SP value ( ⁇ ) of 14 to 17 is 80% by mass or less, for example, 65% by mass or less, and less than 50% by mass, based on 100 parts by mass of the release layer forming composition. There may be.
• the SP value ( ⁇ ) in the present specification adopts the Hildebrand solubility parameter.
• the Hildebrand solubility parameter can be experimentally calculated from the Hansen Solubility Parameter (HSP value) as shown in Equation 1.
• SP value ( ⁇ ) (( ⁇ d ) 2 + ( ⁇ p ) 2 + ( ⁇ h ) 2 ) 1/2 ...
• ( ⁇ D ) is a dispersion force term
• ( ⁇ P ) is a polarity term
• ( ⁇ H ) is a hydrogen bond force term
• the Hansen solubility parameter is the idea of decomposing the Hildebrand solubility parameter into three components.
• HSPiP Hydrophilility Parameters in Practice
• Examples of the organic solvent having an SP value ( ⁇ ) of 14 to 17 include normal hexane ( ⁇ : 14.9), normal heptane ( ⁇ : 15.3), normal octane ( ⁇ : 15.5), and isopropyl ether ( ⁇ : 15.5). ⁇ : 15.8), 1,1-diethoxyethane ( ⁇ : 15.9), methylcyclohexane ( ⁇ : 16.0), cyclopentane ( ⁇ : 16.5), cyclohexane ( ⁇ : 16.8) And so on as an example.
• the coating amount of the release layer forming composition is preferably 10 g / m 2 or less, and more preferably 8 g / m 2 or less.
• the coating amount is 10 g / m 2 or less, for example, when coated by the gravure coating method, liquid turbulence is less likely to occur at the kiss portion between the film and the gravure roll, and a release layer having excellent smoothness can be obtained. Therefore, it is preferable.
• the solvent contained in the release layer forming composition is preferably two or more kinds, and at least one of them is a solvent having an SP value ( ⁇ ) of 14 to 17 as described above, and at least one.
• the boiling point is preferably 100 ° C. or higher.
• toluene xylene, normal octane, cyclohexanone, methyl isobutyl ketone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, isobutyl acetate, normal butanol and the like.
• the coating liquid of the release layer forming composition is filtered before coating.
• the filtration method is not particularly limited, and a known method can be used, but it is preferable to use a surface type, depth type, or adsorption type cartridge filter. It is preferable to use a cartridge type filter because it can be used when the coating liquid is continuously sent from the tank to the coating portion, and thus it can be filtered efficiently with high productivity.
• As the filtration accuracy of the filter it is preferable to use one that removes 99% or more of a filter having a size of 1 ⁇ m, and more preferably 99% or more of a filter having a size of 0.5 ⁇ m can be filtered.
• any known coating method can be applied as the coating method, for example, a roll coating method such as a gravure coating method or a reverse coating method, a bar coating method such as a wire bar, a die coating method, a spray coating method, or an air knife. Conventionally known methods such as the coat method can be used.
• Examples of the method of applying the release layer forming composition on the base film and drying it include known hot air drying and infrared heaters, but hot air drying having a high drying speed is preferable. It is preferable to dry in a drying oven, and a known drying oven can be used without particular limitation. Regarding the method of the drying furnace, either the roll support method or the floating method may be used, but since the roll support method has a wider range in which the air volume during drying can be adjusted, the air volume etc. is adjusted according to the type of release layer. It is preferable because it can be done.
• the drying step can be divided into two drying steps, a constant rate drying step (hereinafter referred to as a first drying step) and a reduced rate drying step (hereinafter referred to as a second drying step) at the initial stage of drying.
• the two steps are preferably continuous in the order of the first drying step and the second drying step, and can be distinguished by zoning in the drying furnace, and the first (initial) drying step is The first drying oven and the second (late) drying step can be dried using the second drying oven.
• the present inventors have found that it is important that the drying temperature T1 in the first drying step is higher than the drying temperature T2 in the second drying step in order to improve the smoothness of the release layer. rice field. It is preferable that the temperature of the first drying oven and the temperature of the second drying oven are in the range described later. By manufacturing under such conditions, the constant rate drying time in the first drying step can be short, the reduced rate drying time in the second drying step can be lengthened, and a release layer having excellent flatness can be obtained. It is preferable because it is possible.
• the drying temperature T1 is preferably 90 ° C. or higher and 180 ° C. or lower, and preferably 100 ° C. or higher and 150 ° C. or lower. It is preferable to raise the temperature in the first drying furnace and shorten the constant rate drying time because it is possible to prevent the agglomeration of the cationically cured polydimethylsiloxane (a) contained in the release layer forming composition.
• the higher the temperature of the first drying furnace the shorter the constant rate drying time, which is preferable.
• the temperature is preferably 180 ° C. or lower.
• the temperature is 90 ° C. or higher, the drying capacity is sufficient, which is preferable.
• the temperature inside the second drying oven is preferably 60 ° C. or higher and 140 ° C. or lower, and more preferably 80 ° C. or higher and 120 ° C. or lower.
• it is preferable to slow down the drying time because the release layer surface before photo-curing can be dried without being roughened and the smoothness of the release layer is improved.
• the constant rate drying time in the first drying step is preferably shorter than the reduced rate drying time in the second drying step.
• the constant rate drying time in the first drying step is preferably shorter than the reduced rate drying time in the second drying step.
• the time from application to entering the first drying furnace is preferably 0.1 seconds or more and 2.5 seconds or less, preferably 0.1 seconds or more and 2.0 seconds or less, which is short. The more preferable.
• the drying time in the first drying step can be shortened, the aggregation of the cationically cured polydimethylsiloxane (a) is suppressed, and the smoothness is improved. It is preferable because an excellent release layer can be obtained.
• the time to enter the drying oven can be calculated from the processing speed and the structure of the processing machine base.
• the production method of the present invention includes a photocuring step of irradiating with active energy rays after the drying step to cure the release layer forming composition.
• the cation curing reaction of the release layer forming composition after drying proceeds by irradiating with active energy rays.
• active energy ray known techniques such as ultraviolet rays and electron beams can be used, and it is preferable to use ultraviolet rays.
• the integrated amount of light when ultraviolet rays are used can be expressed by the product of illuminance and irradiation time. For example, it is preferably 10 to 500 mJ / cm 2 . It is preferable that the content is not less than the lower limit because the release layer can be sufficiently cured. When the value is not more than the upper limit, heat damage to the film due to heat during irradiation can be suppressed and the smoothness of the release layer surface can be maintained, which is preferable.
• the film When irradiating with active energy rays, it is preferable to hold the back surface of the film with a backup roll.
• a backup roll By providing a backup roll, the distance from the active energy radiation source can be kept constant, so that uniform irradiation is preferable. Further, it is preferable to irradiate the surface of the backup roll with active energy rays while cooling the film. By cooling, the film is less likely to be damaged by heat even when irradiated with active energy rays, and the smoothness of the release layer surface can be maintained, which is preferable.
• the production method of the present invention provides a method for producing a release film for producing a resin sheet containing an inorganic compound.
• the resin sheet in the present invention is not particularly limited as long as it is a sheet containing a resin.
• the release film of the present invention is a release film for molding a resin sheet containing an inorganic compound.
• the inorganic compound include metal particles, metal oxides, minerals and the like, and examples thereof include calcium carbonate, silica particles, aluminum particles, barium titanate particles and the like. Since the present invention has a release layer having high smoothness, even if the resin sheet contains these inorganic compounds, there are drawbacks that may be caused by the inorganic compounds, such as breakage of the resin sheet and the release layer to the resin sheet. It is possible to suppress the problem that the peeling becomes difficult.
• the resin component forming the resin sheet can be appropriately selected depending on the intended use.
• the resin sheet containing the inorganic compound is a ceramic green sheet.
• the ceramic green sheet can contain barium titanate as an inorganic compound.
• a polyvinyl butyral-based resin can be contained.
• the resin sheet has a thickness of 0.2 ⁇ m or more and 1.0 ⁇ m or less.
• the present invention can provide a method for producing a release film for producing a resin sheet containing such an inorganic compound.
• the method for producing a release film for molding a resin sheet in the present invention may include a step of molding a resin sheet having a thickness of 0.2 ⁇ m or more and 1.0 ⁇ m or less.
• a monolithic ceramic capacitor has a rectangular parallelepiped ceramic prime field. Inside the ceramic prime field, first internal electrodes and second internal electrodes are alternately provided along the thickness direction. The first internal electrode is exposed on the first end face of the ceramic prime field. A first external electrode is provided on the first end face. The first internal electrode is electrically connected to the first external electrode at the first end face. The second internal electrode is exposed on the second end face of the ceramic prime field. A second external electrode is provided on the second end face. The second internal electrode is electrically connected to the second external electrode at the second end face.
• the release film of the present invention is a release film for manufacturing a ceramic green sheet, and is used for manufacturing such a laminated ceramic capacitor.
• the method for manufacturing a ceramic green sheet using the release film for manufacturing a ceramic green sheet of the present invention can mold a ceramic green sheet having a thickness of 0.2 ⁇ m or more and 1.0 ⁇ m or less in more detail.
• the ceramic green sheet is manufactured as follows. First, the release film of the present invention is used as a carrier film, and a ceramic slurry for forming a ceramic prime field is applied and dried. An ultra-thin product having a thickness of 0.2 to 1.0 ⁇ m is required for the ceramic green sheet.
• a conductive layer for forming the first or second internal electrode is printed on the coated and dried ceramic green sheet.
• a ceramic green sheet, a ceramic green sheet on which a conductive layer for forming a first internal electrode is printed, and a ceramic green sheet on which a conductive layer for forming a second internal electrode is printed are appropriately laminated and pressed. Thereby, a mother laminated body is obtained.
• the mother laminate is divided into a plurality of pieces to prepare a raw ceramic prime field.
• a ceramic prime is obtained by firing a raw ceramic prime. After that, the multilayer ceramic capacitor can be completed by forming the first and second external electrodes.
• the cut release film was embedded in a resin and ultrathin sectioned using an ultramicrotome. Then, a cross-sectional observation was performed using a JEM2100 transmission electron microscope manufactured by JEOL Ltd., and the film thickness of the release layer was measured from the observed TEM image. When the thickness was too thin to be evaluated accurately by cross-sectional observation, it was measured using a reflection spectroscopic film thickness meter (FE-3000, manufactured by Otsuka Electronics Co., Ltd.).
• Weight of release layer In the present specification, the value of the weight calculated assuming that the weight per 1 ⁇ m of the release layer thickness is 1 g / m 2 is adopted. For example, when the release layer thickness measured by the above method is 0.2 ⁇ m, the total weight of the release layer is 0.2 g / m 2 . Further, the weight of the cationically cured polydimethylsiloxane (a), the weight of the cationically cured resin (b), and the weight of the acid generator (c) contained in the release layer are contained in the release layer forming composition. The value calculated from the compounding ratio of each component and the total weight of the release layer was adopted.
• the release layer thickness is 0.2 ⁇ m and the release layer weight ratio of the cationically cured polydimethylsiloxane (a) is 5 parts by mass
• the weight of (a) contained in the release layer is 0.01 g / g. It is m 2 .
• the release layer weight ratio (% by mass) was calculated with the total of the component (a) and the component (b) as 100 parts by mass.
• the slurry composition I made of the following materials was stirred and mixed for 10 minutes, and dispersed with zirconia beads having a diameter of 0.5 mm for 10 minutes using a bead mill to obtain a primary dispersion.
• Secondary dispersion was performed with 5.5 mm zirconia beads for 10 minutes to obtain a ceramic slurry.
• Eslek BM-S 16.3 parts by mass 1-Ethyl-3-methylimidazolium ethyl sulfate 0.5 parts by mass
• an electric eliminator SJ-F020 manufactured by Keyence
• a peeling tester (VPA-3 manufactured by Kyowa Interface Science Co., Ltd., load cell load 0.1N) was used.
• the peeling was performed at a peeling angle of 90 degrees, a peeling temperature of 25 ° C., and a peeling speed of 10 m / min.
• a double-sided adhesive tape (Nitto Denko Co., Ltd., No. 535A) is attached on the SUS plate attached to the peeling tester, and the ceramic green sheet side is bonded to the double-sided tape on the release film.
• the ceramic green sheet side is bonded to the double-sided tape on the release film.
• the average value of the peeling force having a peeling distance of 20 mm to 70 mm was calculated, and the value was used as the peeling force.
• the measurement was carried out a total of 5 times, and the value of the average value of the peeling force was adopted and evaluated. Judgment was made according to the following criteria from the obtained numerical values of the peeling force. ⁇ : 0.1 mN / mm or more, less than 1.0 mN / mm ⁇ : 1.0 mN / mm or more
• PET polyethylene terephthalate pellets
• esterification reaction device a continuous esterification reaction device consisting of a stirrer, a splitter, a raw material charging port, and a three-stage complete mixing tank having a raw material charging port and a product outlet was used.
• TPA terephthalic acid
• EG ethylene glycol
• antimony trioxide is made up to 160 ppm of Sb atoms with respect to the PET produced, and these slurrys are esterified.
• the reaction product in the first esterification reaction can is continuously taken out of the system and supplied to the second esterification reaction can, and distilled off from the first esterification reaction can in the second esterification reaction can.
• EG is supplied in an amount of 8% by mass with respect to the produced PET, and an EG solution containing an amount of magnesium acetate tetrahydrate having an amount of Mg atoms of 65 ppm with respect to the produced PET and 40 ppm of P atoms with respect to the produced PET.
• PET (I) After filtering with a filter, it was subjected to ultrafiltration and extruded into water, and after cooling, it was cut into chips to obtain PET chips with an intrinsic viscosity of 0.60 dl / g (hereinafter abbreviated as PET (I)). ..
• PET (I) an intrinsic viscosity of 0.60 dl / g
• the lubricant content in the PET chip was 0.6% by mass.
• PET (II) Preparation of polyethylene terephthalate pellets (PET (II))
• PET (II) a PET chip having an intrinsic viscosity of 0.62 dl / g containing no particles such as calcium carbonate and silica was obtained (hereinafter abbreviated as PET (II)).
• layer A separation surface side layer
• extruded casting
• An unstretched polyethylene terephthalate sheet having an intrinsic viscosity of 0.59 dl / g was obtained.
• the unstretched sheet was heated with an infrared heater and then stretched 3.5 times in the vertical direction at a roll temperature of 80 ° C. due to the speed difference between the rolls.
• E5101 Toyobo Ester (registered trademark) film, manufactured by Toyobo Co., Ltd.) having a thickness of 25 ⁇ m was used.
• E5101 has a structure in which particles are contained in the surface layer A and the surface layer B.
• the Sa of the surface layer A of the laminated film X2 was 24 nm, and the Sa of the surface layer B was 24 nm.
• Example 1 After passing the release layer forming composition 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 ⁇ m or more, the coating amount is 5.0 g using reverse gravure. It was painted to be / m 2 . Then, the processing speed was adjusted so as to enter the first drying oven after 0.5 seconds, and the heating and drying were continuously performed at a temperature of the first drying oven of 120 ° C. and a temperature of the second drying oven of 90 ° C.
• a release film for resin sheet molding is formed by irradiating a cooling roll with ultraviolet rays having an integrated light intensity of 100 mJ / cm 2 using an ultraviolet irradiator (H-bulb manufactured by Heleus) to cure the release layer.
• H-bulb ultraviolet irradiator
• good results were obtained as shown in Table 1.
• the obtained release film for molding a resin sheet was, for example, a release film capable of producing a resin sheet having a thickness of 0.2 ⁇ m or more and 1.0 ⁇ m or less.
• each component (a), (b), (c) shown in the table indicates the content ratio per solid content (weight of each component with respect to the total weight of the release layer).
• (Release layer forming composition 1) Methyl ethyl ketone 24.000 parts by mass (SP value ( ⁇ ): 19.1, ( ⁇ D ): 16.0, ( ⁇ P ): 9.0, ( ⁇ H ): 5.1) Toluene 24.000 parts by mass (SP value ( ⁇ ): 18.2, ( ⁇ D ): 18.0, ( ⁇ P ): 1.4, ( ⁇ H ): 2.0) Normal heptane 48.000 parts by mass (SP value ( ⁇ ): 15.3, ( ⁇ D ): 15.3, ( ⁇ P ): 0.0, ( ⁇ H ): 0.0) (A) -1 0.039 parts by mass (b) -1 3.883 parts by mass (c) -1 0.078 parts by mass
• Example 2 A release film for molding a resin sheet was obtained by the same method as in Example 1 except that the composition of the release layer and the production method shown in Table 1 were changed.
• Example 5 A release film for molding a resin sheet was obtained in the same manner as in Example 1 except that the release layer forming composition 2 having the following composition was used.
• (Release layer forming composition 2) Methyl ethyl ketone 38.400 parts by mass (SP value ( ⁇ ): 19.1, ( ⁇ D ): 16.0, ( ⁇ P ): 9.0, ( ⁇ H ): 5.1) Toluene 38.400 parts by mass (SP value ( ⁇ ): 18.2, ( ⁇ D ): 18.0, ( ⁇ P ): 1.4, ( ⁇ H ): 2.0) Normal heptane 19.200 parts by mass (SP value ( ⁇ ): 15.3, ( ⁇ D ): 15.3, ( ⁇ P ): 0.0, ( ⁇ H ): 0.0) (A) -1 0.196 parts by mass (b) -1 3.726 parts by mass (c) -1 0.078 parts by mass
• Example 6 Normal heptane in the release layer forming composition is cyclohexane (SP value ( ⁇ ): 16.8, ( ⁇ D ): 16.8, ( ⁇ P ): 0.0, ( ⁇ H ): 0.2).
• a release film for molding a resin sheet was obtained in the same manner as in Example 2 except that the film was changed to.
• Example 7 A release film for molding a resin sheet was obtained by the same method as in Example 2 except that the coating amount and the solid content ratio were changed to those shown in Table 1. At this time, the organic solvent ratio was adjusted to be the same as that of the release layer forming composition 1.
• Example 9 A release film for molding a resin sheet was obtained in the same manner as in Example 1 except that the composition was changed to the release layer forming composition 3 having the following composition.
• Composition for forming a release layer 3 Methyl ethyl ketone 24.000 parts by mass (SP value ( ⁇ ): 19.1, ( ⁇ D ): 16.0, ( ⁇ P ): 9.0, ( ⁇ H ): 5.1) Toluene 24.000 parts by mass (SP value ( ⁇ ): 18.2, ( ⁇ D ): 18.0, ( ⁇ P ): 1.4, ( ⁇ H ): 2.0) Normal heptane 48.000 parts by mass (SP value ( ⁇ ): 15.3, ( ⁇ D ): 15.3, ( ⁇ P ): 0.0, ( ⁇ H ): 0.0) (A) -1 0.039 parts by mass (b) -2 3.883 parts by mass (c) -1 0.078 parts by mass
• Example 10 A release film for molding a resin sheet was obtained by the same method as in Example 1 except that the composition of the release layer and the production method shown in Table 1 were changed.
• Example 13 A release film for molding a resin sheet was obtained in the same manner as in Example 1 except that the release layer forming composition 4 having the following composition was used.
• (Release layer forming composition 4) Methyl ethyl ketone 38.400 parts by mass (SP value ( ⁇ ): 19.1, ( ⁇ D ): 16.0, ( ⁇ P ): 9.0, ( ⁇ H ): 5.1) Toluene 38.400 parts by mass (SP value ( ⁇ ): 18.2, ( ⁇ D ): 18.0, ( ⁇ P ): 1.4, ( ⁇ H ): 2.0) Normal heptane 19.200 parts by mass (SP value ( ⁇ ): 15.3, ( ⁇ D ): 15.3, ( ⁇ P ): 0.0, ( ⁇ H ): 0.0) (A) -1 0.196 parts by mass (b) -2 3.726 parts by mass (c) -1 0.078 parts by mass
• Example 14 Normal heptane in the release layer forming composition is cyclohexane (SP value ( ⁇ ): 16.8, ( ⁇ D ): 16.8, ( ⁇ P ): 0.0, ( ⁇ H ): 0.2).
• a release film for molding a resin sheet was obtained in the same manner as in Example 2 except that the film was changed to.
• Example 15 A release film for molding a resin sheet was obtained by the same method as in Example 2 except that the coating amount and the solid content ratio were changed to those shown in Table 1. At this time, the organic solvent ratio was adjusted to be the same as that of the release layer forming composition 3.
• Example 17 A release film for molding an ultrathin layer resin sheet was obtained by the same method as in Example 1 except that the release layer forming composition 5 having the following composition was used.
• Composition for forming a release layer 5 Methyl ethyl ketone 24.950 parts by mass (SP value ( ⁇ ): 19.1, ( ⁇ D ): 16.0, ( ⁇ P ): 9.0, ( ⁇ H ): 5.1) Toluene 24.950 parts by mass (SP value ( ⁇ ): 18.2, ( ⁇ D ): 18.0, ( ⁇ P ): 1.4, ( ⁇ H ): 2.0) Normal heptane 49.900 parts by mass (SP value ( ⁇ ): 15.3, ( ⁇ D ): 15.3, ( ⁇ P ): 0.0, ( ⁇ H ): 0.0) (A) -1 0.196 parts by mass (c) -1 0.004 parts by mass
• Example 18 Mold release for resin sheet molding by the same method as in Example 1 except that the solid content concentration is changed to that shown in Table 1 and the organic solvent ratio is adjusted to be the same as that of the release layer forming composition 5. I got a film.
• Example 19 A release film for molding a resin sheet was obtained by the same method as in Example 17 except that the manufacturing method was changed to that shown in Table 1.
• Example 20 A mold release film for molding an ultrathin layer resin sheet was obtained by the same method as in Example 1 except that the composition was changed to the release layer forming composition 6.
• Composition for forming a release layer 6 Methyl ethyl ketone 39.920 parts by mass (SP value ( ⁇ ): 19.1, ( ⁇ D ): 16.0, ( ⁇ P ): 9.0, ( ⁇ H ): 5.1) Toluene 39.920 parts by mass (SP value ( ⁇ ): 19.1, ( ⁇ D ): 16.0, ( ⁇ P ): 9.0, ( ⁇ H ): 5.1) Normal heptane 19.960 parts by mass (SP value ( ⁇ ): 15.3, ( ⁇ D ): 15.3, ( ⁇ P ): 0.0, ( ⁇ H ): 0.0) (A) -1 0.196 parts by mass (c) -1 0.004 parts by mass
• Example 21 The normal heptane in the release layer forming composition 5 is cyclohexane (SP value ( ⁇ ): 16.8, ( ⁇ D ): 16.8, ( ⁇ P ): 0.0, ( ⁇ H ): 0.2. ) was obtained, and a release film for molding a resin sheet was obtained in the same manner as in Example 1.
• Example 22 A release film for molding a resin sheet was obtained in the same manner as in Example 17 except that the coating amount and solid content concentration were changed to those shown in Table 1. At this time, the organic solvent ratio was adjusted to be the same as that of the release layer forming composition 5.
• Comparative Example 1 since the cationically cured polydimethylsiloxane (a) was not contained, the peeling force of the ceramic sheet was large and it was impossible to peel the ceramic sheet.
• Comparative Examples 2 to 4 the number of protrusions having a height of 10 nm or more exceeded 200 pieces / mm 2 , and pinholes were generated in the green sheet which is a release type. Further, in Comparative Example 4, inorganic particles were present in the entire base material, the smoothness of the release film was remarkably poor, and the green sheet was damaged, pinholes and the like occurred.
• a release film capable of molding a resin sheet having few defects even in an ultrathin layer product having a thickness of 1 ⁇ m or less can be provided to obtain a resin sheet. It can be manufactured without the risk of defects.

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