JP6414424B2 - Release film for ceramic sheet production - Google Patents

Description

  The present invention relates to a release film for producing an ultra-thin layer ceramic sheet, and more specifically, it is possible to produce an ultra-thin layer ceramic sheet capable of suppressing the occurrence of process defects due to pinholes and thickness unevenness during production. The present invention relates to a release film for producing a thin ceramic sheet.

  Conventionally, a release film in which a polyester film is used as a base material and a release layer is laminated thereon is used for molding ceramic sheets such as laminated ceramic capacitors and ceramic substrates. In recent years, with the reduction in size and increase in capacity of multilayer ceramic capacitors, the thickness of the ceramic sheet tends to be reduced. Therefore, when molding a ceramic sheet on the surface of the release layer of the polyester film, there is a problem that minute projections on the surface of the release layer affect the molded ceramic sheet, and defects such as repelling and pinholes are likely to occur. there were. Therefore, various techniques for realizing a release layer surface having excellent flatness have been developed.

  However, in recent years, further thinning of ceramic sheets has progressed, and a ceramic sheet having a thickness of 1.0 μm or less, more specifically 0.2 μm to 1.0 μm, has been required. Therefore, no matter how flat the release layer surface is, the protrusion on the opposite side of the release layer affects the wound ceramic sheet during winding after applying the ceramic sheet, resulting in poor thickness and pinhole defects. A problem has arisen. For this reason, high flatness is required not only on the surface of the release layer but also on the opposite surface of the release layer, but not only on the surface of the release layer but also on the opposite surface of the release layer. In addition, there is a problem in that the slipperiness and the air release property are lowered, and the wrinkles and flatness are lowered when the release film roll is formed. Moreover, when slipperiness fell, there also existed a problem that the slipperiness with respect to the conveyance roll in a release film manufacturing process or a ceramic sheet manufacturing process fell, and it was inferior to handling property.

  Therefore, as a study for flattening the opposite surface of the release layer, a release film in which the surface of the release layer and the protrusions on the opposite surface are controlled by controlling particles in the polyester base material has been proposed (Patent Document). 1 and 2). However, in this method, the maximum protrusion may become large due to the aggregation of particles, and in the process of manufacturing a ceramic sheet with a thinner film, it may be impossible to completely eliminate defects such as pinholes.

  Further, a method has been proposed in which handling properties are not lowered even if particles are contained in the release layer and the surface opposite to the release layer is smoothed (see Patent Document 3). Furthermore, as a method for achieving both handling properties and smoothness, after creating a smooth release layer on a polyester base material that does not contain particles, a resin layer is applied to the opposite side of the release layer, A method has been proposed in which a phase separation phenomenon is used to make unevenness only with a resin layer (see Patent Document 4).

  However, according to the method described in Patent Document 3, moderate protrusions can be provided on the surface by the filler, but there are problems of generation of coarse protrusions due to aggregation of particles and process contamination due to particle falling off. . On the other hand, when the method described in Patent Document 4 is used, since neither the base material nor the coating layer contains filler, the problem of coarse protrusion does not occur, but the unevenness is controlled by utilizing the phase separation phenomenon of the resin. For this reason, the unevenness is insufficient, the slipping property is deteriorated, and the handling property may be lowered.

  Therefore, a film roll made of a film as described in Patent Document 3 or Patent Document 4 is poor in slipperiness and does not have enough air to escape. Over time, the flatness may deteriorate and the smoothness may be lost due to the occurrence of band-like wrinkles.

JP 2007-62179 A JP 2014-12372 A JP 2010-69868 A JP2013-60555A

  The present invention has been obtained as a result of intensive studies in view of the above circumstances, and has excellent handling properties without substantially causing defects such as thickness defects and pinholes during the production of ultra-thin ceramic sheets. An object of the present invention is to provide a release film for producing an ultra-thin ceramic sheet.

  As a result of intensive studies to solve the above problems, the inventors of the present invention further used a polyester film with a controlled surface roughness, and provided a release coating layer on one side and a smoothing coating layer on the other surface. High-order surface roughness and slipperiness can be controlled, and defects such as defective thickness and pinholes are not substantially generated during the production of an ultra-thin ceramic sheet having a thickness of 0.2 to 1.0 μm. It has been found that an ultra-thin layer release film for producing a ceramic sheet having excellent handling properties can be provided.

That is, the present invention has the following configuration.
1. A biaxially oriented polyester film composed of two or more layers is used as a base material, and the base material has a surface layer A substantially free of particles and a surface layer B containing particles, on the surface of the surface layer A A release coating layer is laminated on the surface layer B, and a smoothing coating layer is laminated on the surface of the surface layer B. The smoothing coating layer contains a slippery resin and a crosslinking agent, and the slippery resin is a silicone graft acrylic. A ceramic sheet characterized in that it is a resin, the cross-linking agent is isocyanate or carbodiimide, the surface average roughness (Sa) of the smoothing coating layer is 5 nm or more and 25 nm or less, and the maximum protrusion height (P) is 800 nm or less. Release film for manufacturing.
(However, the slippery resin refers to one having a surface free energy γs of 25 mN / m or less when laminated on a polyester film.)
2. The ceramic sheet production according to the first aspect, wherein the particles contained in the surface layer B are silica particles and / or calcium carbonate particles, and the total amount of the particles is contained in the surface layer B at 5000 to 15000 ppm. Release film.
3. 3. The mold release for producing a ceramic sheet according to the first or second aspect, wherein the average surface roughness (Sa) of the release coating layer of the release film is 5 nm or less and the maximum protrusion height is 30 nm or less. the film.
4). The static friction coefficient μs when the release coating layer and the smoothing coating layer of the release film are overlapped is 0.1 or more and 2.0 or less, according to any one of the first to third aspects. Release film for manufacturing ceramic sheets.
5. It produces using the release film for ceramic sheet manufacture in any one of the said 1st- 4th , The manufacturing method of the ceramic sheet characterized by the above-mentioned.
6). The method for producing a ceramic sheet according to the fifth aspect, wherein the ceramic sheet has a thickness of 0.2 μm to 1.0 μm.
7). Method for manufacturing a ceramic capacitor, characterized in that there use a method for producing a ceramic sheet according to the fifth or sixth.

  The release film for producing an ultra-thin ceramic sheet according to the present invention has a higher flatness on the surface of the release layer compared to a conventional release film for producing a ceramic sheet, and further provides flatness and handling properties on the opposite surface. Therefore, an ultrathin layer ceramic sheet can be produced without substantially causing defects such as defective thickness and pinholes at the time of producing a 0.2 to 1.0 μm ultrathin layer ceramic sheet. Furthermore, since the roll using the release film of the present invention has a good winding shape with the passage of time after the film roll is formed, it is possible to maintain good handling properties during the production of the ultra-thin ceramic sheet.

  Hereinafter, the present invention will be described in detail.

  The base film constituting the release film for producing an ultrathin ceramic sheet according to the present invention is a biaxial film composed of at least two layers having a surface layer A substantially free of particles and a surface layer B containing particles. It is an oriented polyester film, in which a release layer is laminated on the surface layer A, and a smoothing coating layer is provided on the surface layer B.

  The static friction coefficient μs between the release layer and the smoothing coating layer of the release film for producing the ultrathin ceramic sheet of the present invention is preferably 0.1 or more and 2.0 or less. If μs is 2.0 or less, the slipperiness is good, wrinkles are not generated when the film is wound on a roll, the flatness is good, and it can be suitably used for molding a ceramic sheet. Further, if μs is 0.1 or more, the slipperiness is not too high, and it is preferable that no deviation occurs when it is wound on a roll.

(Polyester film)
The polyester constituting the biaxially oriented polyester film used as the base material of the present invention is not particularly limited, and it is possible to use a film-molded polyester that is generally used as a release film base material. Is preferably 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 having a resin component as a main component is more preferable, and a polyester film formed from polyethylene terephthalate is particularly preferable. 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 a small amount, but from the viewpoint of cost. Those produced only from terephthalic acid and ethylene glycol are preferred. Moreover, you may add a well-known additive, for example, antioxidant, a light stabilizer, a ultraviolet absorber, a crystallizing agent, etc. within the range which does not inhibit the effect of the film of this invention.

  The intrinsic viscosity of the polyethylene terephthalate film is preferably 0.50 to 0.70 dl / g, and more preferably 0.52 to 0.62 dl / g. When the intrinsic viscosity is 0.50 dl / g or more, it is preferable because many breakage does not occur in the stretching process. On the other hand, when it is 0.70 dl / g or less, it is preferable because cutting property when cutting to a predetermined product width is good and dimensional defects do not occur. Moreover, it is preferable that the raw material is sufficiently vacuum-dried.

  The production method of the biaxially oriented polyester film in the present invention is not particularly limited, and a conventionally used method can be used. For example, the polyester can be melted with an extruder, extruded into a film, cooled with a rotary cooling drum to obtain an unstretched film, and the unstretched film can be obtained by biaxial stretching. A biaxially stretched film can be obtained by a method of sequentially biaxially stretching a uniaxially stretched film in the longitudinal direction or the transverse direction in the transverse direction or the longitudinal direction, or a method of simultaneously biaxially stretching an unstretched film in the longitudinal direction and the transverse direction. I can do it.

  In this invention, it is preferable that the extending | stretching temperature at the time of extending | stretching a polyester film shall be more than the secondary transition point (Tg) of polyester. It is preferable to stretch 1 to 8 times, particularly 2 to 6 times in the longitudinal and lateral directions.

  The polyester film preferably has a thickness of 12 to 50 μm, more preferably 15 to 38 μm. If the thickness of the film is 12 μm or more, it is preferable that there is no risk of deformation due to heat during film production, processing steps, and molding. On the other hand, if the thickness of the film is 50 μm or less, the amount of the film discarded after use is not extremely increased, which is preferable in reducing the environmental load.

  The biaxially oriented polyester film substrate is preferably a laminated polyester film having a multilayer structure of at least two layers. This polyester film has at least a surface layer A substantially free of particles and a surface layer B containing particles. The layer on the side to which the release layer is applied is the A layer, and the smoothing coating layer on the opposite side If the layer on the side to be coated is B layer and the core layer other than these is C layer, the layer structure in the thickness direction is release layer / A / B / smoothing coating layer or release layer / A / C / B / Laminated structure such as a smoothing coating layer. Of course, the C layer may have a plurality of layers.

  In the biaxially oriented polyester film substrate of the present invention, it is preferable that the surface layer A forming the surface on which the release layer is applied does not substantially contain particles. At this time, the area surface average roughness (Sa) of the surface layer A is preferably 7 nm or less. When Sa is 7 nm or less, pinholes and the like are less likely to occur during the formation of the laminated ultrathin ceramic sheet. Although it can be said that the region surface average roughness (Sa) of the surface layer A is preferably as small as possible, it may be 0.1 nm or more. This “substantially free of particles” means, for example, in the case of inorganic particles, a content that is 50 ppm or less, preferably 10 ppm or less, most preferably the detection limit or less when inorganic elements are quantified by fluorescent X-ray analysis. Means. This means that even if particles are not actively added to the film, contaminants derived from foreign substances, raw resin, or dirt adhering to the lines and equipment in the film manufacturing process may be peeled off and mixed into the film. Because there is.

  In the biaxially oriented polyester film substrate of the present invention, the surface layer B forming the surface opposite to the surface on which the release layer is applied may contain particles from the viewpoint of film slipperiness and ease of air removal. In particular, it is preferable to use silica particles and / or calcium carbonate particles. The contained particle content is preferably 5000 to 15000 ppm in total 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 20-40 nm. When the total of silica particles and / or calcium carbonate particles is 5000 ppm or more and Sa is 20 nm or more, when the film is rolled up, air can be released uniformly, and the winding shape is good and the flatness is good. This is suitable for the production of an ultrathin layer ceramic sheet. In addition, when the total of silica particles and / or calcium carbonate particles is 15000 ppm or less and Sa is 40 nm or less, the aggregation of the lubricant is difficult to occur and coarse protrusions cannot be formed. preferable.

  As the particles contained in the layer B, inactive inorganic particles and / or heat-resistant organic particles other than silica and / or calcium carbonate can be used. From the viewpoint of transparency and cost, silica particles and / or Although it is more preferable to use calcium carbonate particles, other usable inorganic particles 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. 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 polymer compound is preferable from the viewpoint of preventing the lubricant from falling off. .

  The average particle size of the particles added to the surface layer B is preferably 0.1 μm or more and 2.0 μm or less, and particularly preferably 0.5 μm or more and 1.0 μm or less. If the average particle diameter of the particles is 0.1 μm or more, the slipping property of the release layer is good, which is preferable. Moreover, if an average particle diameter is 2.0 micrometers or less, there is no possibility that the pinhole by a coarse particle may generate | occur | produce on the mold release layer surface, and it is preferable.

  The surface layer B may contain two or more kinds of particles having different materials. Moreover, you may contain the same kind of particle | grains from which an average particle diameter differs.

  From the viewpoint of reducing pinholes, it is preferable not to use a regenerated raw material or the like for the surface layer A, which is a layer on the side where the release layer is provided, from the viewpoint of reducing pinholes.

  The thickness ratio of the surface layer A, which is the layer on the side where the release layer is provided, is preferably 20% to 50% of the total thickness of the base film. If it is 20% or more, the influence of particles contained in the surface layer B or the like is not easily received from the inside of the film, and the area surface average roughness Sa is easy to satisfy the above range, which is preferable. When the thickness is 50% or less of the total thickness of the base film, the use ratio of the recycled raw material in the surface layer B can be increased, and the environmental load is small.

  Further, from the viewpoint of economy, 50 to 90% by mass of film scraps and recycled materials for PET bottles can be used for layers other than the surface layer A (surface layer B or the aforementioned intermediate layer C). Even in this case, it is preferable that the type and amount of the lubricant contained in the B layer, the particle diameter, and the area surface average roughness (Sa) satisfy the above range.

  In addition, the surface layer A and / or the surface layer B may be applied to the surface of the surface layer A and / or the surface layer B before stretching in the film forming process in order to improve adhesion with a release layer or a smoothing coating layer to be applied later, or to prevent charging. A coat layer may be provided on the film after uniaxial stretching. Corona treatment can also be applied.

(Release coating layer)
The resin constituting the release coating layer in the present invention is not particularly limited, and silicone resins, fluororesins, alkyd resins, various waxes, aliphatic olefins and the like can be used, and each resin can be used alone or in combination of two or more. You can also

  As the release coating layer of the present invention, for example, a silicone resin is a resin having a silicone structure in the molecule, and examples thereof include a curable silicone, a silicone graft resin, and a modified silicone resin such as alkyl modification. It is preferable to use a reactive cured silicone resin from the viewpoint of properties. As the reactive cured silicone resin, an addition reaction type, a condensation reaction type, an ultraviolet ray or electron beam curing type, or the like can be used. More preferably, a low-temperature curable addition reaction system that can be processed at a low temperature, and an ultraviolet ray or electron beam curing system are preferable. By using these materials, the polyester film can be processed at a low temperature. Therefore, there is little thermal damage to the polyester film during processing, a polyester film with high flatness is obtained, and a ceramic sheet with few defects such as pinholes even when manufacturing an ultra-thin ceramic sheet with a thickness of 0.2 to 1.0 μm Can be obtained.

  Examples of the addition reaction type silicone resin include those obtained by reacting and curing polydimethylsiloxane having a vinyl group introduced into the terminal or side chain thereof with hydrodienesiloxane using a platinum catalyst. At this time, it is more preferable to use a resin that can be cured at 120 ° C. within 30 seconds because processing at a low temperature is possible. As an example, low temperature addition curing type (LTC1006L, LTC1056L, LTC300B, LTC303E, LTC310, LTC314, LTC350G, LTC450A, LTC371G, LTC750A, LTC755A, LTC85A, and the like, and LTC760A) manufactured by Toray Dow Corning Co., Ltd. BY24-510, BY24-561, BY24-562, etc.), Shin-Etsu Chemical Co., Ltd. solvent addition + UV curing type (X62-5040, X62-5065, X62-5072T, KS5508, etc.), dual cure curing type (X62-2835, X62-2834, X62-1980, etc.).

  As a silicone resin of the condensation reaction system, for example, a polydimethylsiloxane having an OH group at the end and a polydimethylsiloxane having an H group at the end are subjected to a condensation reaction using an organotin catalyst to form a three-dimensional crosslinked structure. Can be mentioned.

  Examples of UV curable silicone resins include those that use the same radical reaction as ordinary silicone rubber crosslinks as the most basic types, those that introduce photopolymerization by introducing unsaturated groups, and those that decompose onium salts with UV light. Examples include those that generate a strong acid and then cleave the epoxy group to crosslink, and those that crosslink by the addition reaction of thiol to vinylsiloxane. Further, an electron beam can be used instead of the ultraviolet rays. Electron beams have stronger energy than ultraviolet rays, and can use a radical crosslinking reaction without using an initiator as in the case of ultraviolet curing. Examples of the resin used include UV curable silicones (X62-7028A / B, X62-7052, X62-7205, X62-7622, X62-7629, X62-7660, etc.) manufactured by Shin-Etsu Chemical, Momentive Performance UV curable silicones manufactured by Materials (TPR6502, TPR6501, TPR6500, UV9300, UV9315, XS56-A2982, UV9430, etc.), UV curable silicones manufactured by Arakawa Chemical (Silicolys UV POLY200, POLY215, POLY201, KF-UV265AM, etc.) ).

  As the ultraviolet curable silicone resin, polydimethylsiloxane modified with acrylate or glycidoxy may be used. Mixing these modified polydimethylsiloxanes with polyfunctional acrylate resins or epoxy resins and using them in the presence of an initiator can also provide good release performance.

  Other examples of resins that can be used are stearyl-modified alkyd resins and alkyd resins obtained by the reaction of methylated melamine.

  When using the said resin for the mold release coating layer of this invention, it may be used by 1 type and may be used in mixture of 2 or more types. Moreover, in order to adjust peeling force, it is also possible to mix additives, such as a light peeling additive and a heavy peeling additive.

  The release coating layer of the present invention can contain particles having a particle size of 1 μm or less, but it is preferable not to contain particles that form protrusions from the viewpoint of generating pinholes.

  You may add additives, such as a contact | adherence improving agent and an antistatic agent, to the mold release coating layer of this invention. In order to improve the adhesion to the substrate, it is also preferable that the polyester film surface is subjected to pretreatment such as anchor coating, corona treatment, plasma treatment, atmospheric pressure plasma treatment, etc. before providing the release coating layer.

In the present invention, the thickness of the release coating layer may be set according to the purpose of use and is not particularly limited, but preferably the weight of the release coating layer after curing is 0.01 to 0.5 g / m ^2. The range is good. If the thickness of the release layer is smaller than the above range, the peeling performance tends to be lowered. Moreover, when larger than the said range, hardening time will become long and there exists a possibility that the thickness nonuniformity of the ceramic sheet | seat by the fall of the planarity of a release film may arise easily. In addition, when the curing time becomes long, the resin constituting the release layer is likely to aggregate, forming protrusions, which may cause a pinhole defect of the ceramic sheet.

  The surface of the film on which the release coating layer is formed is preferably flat so as not to cause defects in the ceramic sheet to be coated / molded thereon, and the area surface average roughness (Sa) is 5 nm or less and the maximum protrusion. The height (P) is preferably 30 nm or less. More preferably, the area surface average roughness is 5 nm or less and the maximum protrusion height is 20 nm or less. If the surface roughness of the region is 5 nm or less and the maximum protrusion height is 30 nm or less, there is no occurrence of defects such as pinholes when forming the ceramic sheet, and the yield is favorable. The smaller the surface average surface roughness (Sa), the better. However, it may be 0.1 nm or more, or 0.3 nm or more. It can be said that the smaller the maximum protrusion height (P) is, the better, but it may be 1 nm or more, or 3 nm or more.

  In the present invention, the method for forming the release coating layer is not particularly limited, and a coating solution in which a release resin is dissolved or dispersed is spread on one surface of the polyester film of the substrate by coating or the like, Etc. are removed by drying, followed by heat drying, heat curing or ultraviolet curing. At this time, the drying temperature at the time of solvent drying and thermosetting is preferably 180 ° C. or less, more preferably 150 ° C. or less, and most preferably 120 ° C. or less. The heating time is preferably 30 seconds or less, and more preferably 20 seconds or less. When the temperature is 180 ° C. or lower, the flatness of the film is maintained, and the possibility of causing uneven thickness of the ceramic sheet is small and preferable. When the temperature is 120 ° C. or lower, the film can be processed without impairing the flatness of the film, and the possibility of causing uneven thickness of the ceramic sheet is further reduced, which is particularly preferable.

  In the present invention, the surface tension of the coating liquid when applying the release coating layer is not particularly limited, but is preferably 30 mN / m or less. By making the surface tension as described above, the paintability after coating can be improved, and the unevenness of the coating film surface after drying can be reduced.

  In the present invention, the coating liquid for applying the release coating layer is not particularly limited, but it is preferable to add a solvent having a boiling point of 90 ° C. or higher. By adding a solvent having a boiling point of 90 ° C. or higher, bumping during drying can be prevented, the coating film can be leveled, and the smoothness of the coating film surface after drying can be improved. As the addition amount, it is preferable to add about 10-80 mass% with respect to the whole coating liquid.

  As the coating method of the coating liquid, any known coating method can be applied, for example, a roll coating method such as a gravure coating method or a reverse coating method, a bar coating method such as a wire bar, a die coating method, a spray coating method, an air knife. Conventionally known methods such as a coating method can be used.

(Smoothing coating layer)
In the release film of the present invention, a smoothing coating layer is provided on the surface layer B.
By further providing a smoothing coating layer on the surface layer B in which the area surface average roughness is controlled, the area surface average roughness and the maximum protrusion height can be controlled to a higher degree. Therefore, even after a 0.2-1.0 μm ultra-thin ceramic sheet is formed into a release coating layer and wound into a roll, there is no uneven transfer of the smoothing coating layer and pinholes in the ultra-thin ceramic sheet Etc. can be suppressed.

  The average surface roughness (Sa) of the smoothing coating layer in the present invention is preferably 5 nm or more and 25 nm or less, and the maximum protrusion height (P) is preferably 800 nm or less. More preferably, the region surface average roughness (Sa) is 7 nm or more and 23 nm or less, the maximum protrusion height (P) is 750 nm or less, Sa is 10 nm or more and 20 nm or less, and P is 700 nm or less. If the surface roughness of the region (Sa) is 5 nm or more, it is preferable because the slipping property is good and the flatness is maintained without causing wrinkles or the like during winding. On the other hand, when the area surface average roughness (Sa) is 25 nm or less and the maximum protrusion height (P) is 800 nm or less, in the winding after the ceramic sheet application, The unevenness of the protrusions of the smoothing coating layer is not transferred, and this is preferable because there is little possibility of causing defects such as pinholes. The maximum protrusion height (P) is preferably small, but may be 10 nm or more, or 20 nm or more.

  Although the resin which comprises the smoothing application layer in this invention is not specifically limited, A polyester resin, an acrylic resin, a polyurethane resin, a silicone resin, a fluorine resin etc. can be used. These resins may be used alone or in combination of two or more.

  For part of the resin constituting the smoothing coating layer, it is preferable to use a slippery resin in order to maintain slipperiness even on a highly smooth surface. The slippery resin refers to a resin layer having a surface free energy γs of 25 mN / m or less after being dried and / or cured after being applied on a polyester film. Examples thereof include silicone resins and fluorine resins. And long-chain alkyl-modified resins.

  The ratio of the slippery resin in the resin in the smoothing coating layer of the present invention is not particularly limited, but it is preferably 1% by mass to 100% by mass. The effect of improving slipperiness can be expected from 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% or more. Of course, the upper limit is 100% by mass.

  Examples of the silicone resin used as the slippery resin in the present invention include curable silicone, silicone graft acrylic resin, epoxy-modified silicone, acrylate-modified silicone, amino-modified silicone and the like.

  Examples of the fluororesin used as the slippery resin in the present invention include a resin grafted with a perfluoroalkyl group and a resin copolymerized with an olefin compound having a fluorine atom.

  An example of a long-chain alkyl-modified resin used as a slippery resin in the present invention is a polymer having (meth) acrylic acid ester as a main repeating unit, and the transesterified portion has 12 to 30 carbon atoms. And a resin having a long-chain alkyl group.

  The number average molecular weight Mn of the resin used for the smoothing coating layer of the present invention is preferably 250 to 20,000. More preferably, it is 300-15000, More preferably, it is 500-10000. When the number average molecular weight is 20000 or less, the fluidity at the time of applying the surface layer B is good and the leveling property is good, so that the unevenness can be effectively filled and the surface roughness of the region can be easily within the above range. It is preferable. Further, when the number average molecular weight Mn is 250 or more, the resin is less likely to aggregate during drying and coarse protrusions are not generated.

  The thickness of the smoothing coating layer of the present invention is preferably 0.2 to 2.0 μm, more preferably 0.3 to 1.5 μm. When the thickness is 0.2 μm or more, it is easy to fill the irregularities of the B layer, and it is easy to make the maximum height within the above range, which is preferable. Moreover, if thickness is 2.0 micrometers or less, since smoothness does not improve too much and slipperiness can be satisfied, it is preferable.

  The surface free energy γs of the smoothing coating layer of the present invention is preferably 30 mN / m or less, more preferably 23 mN / m or less. Thereby, even a highly smoothed polyester film can prevent deterioration of slipperiness with respect to the transport roll in the production process of the release polyester film and the ceramic sheet production process, and can prevent wrinkles and blocking. However, if the surface free energy γs of the smoothing coating layer is too small, there is a risk that winding will be lost when the film is wound into a roll. Therefore, the lower limit is preferably 12 mN / m or more.

  It is also preferable to add a crosslinking agent to the coating layer of the present invention as necessary. By adding a crosslinking agent, the solvent resistance and migration of the smoothing coating layer can be suppressed. The type of the crosslinking agent that can be added is not particularly limited, and isocyanate-based, carbodiimide-based, epoxy-based, melamine-based, oxazoline-based, and the like can be used.

  For example, when a silicone graft acrylic resin is used for the smoothing coating layer of the present invention, by using isocyanate or carbodiimide as a cross-linking agent, the silicone graft acrylic resin moves to the release layer, and the release layer is peelable. This is preferable because it can suppress the possibility of adversely affecting the above.

  It is preferable that a part of the resin constituting the smoothing coating layer of the present invention contains the same charge train as the resin used in the release layer. For example, when a silicone resin is used for the release layer, it is preferable that the coating layer also contains a silicone resin. By mixing the resins of the same charge series, charging at the time of contact can be suppressed, and peeling charge when the film is unwound from the film roll can be reduced.

  The processing method of the smoothing coating layer in the present invention is not particularly limited, but the smoothing coating layer can be processed by a method of processing both sides simultaneously with the release coating layer or a method of processing the opposite surface after processing one surface. In the latter case, it is preferable to process the coating layer after processing the release layer. Since the release layer is formed by laminating a ceramic sheet layer, the release layer needs to be more uniform than the coating layer. For this reason, when the release layer is applied, if the slipperiness of the opposite surface of the release layer is better, wrinkles and the like are less likely to enter during application, and the coating can be applied more uniformly.

  Moreover, it is preferable to process the smoothing coating layer not by an in-line coating applied at the time of forming a polyester film but by an off-line coating processed after forming a polyester film. The off-line method can control the tension at the time of coating and the tension at the time of winding highly, so that both smoothness and slipperiness can be achieved at a high level.

  As the coating method of the coating liquid, any known coating method can be applied, for example, a roll coating method such as a gravure coating method or a reverse coating method, a bar coating method such as a wire bar, a spray coating method, an air knife coating method, etc. Conventionally known methods can be used.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. The characteristic values used in the present invention were evaluated using the following methods. In addition, the following Examples 1-7, 10 and 11 shall be read as Reference Examples 1-7, 10 and 11, respectively.

(Surface roughness)
It is the value measured on condition of the following using non-contact surface shape measurement system (VertScan R550H-M100). For the area surface average roughness (Sa), an average value of five measurements was adopted, and for the maximum protrusion height (P), a maximum value of five measurements was adopted.
(Measurement condition)
・ Measurement mode: WAVE mode ・ Objective lens: 50 × ・ 0.5 × Tube lens ・ Measurement area 187 × 139 μm

(Static friction coefficient)
The sample film was cut out from the release film roll into an area of 8 cm × 5 cm. This was fixed on the bottom of a metal rectangular parallelepiped having a size of 6 cm × 5 cm and having a weight of 1.4 kg so that the smoothing coating layer appeared on the surface. At this time, the 5 cm width direction of the sample film and the 5 cm width direction of the metal cuboid were matched, one side in the longitudinal direction of the sample film was bent, and fixed to the side surface of the metal cuboid with an adhesive tape.

Next, a sample film was cut out to an area of 20 cm × 10 cm from the same release film roll, and the end in the longitudinal direction was fixed on a flat metal plate with an adhesive tape so that the surface of the release layer appeared on the surface. The measurement surface of the metal rectangular parallelepiped on which the sample film was adhered was placed in contact with this, and the static friction coefficient (μs) was measured under the conditions of a pulling speed of 200 mm / min, 23 ° C. and 65% RH.
The slip property was judged according to the following criteria.
○: 0.1 <μs <1.5
Δ: 1.5 <μs <2.5
×: The coefficient of friction is too high to measure

(Surface free energy)
Contact angles: θw and θy of water having a known surface tension and methylene iodide to the film or resin described in the present invention were measured using a contact angle meter (Kyowa Interface Science Co., Ltd .: CA-X type), 25 The measurement was performed under the conditions of ° C and 50% RH. Using these measured values, the surface tension γs of the film or resin described in the present invention was calculated as follows.

The surface free energy γs is the sum of the dispersive component γsd and the polar component γsp. That is,
γs = γsd + γsp (Formula 1)
From Young's formula,
γs = γsw + γw × cosθw (Formula 2)
γs = γsy + γy × cosθy (Formula 3)
Where γsw is the tension acting between the film or resin and water, γsw is the tension acting between the film or resin and methylene iodide, γw is the surface tension of water, and γy is the surface tension of methylene iodide. .
From the Fowkes equation,
γsw = γs + γw−2 × (γsd × γwd) 1 / 2−2 × (γsp × γwp) 1/2 (Formula 4)
γsy = γs + γy−2 × (γsd × γyd) 1 / 2−2 × (γsp × γyp) 1/2 (Formula 5)
It is. Where γwd is the dispersive component of the surface tension of water, γwp is the polar component of the surface tension of water, γyd is the dispersible component of the surface tension of methylene iodide, and γyp is the polar component of the surface tension of methylene iodide. .
The surface tension γs = γsd + γsp of the film or resin can be calculated by solving the simultaneous equations of Formulas 1 to 5. At this time, the surface tension (γw) of water is 72.8 dyne / cm, the surface tension (γy) of methylene iodide is 50.5 dyne / cm, and the dispersive component (γwd) of the surface tension of water is 21.8 dyne / cm. The polar component (γwp) of the surface tension of water is 51.0 dyne / cm, the dispersive component (γyd) of the surface tension of methylene iodide is 49.5 dyne / cm, and the polar component of the surface tension of methylene iodide (γyp) Used 1.3 dyne / cm.

(Ceramic green sheet pinhole evaluation)
The composition consisting of the following materials was stirred and mixed, and dispersed for 2 hours using a paint shaker using 2.0 mm glass beads as a dispersion medium to obtain a ceramic slurry.
Toluene 22.5% by mass
Ethanol 22.5% by mass
Barium titanate (HPBT-1 manufactured by Fuji Titanium) 50% by mass
Polyvinyl butyral (Sekisui Chemical Co., Ltd. S-REC BH-3) 5% by mass
Next, using an applicator on the release surface of the obtained release film sample, the slurry after drying was applied to a thickness of 1 μm, dried at 90 ° C. for 1 minute, and then the slurry surface and the smoothing coating layer surface were overlaid, After applying a load of 1 kg / cm ² for 10 minutes, 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 applied from the opposite side of the ceramic slurry coating surface within a range of 25 cm ² , and the occurrence of pinholes through which light was transmitted was observed. Visual judgment was made.
○: No occurrence of pinholes △: Almost no occurrence of pinholes ×: Many occurrences of pinholes

(Solvent resistance)
Evaluation was made from the change in appearance when the smoothing coating layer of the film of the present invention was rubbed with a cotton swab in which a solvent of toluene / ethanol = 1/1 was attached.
○: No change in appearance △: Some change in appearance (whitening)
×: Appearance changed significantly (whitening)

(Evaluation of migration of smoothing coating layer)
The smoothing coating layer of the film of the present invention is superposed on an untreated PET film, a weight of 1 kg / cm ² is applied for 10 minutes, and then the silicone component transferred to the untreated PET film is repelled by a magic pen. It was evaluated with. Evaluation criteria were visually judged as follows.
○: Magic pen does not play at all △: Magic pen plays a little ×: Magic pen plays remarkably

(Preparation of polyethylene terephthalate pellets (PET))
As the esterification reaction apparatus, a continuous esterification reaction apparatus comprising a three-stage complete mixing tank having a stirrer, a partial condenser, a raw material charging port and a product outlet was used. TPA (terephthalic acid) is 2 tons / hour, EG (ethylene glycol) is 2 moles per mole of TPA, antimony trioxide is made into an amount that makes Sb atoms 160 ppm with respect to the produced PET, and these slurries are esterified. Was continuously supplied to the first esterification reactor of the chemical reaction apparatus, and allowed to react at 255 ° C. at an average residence time of 4 hours at normal pressure. Next, the reaction product in the first esterification reaction can is continuously taken out of the system and supplied to the second esterification reaction can, and is distilled off from the first esterification reaction can in the second esterification reaction can. EG solution containing 8 mass% of EG with respect to the generated PET, and further containing EG solution containing magnesium acetate tetrahydrate in an amount of 65 ppm of Mg atoms relative to the generated PET, and 40 ppm of P atoms relative to the generated PET An EG solution containing a quantity of TMPA (trimethyl phosphate) was added and reacted at 260 ° C. at normal pressure for an average residence time of 1 hour. Next, the reaction product of the second esterification reaction can was continuously taken out of the system and supplied to the third esterification reaction can, and 39 MPa (400 kg / cm ² ) using a high pressure disperser (manufactured by Nippon Seiki Co., Ltd.). An average particle of 0.2 mass% of porous colloidal silica having an average particle diameter of 0.9 μm and an ammonium salt of polyacrylic acid adhered to 1 mass% of calcium carbonate, which was dispersed at an average number of treatments of 5 passes under the pressure of While adding 0.4% by mass of synthetic calcium carbonate having a diameter of 0.6 μm as an EG slurry of 10%, the reaction was carried out at 260 ° C. at an average residence time of 0.5 hours at normal pressure. The esterification reaction product produced in the third esterification reaction can was continuously supplied to a three-stage continuous polycondensation reaction apparatus to perform polycondensation, and sintered with a stainless steel fiber having a 95% cut diameter of 20 μm. After filtering with a filter, ultrafiltration was performed 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 referred to as PET (I)). . The lubricant content in the PET chip was 0.6% by mass.

(Preparation of polyethylene terephthalate pellets (PETII))
On the other hand, in the production of the above PET chip, 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)).

(Manufacture of laminated film X1)
These PET chips were dried, melted at 285 ° C., melted at 290 ° C. with a separate melt extruder extruder, sintered with stainless steel fibers having a 95% cut diameter of 15 μm, and a 95% cut diameter Two-stage filtration of a 15 μm stainless steel particle-sintered filter is performed and merged in the feed block, PET (I) is surface layer B (reverse mold release side layer), and PET (II) is surface Layer A (release surface side layer) is laminated, extruded into a sheet at a speed of 45 m / min (casting), electrostatically contacted and cooled on a 30 ° C. casting drum by electrostatic contact method, An unstretched polyethylene terephthalate sheet having an intrinsic viscosity of 0.59 dl / g was obtained. The layer ratio was adjusted so that PET (I) / (II) = 60% / 40% in the discharge amount calculation of each extruder. Next, this unstretched sheet was heated with an infrared heater, and then stretched 3.5 times in the longitudinal direction at a roll temperature of 80 ° C. due to the speed difference between the rolls. Thereafter, the film was guided to a tenter and stretched 4.2 times in the transverse direction at 140 ° C. Subsequently, it heat-processed at 210 degreeC in the heat setting zone. Thereafter, a relaxation treatment of 2.3% was performed at 170 ° C. in the transverse direction to obtain a biaxially stretched polyethylene terephthalate film X1 having a thickness of 31 μm. Sa of surface layer A of the obtained film X1 was 2 nm, and Sa of surface layer B was 28 nm.

(Formation of release layer Y1)
In Examples 1 to 11 and Comparative Examples 1 to 5 below, 100 parts by mass of UV-curable silicone resin (UV9300 manufactured by Momentive) and 1 part by mass of a curing catalyst bis (alkylphenyl) iodonium hexafluoroantimonate were added to toluene / methyl ethyl ketone / It was diluted with a heptane (= 3: 5: 2) solution to prepare a release agent solution having a solid content of 2% by mass. This releaser solution was applied to the surface layer A containing no particles of the laminated film X1 with a reverse gravure coater so as to have a dry weight of 0.1 g / m ^2, and then dried with hot air at 90 ° C. for 30 seconds. Immediately, ultraviolet irradiation (300 mJ / cm ² ) was performed with an electrodeless lamp (H bulb manufactured by Fusion Co., Ltd.) to form a release layer Y1.

  However, in Comparative Example 2 using E5100 as the substrate film, a release layer was applied to any one side in the same manner as in Example 1, and then the smooth coating layer was applied to the release layer of the substrate. It was applied to the surface opposite to the finished surface.

(Formation of release layer Y2)
In Example 12 below, 100 parts by mass of a heat addition type silicone resin (LTC310 manufactured by Toray Dow Corning) and 2 parts by mass of a curing catalyst (SRX212 manufactured by Toray Dow Corning) were diluted with a toluene / methyl ethyl ketone = 5/5 solution. Then, a release agent solution having a solid content of 2% by mass was prepared. The release agent solution was applied to the surface layer A containing no particles of the laminated film X1 with a reverse gravure coater so as to have a dry weight of 0.1 g / m ^2, and then dried with hot air at 120 ° C. for 30 seconds to release the mold. Layer Y2 was formed.

(Smoothing coating layer)
(Easily slippery resin (1))
(1) -1: Silicone-modified acrylic resin (γs: 18 mN / m, calculation of acrylic skeleton Tg: 120 ° C., acid value: 65 mgKOH / g,)
(1) -2: Modified polydimethylsiloxane having an acrylate group (BYK3505 γs: 19 mN / m, manufactured by BYK Japan)
(1) -3: Alicyclic epoxy-modified silicone resin (γs17 mN / m, UV9430 manufactured by Momentive)

(Resin (2))
(2) -1: Polyester resin (Toyobo's Byron 220, Mn3000)
(2) -2: Polyester resin (Byron 226 Mn8000 manufactured by Toyobo)
(2) -3: Polyester resin (Byron 270 Mn23000, manufactured by Toyobo)
(2) -4: Acrylate compound (manufactured by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol hexaacrylate molecular weight 578)
(2) -5: Epoxy-modified acrylic resin (Tg 100 ° C., Mn 11000)

(Crosslinking agent (3))
(3) -1: Isocyanate-based crosslinking agent (Nippon Polyurethane Industry, Coronate L)
(3) -2: Carbodiimide crosslinking agent (Nisshinbo Chemical, Carbodilite V-05)

(Formation of smoothing coating layer Z1)
Silicone-modified acrylic resin (1) -1 (γs: 18 dyne / cm, acrylic skeleton calculation Tg: 120 ° C., acid value: 65 mg KOH / g) is diluted with a toluene / methyl ethyl ketone (= 1: 1) solution to obtain a solid content. A 10 mass% coating solution z1 was prepared. The coating solution z1 is applied to the opposite surface of the release layer of the laminated film with a reverse gravure coater so that the dry weight is 0.7 g / m ^2, and dried at 120 ° C. for 30 seconds to form the smoothed coating layer C1. Formed.

(Formation of smoothing coating layers Z2 to Z7)
The smoothing coating layers Z2 to Z7 were formed in the same manner as the smoothing coating layer Z1 by adjusting the resin, mixing ratio, and film thickness shown in Table 1.

(Formation of smoothing coating layers Z8 and Z9)
As indicated in Table 1, smoothing coating layers Z8 and Z9 were formed in the same manner as the smoothing coating layer Z1, except that a crosslinking agent was added and dried at 160 ° C. for 30 seconds.

(Formation of smoothing coating layer Z10)
The resins listed in Table 1 were mixed, a photoinitiator (Irgacure 184, manufactured by BASF) was added, and after coating, dried at 90 ° C. for 30 seconds, and then immediately irradiated with an electrodeless lamp (H bulb manufactured by Fusion Corporation). A smoothing coating layer Z10 was formed in the same manner as the smoothing coating layer Z1, except that irradiation (300 mJ / cm ² ) was performed.

(Formation of smoothing coating layer Z11)
A smoothing coating layer Z11 was formed in the same manner as the smoothing coating layer Z10 except that the resins listed in Table 1 were mixed and 1 part by mass of the curing catalyst bis (alkylphenyl) iodonium hexafluoroantimonate was added.

Example 1
After forming the release layer Y1 on the surface layer A of the laminated film X1, a release film for producing an ultrathin layer ceramic sheet was obtained by forming the smoothing coating layer Z1 on the surface layer B.

Examples 2-12
A release film for producing an ultrathin layer ceramic sheet was obtained by the combination shown in Table 1.

Comparative Example 1
A release film for producing an ultrathin layer ceramic sheet was obtained in the same manner as in Example 1 except that the smoothing coating layer was not formed.

Comparative Example 2
A release film for producing an ultrathin layer ceramic sheet was obtained in the same manner as in Example 1 except that the film was changed to E5100-25 μm (manufactured by Toyobo) instead of the laminated film X1. In E5100, both the surface layer A and the surface layer B contained particles, and the Sa of both the surface layer A and the surface layer B was 31 nm.

Comparative Examples 3-5
With the combinations described in Table 1, a release film for producing an ultrathin ceramic sheet was obtained.

  Since the release film for producing a ceramic sheet of the present invention has a higher flatness on the surface of the release layer compared to a conventional release film for producing a ceramic sheet, and also has excellent flatness and handling properties on the opposite surface, It was possible to produce an ultra-thin ceramic sheet without substantially causing defects such as defective thickness and pinholes when producing an ultra-thin ceramic sheet of 0.2 to 1.0 μm. Furthermore, since the film roll using the release film of the present invention has a good winding shape with the passage of time after the film roll is formed, the handling property at the time of producing an ultra-thin ceramic sheet can be kept good.

Claims (7)

A biaxially oriented polyester film composed of two or more layers is used as a base material, and the base material has a surface layer A substantially free of particles and a surface layer B containing particles, on the surface of the surface layer A A release coating layer is laminated on the surface layer B, and a smoothing coating layer is laminated on the surface of the surface layer B. The smoothing coating layer contains a slippery resin and a crosslinking agent, and the slippery resin is a silicone graft acrylic. A ceramic sheet characterized in that it is a resin, the cross-linking agent is isocyanate or carbodiimide, the surface average roughness (Sa) of the smoothing coating layer is 5 nm or more and 25 nm or less, and the maximum protrusion height (P) is 800 nm or less. Release film for manufacturing.
(However, the slippery resin refers to one having a surface free energy γs of 25 mN / m or less when laminated on a polyester film.)   2. The ceramic sheet production according to claim 1, wherein the particles contained in the surface layer B are silica particles and / or calcium carbonate particles, and the total of the particles is contained in the surface layer B at 5000 to 15000 ppm. Release film.   3. The release film for producing a ceramic sheet according to claim 1, wherein an area surface average roughness (Sa) of the release coating layer of the release film is 5 nm or less and a maximum protrusion height is 30 nm or less. . According to any one of claims 1 to 3, static friction coefficient μs when superimposed a release coating layer and smoothing coating layers of the release film is characterized in that 0.1 to 2.0 Release film for ceramic sheet manufacturing. Method for producing a ceramic sheet, characterized by creating with the release film ceramic sheet production according to any one of claims 1-4. The method for producing a ceramic sheet according to claim 5 , wherein the ceramic sheet has a thickness of 0.2 μm to 1.0 μm. Method for manufacturing a ceramic capacitor, characterized in that there use a method for producing a ceramic sheet according to claim 5 or 6.