JP2011206995A - Peeling film, peeling film roll, ceramic component sheet, and method for manufacturing ceramic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a peeling film having a peeling surface combining excellent releasability and applicability and easy to be manufactured, and a peeling film roll.SOLUTION: The peeling film 10 includes a base material film 12 and a polymer layer 14 provided on one surface of the base material film 12. The polymer layer 14 has a layer including cured material of a (meth)acrylate component and a film including a silicone polymer component which covers a part of a surface on the opposite side of the base material film side of the layer 14. The silicone polymer component is a polymer of modified silicone oil modified by a (meth)acryloyl group and/or a vinyl group. On a surface 14a of the polymer layer, surface adhesion energy of water is equal to or less than 10 mJ/m. In the peeling film roll of the winded peeling film, a contact angle of water is equal to or less than 80 degrees on the surface opposite from a polymer layer side of the base material film.

Description

  The present invention relates to a release film, a release film roll, a ceramic component sheet, and a method for manufacturing a ceramic component.

  As a manufacturing process of a multilayer ceramic capacitor which is an example of a ceramic component, a method is known in which a dielectric sheet and an electrode formed on a release film are formed and then peeled and laminated.

  In recent years, multilayer ceramic capacitors have been reduced in size, and the thickness of a dielectric layer obtained by firing a dielectric sheet has been increasingly reduced. In connection with this, the peeling film used for formation of a dielectric sheet is calculated | required to have the surface where the unevenness | corrugation was fully reduced, and to have favorable peelability.

  A release film has been proposed that has a laminated structure in which a smoothing layer and a release layer formed of a silicone resin are sequentially laminated on a base film containing a filler (for example, Patent Document 1). It is described that by having such a laminated structure, both good smoothness with less surface irregularities and releasability are achieved.

JP 2006-159651 A

  However, in the case of the release film as described above, it is necessary to provide at least two layers of a smoothing layer and a release layer on the base film. For this reason, it is required that the smoothing layer and the release layer be integrated to form a single layer structure and simplify the manufacturing process.

  However, when only the release layer is formed on the base film without forming a smoothing layer, it is necessary to make the thickness larger than the conventional release layer in order to sufficiently reduce the unevenness of the surface (release surface). There is. However, the release layer is usually formed of a thermosetting silicone resin or the like so that good release properties can be exhibited, and if the thickness of the release layer is increased, it becomes difficult to sufficiently cure the inside of the release layer. It has been found that there is a problem that unevenness tends to occur on the surface of the release layer.

  On the other hand, when a light (ultraviolet) curable silicone resin is used for the release layer, if a paste containing a dielectric component or an electrode component is applied on the release surface, the paste tends to repel and good applicability is obtained. There was a problem that it was difficult to be.

  Here, as a measure for reducing the unevenness on the surface of the release layer, reducing the amount of filler contained in the base film can be mentioned. However, in this case, there is a problem that the mechanical strength of the base film, that is, the release film is lowered.

  Further, when the thickness of the dielectric sheet is reduced, the strength of the dielectric sheet is lowered and easily broken. As a result, the peelability tends to be further deteriorated. Such a problem is likely to occur particularly when the dielectric sheet is peeled off from the release film during the lamination process.

  Conventionally, as a means for evaluating the quality of peelability, a method of evaluating based on the contact angle of water has been used. In this method, when the contact angle of water is large, it is determined that the peelability is good, and when the contact angle is small, it is determined that the peelability is poor.

  However, even if the contact angle of water is large, the peelability may be poor, and conversely, even if the contact angle is small, the peelability may be good. From a different viewpoint, it was desired to evaluate the peelability.

  Furthermore, the release film is usually stored in a rolled state until it is used. In this case, the peeling surface and the surface of the base film are in contact with each other, and the component of the peeling surface is transferred or moved to the base film side, so that the surface of the peeling surface becomes non-uniform. There was a problem that occurred.

  The present invention has been made in view of the above circumstances, has a release surface that has both excellent peelability and applicability, and can be easily manufactured, and a release film formed by winding the release film. An object is to provide a film roll. In addition, by using such a release film, it is possible to form a green sheet with sufficiently reduced pinholes and thickness variations, and to provide a ceramic component sheet suitable for the production of multilayer ceramic products. To do. Furthermore, it aims at providing the manufacturing method of the ceramic component which can make the yield in manufacture of a ceramic component sufficiently high by using the said ceramic component sheet | seat.

  As a result of intensive studies, the present inventors have focused not on the contact angle of water but on the surface adhesion energy between the release layer surface and water (hereinafter referred to as water surface adhesion energy) as the evaluation standard for peelability. The present inventors have found that the peelability can be evaluated by the energy value. And it discovered that the said objective could be achieved by making surface adhesion energy in a peeling surface into a specific range, and making a composition of a peeling surface into a specific composition, and came to complete this invention.

That is, the release film according to the present invention is
A release film comprising a base film and a polymer layer provided on one surface of the base film,
The polymer layer has a layer containing a cured product of a (meth) acrylate component, and a film containing a silicone polymer component that covers a part of the surface of the layer opposite to the base film side. ,
The silicone polymer component is a polymer of a modified silicone oil modified with a (meth) acryloyl group and / or a vinyl group,
The surface adhesion energy of water is 10 mJ / m ² or less on the surface of the polymer layer.

  Such a release film has a polymer layer containing a cured product of a (meth) acrylate component. This polymer layer has a film containing a silicone polymer component on a part of the surface opposite to the base film. The surface of the polymer layer on the side having the film containing the silicone polymer component is a release surface on which a ceramic green sheet or an electrode green sheet is formed. The configuration of the release surface is as described above. By making the surface adhesion energy of water on the peeling surface within the above range, the peelability can be improved. In addition, since the cured product of the (meth) acrylate component is also exposed on the release surface, these pastes are difficult to be repelled and excellent in applicability when a paste containing a dielectric material or electrode material is applied. It becomes.

  In addition, such a release film does not need to form a release layer and a flattening layer separately on the base film, and can be made only of a polymer layer, so that the manufacturing process is simplified and easily performed. It can be manufactured.

The release film roll according to the present invention is
A release film roll formed by winding a release film into a roll,
The release film comprises a base film and a polymer layer provided on one surface of the base film,
The base film is made of a polyester resin,
The polymer layer has a layer containing a cured product of a (meth) acrylate component, and a film containing a silicone polymer component that covers a part of the surface of the layer opposite to the base film side. ,
The silicone polymer component is a polymer of a modified silicone oil modified with a (meth) acryloyl group and / or a vinyl group,
On the surface of the polymer layer, the surface adhesion energy of water is 10 mJ / m ² or less,
The contact angle of water is 80 ° or less on the surface of the base film opposite to the polymer layer side.

  The release film used for producing ceramic parts is usually stored or transported in the state of a release film roll wound in a roll until just before use. In such a release film roll, the release surface (the surface of the polymer layer in the present invention) and the surface of the base film opposite to the release surface come into contact.

  Further, unpolymerized silicone oil may be present on the surface of the polymer layer of the release film. Such unreacted silicone oil is present in a state of not being fixed to the surface of the polymer layer. Therefore, in the release film roll, unreacted silicone oil may be transferred or moved from the surface of the polymer layer to the base film side. When the unreacted silicone oil is transferred or moved to the base film side, the surface of the polymer layer becomes non-uniform and repelling of a paste or the like occurs.

  Therefore, in the present invention, in the release film roll described above, the contact angle of water on the surface of the base film opposite to the polymer layer side is within the above range. Thus, when the contact angle of water on the surface of the base film is within the range of the present invention, it is considered that there is almost no transfer or movement of unreacted silicone oil from the surface of the polymer layer. It is done.

  That is, in the release film roll described above, by making the contact angle of water on the surface of the base film within the scope of the present invention, unreacted silicone oil present on the surface of the polymer layer can be very small, The repellency of paste or the like can be sufficiently reduced, and good coating properties can be realized. Furthermore, since the surface adhesion energy on the surface of the polymer layer is in the above range, the peelability is also excellent.

  Therefore, the release film unwound from the release film roll and fed out is excellent in peelability and applicability.

  The ceramic component sheet according to the present invention includes any one of the release films described above, and a green sheet made of at least one of a ceramic green sheet and an electrode green sheet on the polymer layer of the release film.

  Since this ceramic component sheet has a release film having excellent releasability while sufficiently reducing unevenness, pinholes and thickness variations of ceramic green sheets and electrode green sheets can be sufficiently reduced. . As a result, it is possible to sufficiently improve the yield of ceramic products such as multilayer ceramic capacitors.

  A method of manufacturing a ceramic component according to the present invention includes a preparation step of preparing a plurality of ceramic component sheets as described above, a lamination step of laminating green sheets of ceramic component sheets to obtain a laminate having a plurality of green sheets, and lamination Firing the body to obtain a sintered body.

  In this method of manufacturing a ceramic component, a ceramic component sheet having a release film having the above-described characteristics is used, so that the ceramic component can be manufactured with a high yield.

  In the present invention, the peelability is evaluated based on a new concept of water surface adhesion energy rather than the contact angle of water normally used for evaluation of peelability. By making this surface adhesion energy in a specific range and making the composition of the release surface specific, a release film that has a release surface that has both excellent peelability and applicability and can be easily manufactured Can be provided. Furthermore, the peeling film roll which can make the applicability | paintability in the peeling surface of a peeling film still more favorable by making the contact angle of water in the surface of the base film opposite to a peeling surface into a specific range can be provided. . Further, by using such a release film, it is possible to form a green sheet with sufficiently reduced pinholes and thickness variations, and to provide a ceramic component sheet suitable for the production of multilayer ceramic products. it can. In addition, by using the ceramic component sheet, it is possible to provide a method for manufacturing a ceramic component capable of sufficiently suppressing the occurrence of defective products and sufficiently increasing the yield in manufacturing the ceramic component.

FIG. 1 is a cross-sectional view schematically showing a release film according to an embodiment of the present invention. 2A to 2C are schematic views for explaining a method of measuring the surface adhesion energy of water. FIG. 3 is a schematic diagram for explaining a method of calculating the surface adhesion energy of water. FIG. 4 is a perspective view schematically showing a release film roll according to an embodiment of the present invention and a release film fed out from the release film roll. FIG. 5 is a schematic enlarged cross-sectional view of a V portion in the release film roll shown in FIG. FIG. 6 is a cross-sectional view schematically showing a ceramic component sheet according to an embodiment of the present invention. FIG. 7 is a schematic cross-sectional view showing an example of a ceramic component obtained by the method for manufacturing a ceramic component according to one embodiment of the present invention.

  Hereinafter, the present invention will be described based on embodiments shown in the drawings.

<Peeling film 10>
As shown in FIG. 1, the release film 10 according to the present embodiment includes a base film 12 and a polymer layer 14 provided on one surface of the base film 12.

<Polymer layer 14>
The polymer layer 14 contains a (meth) acrylate polymer component and a silicone polymer component, and the surface 14a of the polymer layer 14 opposite to the base film 12 side has a (meth) acrylate weight. A portion of the surface of the layer containing the coalescing component is covered with the silicone polymer component. In the present specification, “(meth) acrylate” means acrylate and its corresponding methacrylate, and “(meth) acryloyl” means acryloyl and its corresponding methacryloyl.

  The (meth) acrylate polymer component means a component composed of a polymer (cured product) of (meth) acrylate monomer and / or (meth) acrylate oligomer, and polymerizes (meth) acrylate monomer and / or acrylate oligomer. Can be obtained. Preferable examples of the (meth) acrylate monomer include nonanediol di (meth) acrylate, decanediol di (meth) acrylate, butylpropanediol diacrylate, and trimethylolpropane di (meth) acrylate.

  A silicone polymer component means the component comprised by the polymer of the modified silicone oil modified | denatured by the (meth) acryloyl group and / or vinyl group, and it can obtain by polymerizing this modified silicone oil. Preferred examples of the modified silicone oil include one-end (meth) acrylate-modified silicone oil, both-end (meth) acrylate-modified silicone oil, side-chain (meth) acrylate-modified silicone oil, and both-end side-chain (meth) acrylate-modified silicone oil. , One terminal vinyl modified silicone oil, both terminal vinyl modified silicone oil, side chain vinyl modified silicone oil, both terminal side chain vinyl modified silicone oil, and the like. If necessary, several kinds of the modified silicone oil may be selected and blended.

  When the polymer layer 14 is formed, the (meth) acryloyl group and / or vinyl group of the modified silicone oil reacts with the (meth) acrylate component, whereby the modified silicone oil is fixed to the (meth) acrylate polymer, A film containing a silicone polymer component can be formed. Moreover, in the case of the said reaction, a part of (meth) acryloyl group and / or vinyl group of a modified silicone oil may react. In the release film of this embodiment, the amount of unreacted silicone oil can be greatly reduced, and repelling can be sufficiently reduced when a dielectric paste or the like is applied.

  The thickness t (μm) of the polymer layer 14 is preferably 0.5 to 3 μm, more preferably 1 to 2 μm, and still more preferably 1 to 1.5 μm. When the thickness t (μm) is 0.5 μm or less, the smoothness on the surface 14a of the release film 10 is impaired, and when a green sheet is formed on the surface 14a, pinholes and thickness variations are likely to occur. Tend. On the other hand, when the thickness t (μm) exceeds 3 μm, the release film 10 tends to curl when the base film is thin.

  The content of the (meth) acrylate polymer component and the silicone polymer component in the polymer layer 14 is 0.001 to 10 parts by mass of the silicone polymer component with respect to 100 parts by mass of the (meth) acrylate polymer component. It is preferable that it is 0.01 to 2 parts by mass, and more preferably 0.1 to 0.2 part by mass. When the content of the silicone polymer component with respect to 100 parts by mass of the (meth) acrylate polymer component is less than 0.001 part by mass, sufficiently excellent peelability tends to be impaired on the surface 14 a of the polymer layer 14. On the other hand, when the content of the silicone polymer component with respect to 100 parts by mass of the (meth) acrylate polymer component exceeds 10 parts by mass, when a ceramic paste or an electrode paste is applied to the surface (release surface) 14a of the polymer layer 14 The paste tends to be repelled and difficult to apply to a uniform thickness.

Density d of the polymer layer 14 (g / cm ³⁾ is preferably 0.95~1.25g / cm ^3, more preferably from 1.0~1.2g / cm ^3, more preferably 1 0.05 to 1.15 g / cm ³ . The polymer layer 14 having such a density can sufficiently suppress the occurrence of curling.

The amount (mg / m ² ) of the silicone polymer component per unit area in the polymer layer 14 formed on the surface of the base film 12 can be calculated by 10 × b × t × d (where , B is the content (mass%) of the silicone polymer component in the polymer layer). The amount of silicone polymer component calculated by this formula is preferably 0.2~6mg / ^{m 2,} more preferably 0.2~4mg / ^{m 2,} more preferably 0.2～3Mg / m ² , particularly preferably 0.2 to ² mg / m ² . When the amount of the silicone polymer component is too large, there is a tendency that sufficiently excellent coating properties are impaired when a dielectric paste is applied. On the other hand, if the amount of the silicone polymer component is too small, sufficiently excellent peelability tends to be impaired.

  The polymer layer 14 may contain inorganic particles such as silica in addition to the (meth) acrylate polymer component and the silicone polymer component.

<Surface adhesion energy>
In the present embodiment, the surface 14a of the polymer layer 14, the surface adhesion energy of water 10 mJ / ^{m 2} or less, preferably 8 mJ / ^{m 2} or less, and more preferably not more than 7 mJ / ^{m 2.} This surface adhesion energy of water indicates the magnitude of the interaction between water and the surface. If the surface adhesion energy is too large, the peelability of the dielectric sheet from the release film 10 tends to deteriorate. That is, in this embodiment, peelability is evaluated by surface adhesion energy.

  Conventionally, peelability has been evaluated based on the contact angle of water on the surface of the release layer. As for the contact angle of water, it is generally known that when the contact angle is increased, repelling of paste or the like is likely to occur (water repellency is increased), and when the contact angle is decreased, repelling is less likely to occur. It has been.

  On the other hand, when the release of the dielectric sheet from the release film is lightened (the force required for the release is reduced), repelling tends to occur. For this reason, it is considered that the peelability and the contact angle of water are correlated.

  However, the present inventors have a dielectric sheet with poor peelability (heavy peeling) even when the contact angle is large. Conversely, the contact angle is low, but the dielectric sheet has good peelability. It was found experimentally that there was something (light peeling). That is, it was found that the peelability of the dielectric sheet cannot be evaluated only with the contact angle of water.

  Furthermore, the present inventors have speculated that the interaction between the release layer and the dielectric sheet greatly affects the peelability of the dielectric sheet. As a basis for this, for example, when the butyral resin contained in the dielectric sheet has a hydroxyl group, peeling tends to be heavy. This is because hydrogen bonding causes a dominant interaction between the hydroxyl group and the release film surface on the release film surface.

  The interaction that occurs between the dielectric sheet and the surface of the release film is much different from the hydrogen-bonding interaction that occurs between water and the surface, considering that the interaction is hydrogen-bonding. It can be said that the similarity is high. And the hydrogen bond interaction which arises between this water and the surface can be evaluated by the surface adhesion energy of the above-mentioned water.

  Therefore, the peelability of the dielectric sheet from the release film can be evaluated by the surface adhesion energy of water on the release layer surface of the release film. When the hydrogen bonding interaction is weak, the surface adhesion energy of water is low, and as a result, peeling becomes light. On the other hand, when the hydrogen bond interaction is strong, the adhesion energy of water becomes large and peeling becomes heavy.

  In the release film according to this embodiment, since a part of the polymer of (meth) acrylate may be exposed on the surface thereof, the hydrogen bond that is present so that the surface adhesion energy of water is within the scope of the present invention. In consideration of the properties, it is preferable to adjust the selection and use amount of (meth) acrylate monomer and oligomer species.

  In addition, amine has a property of easily coordinating water due to hydrogen bonding properties, and the interaction with water tends to be strong. Therefore, it is preferable not to use a large amount of the amine-containing compound with respect to the surface of the dielectric sheet or the release film. Examples of the compound containing an amine include an ultraviolet curing agent and an antistatic agent.

  Further, in addition to the above, it is preferable that there are not excessive groups (for example, carboxyl group, chloro group, cyano group, etc.) that are liable to hydrogen bond on the surface of the dielectric sheet or release film.

  Note that the above does not exclude the use of a compound containing a group that easily bonds to hydrogen, and the compound may be included as long as the above-described surface adhesion energy of water is within the scope of the present invention. Of course.

  The surface adhesion energy of water can be measured using, for example, the sliding method shown below. First, a water droplet is dropped on the surface of a test sample (peeling film 10) fixed to a horizontal table, and the droplet 200 is placed on the peeling surface 14a of the peeling film as shown in FIG.

  Subsequently, as shown in FIG. 2B, the sample is gradually and gradually tilted from the horizontal state. Then, the end 200a of the droplet on the lower end side 10a of the sample and the end 200b of the droplet on the upper end side 10b of the sample are observed, and as shown in FIG. 2C, the end 200a of the droplet 200 is observed. , 200b starts to move, and an angle when the droplet 200 clearly starts to slide down from the upper end side 10b to the lower end side 10a is defined as a sliding angle α.

From FIG. 3, assuming that the surface adhesion energy of water is E, E is expressed by the following equation using this sliding angle α. Here, m is the mass of the droplet, g is the acceleration of gravity, and R is the diameter of the droplet.
E = (mgsinα) / 2πR

  Normally, the end portion 200a and the end portion 200b of the droplet start to move at the same time, but may rarely shift. In this case, the angle when the upper end 200b starts to move is defined as the sliding angle α.

  As a device for measuring the surface adhesion energy E of water, for example, DropMaster manufactured by Kyowa Interface Science may be used.

  Further, it is preferable that the one surface 14a of the polymer layer 14 has sufficiently reduced unevenness, that is, is smooth. Thereby, when a ceramic green sheet or an electrode green sheet is formed on the surface 14a, the occurrence of pinholes in the green sheet can be sufficiently suppressed, and the variation in thickness can be sufficiently reduced.

  The maximum protrusion height (SRp) of the surface 14a of the polymer layer 14 is preferably 0.2 μm or less, more preferably 0.1 μm or less, and further preferably 0.05 μm or less. The maximum protrusion height can be adjusted, for example, by changing the thickness t of the polymer layer 14 when the polymer layer 14 is formed. The maximum protrusion height (SRp) can be measured using a Micromap System (optical interference type three-dimensional non-contact surface shape measurement system) of Ryoka System Co., Ltd. in accordance with JIS B0601.

  The polymer layer 14 has a film containing a silicone polymer component covering a part of a layer containing a cured product of the (meth) acrylate polymer component on the surface 14a. The ratio of the portion covered with the film and the portion not covered can be controlled by adjusting the amount of silicone oil added to the (meth) acrylate component when the polymer layer 14 is formed. Note that the (meth) acrylate polymer component is exposed on a part of the surface 14a. If the ratio of the silicone oil to the (meth) acrylate component is reduced during the formation of the polymer layer 14, the amount of (meth) acrylate polymer component exposed on the surface 14a increases. On the other hand, when the usage ratio of the silicone oil to the (meth) acrylate component is increased, the exposure amount of the (meth) acrylate polymer component on the surface 14a is decreased. Thereby, the release film 10 can control the peelability and the applicability.

<Base film 12>
As the base film 12, a film made of a synthetic resin is used. Synthetic resins include polyester resin, polyolefin resin such as polypropylene resin and polyethylene resin, polylactic acid resin, polycarbonate resin, acrylic resin such as polymethyl methacrylate resin and polystyrene resin, polyamide resin such as nylon, polyvinyl chloride resin, polyurethane Resins, fluorine resins, polyphenylene sulfide resins and the like can be mentioned. Among these, a polyester resin is preferable, and polyethylene terephthalate (PET) is more preferable in consideration of mechanical properties, transparency, cost, and the like.

  The thickness s of the base film 12 is preferably 10 to 100 μm, more preferably 20 to 50 μm. When the thickness s (μm) is less than 10 μm, physical properties such as dimensional stability of the release film 10 tend to be impaired, and when it exceeds 100 μm, the manufacturing cost per unit area of the release film tends to increase. There is.

  From the viewpoint of sufficiently increasing the mechanical strength of the release film 10, the base film 12 preferably contains a filler (filler) that does not deteriorate the transparency. The filler is not particularly limited, and for example, calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium oxide, fumed silica, alumina, organic particles, and the like can be used.

<Peeling film roll 16>
In this embodiment, as shown in FIG. 4, the release film roll 16 is the release film 10 described above, and the base film is formed by winding a release film made of a polyester resin. At the time of use, as shown in FIG. 4, the sheet is unwound from the release film roll 16, drawn out, cut, and becomes a sheet-like release film 10. Here, in the peeling film roll 16, as shown in FIG. 5, the surface 14a of the polymer layer 14 and the surface 12a opposite to the polymer layer side in the base film 12 are in contact.

In this embodiment, the release film roll 16, the surface adhesion energy of water on the surface 14a of the polymer layer 14 is 10 mJ / ^{m 2} or less, preferably 8 mJ / ^{m 2} or less, and more preferably not more than 7 mJ / ^{m 2.} By doing in this way, the peelability in the peeling surface 14a can be made favorable.

  Moreover, in the above-mentioned release film, when the polymer layer is formed, a film containing the silicone polymer component is formed by the reaction of the (meth) acryloyl group of the modified silicone oil and the (meth) acrylate component. The However, unreacted silicone oil may be present in an unfixed state on the surface of the polymer layer.

  The presence of such unreacted silicone oil on the surface 14a of the polymer layer 14 can reduce the water surface adhesion energy. However, it is necessary to reduce the amount of unreacted silicone oil on the surface 14a for the following reason.

  As shown in FIG. 5, when the release film is wound in a roll shape, the surface 14a of the polymer layer and the surface 12a of the base film opposite to the polymer layer side are in contact with each other. Unreacted silicone oil may be transferred or moved from the surface of the polymer layer to the surface of the base film. In addition, since the degree of contact between the surface 14a of the polymer layer and the surface 12a of the base film is not constant, such oil has a high degree of contact, that is, the surface 14a and the surface 12a are in close contact with each other. It may gather due to capillary force etc.

  As a result, the surface 14a of the polymer layer 14 is considered to be non-uniform, and repellency such as paste is generated, resulting in poor applicability.

  Therefore, in the present embodiment, in the release film roll, the contact angle of water is 80 ° or less, preferably 75 ° or less, more preferably 70 ° or less, on the surface 12a opposite to the polymer layer side of the base film. It is said.

  In this embodiment, the base film is made of a polyester resin, and the contact angle of water (on the base film surface itself) with no other substance present on the surface 12a of the base film is set. When measured, it is about 60 °.

  That is, in the release film roll, that the contact angle of water on the surface 12a of the base film is within the above range indicates that the change in the contact angle on the base film surface 12a is small. In other words, it shows that the transfer or movement of the unreacted silicone oil present on the surface 14a of the polymer layer is very small.

  Therefore, in the release film roll 16, by making the contact angle of water on the surface 12a of the base film within the above range, the presence of unreacted silicone oil can be extremely reduced on the surface 14a of the polymer layer. Therefore, the coating property on the surface 14a of the polymer layer can be improved.

  By doing in this way, the peeling film which has the peeling surface which has the outstanding peelability and applicability | paintability is obtained.

  Next, the manufacturing method of the peeling film 10 of this embodiment is demonstrated below.

  The method for producing the release film 10 of the present embodiment contains a (meth) acrylate component that is incompatible with the photopolymerization initiator and the organic solvent, and a modified silicone oil modified with a (meth) acryloyl group and / or a vinyl group. A coating solution preparing step for preparing a coating solution to be performed, a precursor layer forming step for forming the precursor layer by applying the prepared coating solution on the base film 12 and drying, and irradiating the precursor layer with light. A polymer layer forming step of polymerizing (curing) the (meth) acrylate component and the modified silicone oil contained in the precursor layer to form the polymer layer 14 on the base film 12. Details of each step will be described below.

  In the coating solution preparation step, first, a (meth) acrylate component and a modified silicone oil that are incompatible with each other are prepared. “Incompatible with each other” means that when each component is mixed, phase separation occurs or white turbidity occurs, resulting in a non-uniform solution.

  The (meth) acrylate component means a (meth) acrylate monomer and / or a (meth) acrylate oligomer, and preferred examples thereof include A-NOD-N and A-DOD (above, Shin-Nakamura Chemical Co., Ltd., Product name). Preferred examples of the modified silicone oil include X-22-164A, X-22-164B, X-22-164C, X-22-164E, X-22-174DX, X-22-2426 (Shin-Etsu Chemical Co., Ltd.) Product name). By using these, it is possible to obtain the release film 10 that further reduces the unevenness of the release surface 14a and is further excellent in smoothness.

  As the (meth) acrylate monomer, one represented by the following general formula (1) is preferably used. The modified silicone oil is a silicone oil modified with a (meth) acryloyl group and / or a vinyl group, and the one represented by the following general formula (2) or (3) is preferably used.

  In said general formula (1), n shows the integer of 5-20.

In the general formula (2), R ₃ and R ₄ represent a single bond or a divalent hydrocarbon group, and m represents an integer of 1 or more. R ₃ and R ₄ are preferably a polymethylene group having about 1 to 10 carbon atoms or an alkylene group having 1 to 10 carbon atoms. Moreover, it is preferable that m is about 10-1000.

In the general formula (3), R ₅ and R ₆ represent a single bond or a divalent hydrocarbon group, and k represents an integer of 1 or more. R ₅ and R ₆ are preferably a polymethylene group having about 1 to 10 carbon atoms or an alkylene group having 1 to 10 carbon atoms. Further, k is preferably about 10 to 1000.

  A radical photoinitiator can be used as the photoinitiator. When ultraviolet rays are used, for example, α-hydroxyalkylphenone, α-aminoalkylphenone, etc. may be used. As a commercial item, IRGACURE184, IRGACURE127, IRGACURE907, IRGACURE379, DAROCURE1173 (above, trade name, manufactured by Ciba Specialty Chemicals) can be used.

  Note that IRGACURE 907 has an amine-containing structure, but can be used by adjusting the amount used so that the surface adhesion energy of water on the release surface is within the range of the present invention.

  As the organic solvent, a solvent capable of dissolving both the (meth) acrylate component and the modified silicone oil is used. Thereby, a coating solution for forming the polymer layer 14 in which the (meth) acrylate polymer component and the silicone polymer component are uniformly dissolved can be obtained. If the coating solution is not uniform, the surface characteristics tend to be non-uniform depending on the location. Examples of the organic solvent include toluene, xylene, methyl ethyl ketone, and the like.

  For example, 50 to 150 parts by mass of the (meth) acrylate component, 0.005 to 10 parts by mass of the modified silicone oil, and 1 to 10 parts by mass of the photopolymerization initiator are mixed and stirred with respect to 150 parts by mass of the organic solvent described above. By mixing, a coating solution can be prepared.

  If the amount of the modified silicone oil with respect to the (meth) acrylate component is excessive, unreacted components remain in the polymer layer 14, and there is a tendency that sufficiently excellent coating properties for the dielectric paste are impaired. On the other hand, if the amount of the modified silicone oil relative to the (meth) acrylate component is too small, sufficiently excellent peelability tends to be impaired.

  In the precursor forming step, the coating liquid prepared as described above is applied onto one surface of the base film 12 using, for example, a bar coater. Thereafter, in a dryer, for example, drying is performed at a temperature of 50 to 150 ° C. for 10 seconds to 10 minutes to evaporate and remove the organic solvent, thereby forming a precursor layer on one surface of the base film 12.

  The coating method of the coating solution is not particularly limited, and it may be applied using a reverse coating method, a gravure coating method, a rod coating method, a bar coating method, a Mayer bar coating method, a die coating method, a spray coating method, or the like. Good.

  The specific gravity of the (meth) acrylate component contained in the coating solution is usually about 0.95 to 1.5, and the specific gravity of the silicone oil is usually about 0.95 to 1.5. That is, the specific gravity of the (meth) acrylate component and the modified silicone oil is almost the same, or the modified silicone oil tends to be slightly lighter. Moreover, the modified silicone oil has a lower surface energy than the (meth) acrylate component. Here, in the case of a coating liquid containing a plurality of types of incompatible components, each component moves so that the energy state is lowered. In the stripping solution of this embodiment, as described above, the modified silicone oil has a lower specific gravity and a lower surface energy. Therefore, after applying the stripping solution on one surface of the base film 12 in the precursor forming step, if the solvent is removed by drying, the (meth) acrylate component and the modified silicone component are not compatible with each other. It is easy to move to the surface opposite to the base film 12 side (the surface to be the peeling surface 14a).

  Usually, the modified silicone oil tends to dissolve the photopolymerization initiator less easily than the (meth) acrylate component. When the stripping solution from which the solvent is removed is irradiated with ultraviolet rays, radicals are generated by the reaction initiator, the (meth) acrylate component is radicalized, and the (meth) acrylate component is radically polymerized. Moreover, the (meth) acryloyl group and / or vinyl group of silicone oil also undergo radical polymerization.

  In the polymer forming step, the precursor layer formed on one surface of the base film 12 is irradiated with light or an electron beam to form a polymer layer. As light, it is preferable to use ultraviolet rays. As a UV light source, a commercially available product such as a mercury lamp or a metal halide lamp can be used, and the UV irradiation amount is adjusted according to the thickness of the precursor layer. Thereby, the precursor layer can be sufficiently cured. It is also preferable to irradiate with ultraviolet rays in a nitrogen atmosphere in order to prevent oxygen inhibition during radical polymerization.

  By irradiation with ultraviolet rays, the (meth) acrylate component and the modified silicone oil contained in the precursor layer undergo radical polymerization. The (meth) acrylate component is polymerized to become a (meth) acrylate polymer component, and the modified silicone oil becomes a silicone polymer component. In some cases, the reactive group ((meth) acryloyl group and / or vinyl group) of the modified silicone oil reacts with the reactive group ((meth) acryloyl group) of the (meth) acrylate monomer. As the polymerization reaction proceeds in this way, the polymer layer 14 can be obtained from the precursor layer.

  Water on the surface 14a of the polymer layer 14 is adjusted by adjusting the type of (meth) acrylate component, the molecular weight of the modified silicone oil, the type of reactive group, the modification method (both ends, side ends, side chain combination), and the like. The surface adhesion energy can be adjusted. As a result, the peelability of the release film can be adjusted. In addition, the surface adhesion energy changes on the surface of the layer containing the (meth) acrylate polymer component, depending on the ratio (coverage) that the film containing the silicone polymer component covers the surface of the layer, and the peelability is improved. Can be adjusted. In general, the higher the coverage by the silicone polymer component, the lighter the peeling, and the lower the coverage, the heavier the peeling.

  The coverage of the present invention can be determined by measuring the contact angle of pure water on the surface 14 a of the polymer layer 14. The reason will be described below. In the present invention, since the (meth) acrylate component and the modified silicone oil which are incompatible with each other are used, when the organic solvent is removed by drying, the (meth) acrylate component and the modified silicone oil are separated, and the modified silicone oil becomes (meta ) The acrylate component layer will be coated. Here, the greater the amount of silicone oil in the unit area, the closer the coverage of the polymer layer 14 with the silicone polymer component is to 1 (100% in percentage).

The relationship when a liquid is present on the surface is Young's formula. When θ is the contact angle, γ ₁ is the surface tension of the solid, γ ₂ is the interfacial tension between the individual liquids, and γ _L is the surface tension of the liquid, the following relational expression is shown.
γ ₁ = γ _L × cos θ + γ ₂

Here, when a liquid is present only on the surface of the (meth) acrylate polymer component, the contact angle is θ _A , the surface tension of the (meth) acrylate polymer component is γ _A , and between the liquid and the (meth) acrylate polymer If the interfacial tension of γ is _AL , the following relational expression is shown.
γ _A = γ _L × cos θ _A + γ _AL (i)

Next, when the liquid is present on the surface covered with the silicone polymer component, the contact angle is θ _S , the surface tension of the silicone polymer component is γ _S , and the interfacial tension between the liquid and the silicone polymer component Where γ _SL is the following relational expression (ii).
γ _S = γ _L × cos θ _S + γ _SL (ii)

Apply a liquid to the side of the (meth) acrylate polymer component layer that is partly coated with the silicone polymer component (where the (meth) acrylate polymer component is exposed where it is not coated with the silicone polymer component). When present, when the contact angle is θ _X , the surface tension of the polymer component is γ _X , and the surface tension between the liquid and the polymer component is γ _XL , the following relational expression (iii) is shown.
γ _X = γ _L × cos θ _X + γ _XL (iii)

The ratio (exposure ratio) of the area where the (meth) acrylate polymer component is exposed on the entire surface 14a of the polymer layer 14 is a, and the ratio (coverage ratio) of the area covered with the modified silicone oil is s (unit area). (Area covered with modified silicone oil in ÷ unit area), and a + s = 1. The contribution of γ _A and γ _S in γ _X is proportional to the area ratio. That is, the relationship of the following formula (iv) is established.
γ _X = a × γ _A + s × γ _S (iv)

Considering γ _{XL in the} same way, the relationship of the following formula (v) is established.
γ _XL = a × γ _AL + s × γ _SL (v)

From the above formulas (i), (ii), (iii), (iv) and (v), the following formula (vi) can be derived.
cos θ _X = a × cos θ _A + s × cos θ _S = (1−s) × cos θ _A + s × cos θ _S (vi)

From the above formula (vi), the coverage s by the silicone polymer component can be specified from θ _A , θ _S , and θ _X. If the coverage at the reference amount is known, the coverage by any silicone polymer component can be obtained from the calculation. In particular, when the amount of the silicone polymer component is large, the coverage may be 1 (100% in terms of percentage) hidden behind the error of the contact angle measurement value. In such a case, the coverage can be specified as follows. For example, assuming that 1 mg of the silicone polymer component is present per 1 m ² , the coverage by the silicone polymer component is s _0, and the exposure rate of the (meth) acrylate polymer is a ₀ (a ₀ + s ₀ = 1).

1m coverage _s n when it is coated with a silicone polymer component of ² per any amount n (mg), the exposure rate of (meth) acrylate polymer component and _{a n (a n + s n} = 1).
Where a _n = a ₀ ⁿ = (1−s ₀ ) ⁿ
S _n = 1−a _n = 1− (1−s ₀ ) ⁿ .

If the contact angle at n (mg) is θ _N ,
cos θ _N = (1−s ₀ ) ⁿ × cos θ _A + {1− (1−s ₀ ) ⁿ } × cos θ _S
And s ₀ can also be obtained. In addition, when n is the density of the (meth) acrylate polymer component d (g / cm ³ ), the thickness is t (μm), and the ratio of the modified silicone oil in the polymer layer is b (mass%), n = 10 × b × t × d.

  The coverage by the silicone polymer component is preferably 0.33 to 0.99999 (33% to 99.999% in terms of percentage), and 0.55 to 0.98 (55 to 98% in terms of percentage). Is more preferable.

  According to the method for producing the release film 10 according to the present embodiment, it is not necessary to separately form the release layer and the smoothing layer, and only one polymer layer is formed on the base film using one type of release liquid. Thus, the release film 10 can be obtained. According to this manufacturing method, the unevenness of the release surface 14a can be sufficiently reduced, and the release film 10 that is sufficiently excellent in peelability and applicability can be easily manufactured.

  Moreover, the peeling film roll which concerns on this embodiment can be manufactured by winding the peeling film manufactured as mentioned above further in roll shape. This release film roll is stored or transported until it is used to form a dielectric sheet or the like.

  FIG. 6 is a cross-sectional view schematically showing a preferred embodiment of the ceramic component sheet of the present invention. The ceramic component sheet 20 includes a release film 10, a ceramic green sheet 22 on the release surface 14 a of the polymer layer 14, and an electrode green sheet 24 formed on the ceramic green sheet 22.

  Examples of the ceramic green sheet 22 include a dielectric green sheet for forming a multilayer ceramic capacitor. The thickness of the ceramic green sheet 22 can be set to several μm to several hundred μm, for example. The ceramic green sheet 22 is peeled off from the release film 10 and then fired to become a dielectric containing, for example, calcium titanate, strontium titanate and / or barium titanate.

  The thickness of the electrode green sheet 24 can be set to several μm to several hundred μm, for example. The electrode green sheet 24 is peeled from the release film 10 and then baked to become an electrode containing, for example, copper, copper alloy, nickel, nickel alloy, or the like.

  The method for producing the ceramic component sheet will be described in detail below. The manufacturing method of the ceramic component sheet 20 of the present embodiment includes a (meth) acrylate monomer that is incompatible with a photopolymerization initiator and an organic solvent, and a modified silicone oil modified with a (meth) acryloyl group and / or a vinyl group. A coating solution preparation step for preparing a coating solution to be contained, a precursor layer forming step for forming the precursor layer by applying the prepared coating solution on the base film 12 and drying, and irradiating the precursor layer with light The polymer layer forming step of polymerizing the (meth) acrylate monomer and the modified silicone oil contained in the precursor layer to form the polymer layer 14 on the base film to obtain the release film 10 was obtained. A ceramic paste containing ceramic powder is applied onto the release surface 14a of the polymer layer 14 of the release film 10 and dried to make a ceramic green sheet 2 The electrode green sheet 24 is formed on the ceramic green sheet 22 by applying an electrode paste containing an electrode material and drying, and the ceramic green sheet 22 and the electrode green sheet 24 are sequentially laminated on the release film 10. And a sheet forming step for obtaining a ceramic part sheet. Since the method for producing the release film 10 through the coating liquid preparation step to the polymer layer formation step has already been described, the sheet formation step will be described in detail below.

  In the sheet forming step, a paste containing a ceramic powder (ceramic paste) and a paste containing an electrode material are provided on the surface 14a opposite to the base film 12 side of the release film 10 obtained in the polymer layer forming step. (Electrode paste) is applied respectively.

  The ceramic paste can be prepared, for example, by kneading a dielectric material (ceramic powder) and an organic vehicle. As the dielectric material, various compounds that become composite oxides or oxides upon firing, for example, carbonates, nitrates, hydroxides, organometallic compounds, and the like can be appropriately selected and used. As the dielectric material, a powder having an average particle size of 0.4 μm or less, preferably about 0.1 to 3.0 μm can be used.

  The electrode paste can be prepared by kneading a conductive material made of various conductive metals or alloys, various oxides, organometallic compounds, or resinates that become conductive materials after firing, and an organic vehicle.

  As the conductor material used when manufacturing the electrode paste, it is preferable to use Ni metal, Ni alloy, or a mixture thereof. In order to improve adhesion, the electrode paste may contain a plasticizer. Examples of the plasticizer include phthalic acid esters such as benzylbutyl phthalate (BBP), adipic acid, phosphoric acid esters, glycols, and the like.

  The organic vehicle contained in the ceramic paste and the electrode paste is prepared by dissolving a binder resin in an organic solvent. Examples of the binder resin used in the organic vehicle include ethyl cellulose, acrylic resin, butyral resin, polyvinyl acetal, polyvinyl alcohol, polyolefin, polyurethane, polystyrene, or a copolymer thereof. Among these, it is preferable to use a butyral resin, specifically, a polyvinyl butyral resin. By using a butyral resin, the mechanical strength of the ceramic green sheet 22 and the electrode green sheet 24 can be increased. Further, in this case, by using an alkane (diol) di (meth) acrylate monomer as a raw material for the polymer layer 14, the peelability of the ceramic green sheet 22 and the electrode green sheet 24 can be further improved.

  The polymerization degree of the polyvinyl butyral resin is preferably 1000 to 1700, and more preferably 1400 to 1700.

  As the organic solvent used in the organic vehicle, for example, organic solvents such as terpineol, alcohol, butyl carbitol, acetone, toluene, xylene, and benzyl acetate can be used alone or in admixture of two or more. Examples of the alcohol include methanol, ethanol, propanol and butanol.

  The ceramic paste may contain additives selected from various dispersants, plasticizers, antistatic agents, dielectrics, glass frit, insulators, and the like as necessary.

  The above ceramic paste is applied onto the surface 14a of the release film 10 by, for example, a doctor blade device. Then, the applied ceramic paste is dried in a commercially available drying apparatus at a temperature of, for example, 50 to 100 ° C. for 1 to 20 minutes to form a ceramic green sheet 22. The ceramic green sheet 22 shrinks by 5 to 25% compared to before drying.

  Next, an electrode paste is printed on the surface 22a of the formed ceramic green sheet 22 so as to form a predetermined pattern using, for example, a screen printing apparatus. And the apply | coated electrode paste is dried for 1 to 20 minutes at the temperature of 50-100 degreeC in a commercially available drying apparatus, and the electrode green sheet 24 is formed. Thereby, the ceramic component sheet 20 in which the release film 10, the ceramic green sheet 22, and the electrode green sheet 24 are sequentially laminated can be obtained.

  Since the ceramic component sheet 20 is manufactured using the release film 10 having the polymer layer 14, the ceramic part sheet 20 is sufficiently excellent in the peelability of the green sheet 26 composed of the ceramic green sheet 22 and the electrode green sheet 24. The remaining peeling of 26 can be sufficiently reduced. For this reason, the dispersion | variation in the thickness of the green sheet 26 is fully reduced, and generation | occurrence | production of a pinhole can fully be suppressed.

  Further, when the electrode paste or the ceramic paste is applied to the surface 14a of the polymer layer 14, the occurrence of repellency is sufficiently suppressed, so that the green sheet 26 with little pinhole and thickness variation can be easily formed. be able to. This makes it easier to manufacture the multilayer ceramic capacitor.

  Next, a method for manufacturing a multilayer ceramic capacitor, which is a preferred embodiment of the method for manufacturing a ceramic component of the present invention, will be described below.

  The manufacturing method of the multilayer ceramic capacitor of the present embodiment includes a step of preparing a plurality of ceramic component sheets, a stacking step of stacking a plurality of ceramic component sheet green sheets to obtain a stack, and firing and sintering the stack A firing step for obtaining a body, and an electrode formation step for obtaining a multilayer ceramic capacitor by forming a terminal electrode on the sintered body.

  In the preparation step, a plurality of ceramic component sheets 20 manufactured by the method for manufacturing a ceramic component sheet of the above embodiment are prepared. Next, in the stacking step, the green sheets 26 of the plurality of ceramic component sheets 20 are stacked to obtain a stacked body in which the plurality of green sheets 26 are stacked.

  An example of the lamination process will be described in detail. First, the release film 10 of the ceramic component sheet 20 is peeled to obtain the green sheet 26. The green sheet 26 and the ceramic component sheet 20 are laminated so that the surface 22b of the green sheet 26 and the electrode green sheet 24 of another ceramic component sheet 20 face each other. Thereafter, the release film 10 is peeled from the laminated ceramic component sheet 20. By repeating such a procedure and laminating the green sheets 26, a laminate can be obtained. That is, in this lamination process, after laminating the ceramic component sheet 20 on the green sheet 26, the laminate is formed by repeating the procedure of peeling the release film 10 a plurality of times.

  Another example of the lamination process will be described. The green sheet 26 is laminated so that the surface 22a of the green sheet 26 and the surface 22b of another green sheet 26 from which the release film 10 has been peeled face each other. By repeating such a procedure and sequentially laminating the green sheets 26, a laminate can be obtained. That is, in this lamination process, the laminated body is formed by repeating the procedure of laminating the green sheet 26 from which the release film 10 has been peeled off a plurality of times.

  There is no restriction | limiting in particular in the number of lamination | stacking of the green sheet in a laminated body, For example, tens to hundreds of layers may be sufficient. A thick exterior green sheet on which no electrode layer is formed may be provided on both end faces orthogonal to the stacking direction of the stack. After forming the laminated body, the laminated body may be cut to form a green chip.

In the firing step, the laminate (green chip) obtained in the lamination step is fired to obtain a sintered body. The firing conditions are preferably 1100 to 1300 ° C. in an atmosphere such as a mixed gas of humidified nitrogen and hydrogen. However, the oxygen partial pressure in the atmosphere during firing is preferably 10 ⁻² Pa or less, more preferably 10 ⁻² to 10 ⁻⁸ Pa. Note that before the firing, it is preferable to perform a binder removal treatment on the laminate. The binder removal process can be performed under normal conditions. For example, when a base metal such as Ni or Ni alloy is used as the conductor material of the internal electrode layer (electrode green sheet 24), it is preferably performed at 200 to 600 ° C.

After firing, heat treatment may be performed to reoxidize the dielectric layer constituting the sintered body. The holding temperature or maximum temperature in the heat treatment is preferably 1000 to 1100 ° C. The oxygen partial pressure during the heat treatment is preferably an oxygen partial pressure higher than the reducing atmosphere during firing, and more preferably 10 ⁻² Pa to 1 Pa. The sintered body thus obtained is preferably subjected to end surface polishing by, for example, barrel polishing, sand blasting or the like.

  In the electrode forming step, a multilayer ceramic capacitor can be obtained by baking the terminal electrode paste on the side surface of the sintered body to form the terminal electrode.

  In the ceramic component manufacturing method of the present embodiment, since the ceramic component sheet of the above embodiment is used, generation of pinholes in the obtained ceramic component, that is, the multilayer ceramic capacitor can be sufficiently suppressed. For this reason, a multilayer ceramic capacitor can be formed with a high yield.

  FIG. 7 is a schematic cross-sectional view showing an example of a ceramic component obtained by the manufacturing method of the above embodiment. A multilayer ceramic capacitor 100 shown in FIG. 7 includes an interior portion 40 and a pair of exterior portions 50 that sandwich the interior portion 40 in the stacking direction. In the present embodiment, the multilayer ceramic capacitor 100 has a terminal electrode 60 on a side surface.

  The interior portion 40 includes a plurality (13 layers in this embodiment) of ceramic layers 42 and a plurality (12 layers in this embodiment) of internal electrode layers 44. The ceramic layers 42 and the internal electrode layers 44 are alternately stacked. The internal electrode layer 44 is electrically connected to the terminal electrode 60.

  The exterior part 50 is formed of a ceramic layer. This ceramic layer is formed from an exterior green sheet and contains, for example, the same components as the ceramic layer 42.

  The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

Example 1
<Preliminary experiment>
As raw materials, an acrylate monomer represented by the following formula (4) (specific gravity: 0.99), a modified silicone oil in which both ends represented by the following formula (5) are modified with acryloyl groups (specific gravity: 0.98) Prepared. When 100 parts by mass of the acrylate monomer represented by the following formula (4) and 5 parts by mass of the modified silicone oil represented by the following formula (5) were stirred in a beaker to prepare a mixed solution, the mixed solution was separated into white turbidity. From this, it was confirmed that the acrylate monomer and the modified silicone oil are not compatible. Further, when 100 parts by mass of methyl ethyl ketone and 100 parts by mass of toluene were added to this mixed solution, it was confirmed that the mixture became transparent. Thereafter, a release film was produced as follows.

<Preparation of release film>
With respect to 100 parts by mass of the acrylate monomer of the above formula (4), 0.277 parts by mass of the modified silicone oil of the above formula (5), 100 parts by mass of methyl ethyl ketone, 100 parts by mass of toluene, and a reaction initiator (IRGACURE127) 1.5 A part by mass was placed in a metal container and mixed with stirring to obtain a colorless and transparent coating solution.

The obtained coating solution is applied to a biaxially stretched polyethylene terephthalate (PET) film (base film, thickness 38 μm) with a bar coater, dried with hot air at a heating temperature of 80 ° C. for 30 seconds to evaporate methyl ethyl ketone and toluene. Then, ultraviolet rays were irradiated in a nitrogen atmosphere with an oxygen concentration of 100 ppm to form a 1 μm thick polymer layer on the base film, and a release film roll wound into a roll was obtained. The thickness was measured using a spectrophotometer (trade name: V-670, manufactured by JASCO Corporation). Further, in the ultraviolet irradiation, the integrated light quantity was set to 250 mJ / cm ² .

<Measurement of water surface adhesion energy>
About the obtained peeling film roll, the surface adhesion energy of the water in the peeling surface of the unrolled peeling film was measured using DropMaster of Kyowa Interface Science. The measurement conditions were a temperature of 20 ° C. and a humidity of 60%, and 16 μl of pure water was dropped on the surface of the polymer layer of the release film. The surface adhesion energy was 4.6 mJ / m ² . In addition, in the comparative example which will be described later, when measurement cannot be performed by dropping 16 μl, 12 μl of pure water was dropped twice and measurement was performed at 24 μl. The measurement results are also shown in Table 1.

<Measurement of water contact angle>
Using the Kyowa Interface Science DropMaster, the contact angle of water is measured for the polymer layer surface (peeling surface) opposite to the substrate film side and the substrate film surface opposite to the polymer layer side. It was measured. The measurement conditions were a temperature of 20 ° C. and a humidity of 60%, and 2 μl of pure water was dropped on each surface. The contact angle of the release surface was 104 °. The contact angle of the base film surface was 69 °. The measurement results are also shown in Table 1.

<Formation of dielectric sheet>
BaTiO ₃ system ceramic powder, polyvinyl butyral (PVB) as an organic binder, and methanol as a solvent were prepared. Next, 10 parts by mass of an organic binder and 165 parts by mass of a solvent were kneaded with 100 parts by mass of the ceramic powder to obtain a dielectric slurry. This dielectric slurry was applied to the surface of the polymer layer of the obtained release film, and a dielectric sheet was formed so that the film thickness after drying was 1 μm. About the obtained dielectric sheet, the presence or absence of a pinhole was evaluated by the method shown below, and the applicability | paintability in the peeling film surface was evaluated.

<Presence / absence of pinhole>
Using a pinhole detector, the pinhole was investigated over a length of 3000 m of the dielectric sheet. As a result, no pinhole was detected.

<Formation of electrode>
Ni powder, ethyl cellulose as an organic binder, and terpineol as a solvent were prepared. Next, 4 parts by mass of an organic binder and 100 parts by mass of a solvent were kneaded with respect to 100 parts by mass of the Ni powder to obtain an electrode paste. This electrode slurry was applied onto the above dielectric sheet, and an electrode was formed so that the film thickness after drying was 1 μm, to obtain a lamination sheet (ceramic component sheet). About the obtained sheet | seat for lamination | stacking, the peeling test shown below was done and the peelability of the dielectric material sheet from a peeling film was evaluated.

<Peel test>
The peelability of the dielectric sheet was tested using the peeling mechanism of the laminating apparatus. The dielectric sheet as a test piece was adsorbed on an adsorption plate (200 mm × 200 mm) having an adsorption mechanism by reducing the air pressure, and then the release film was peeled off. At this time, it was confirmed whether the release film could be peeled without breaking the dielectric sheet. As a result, the dielectric sheet could be peeled without tearing.

(Example 2)
With respect to 100 parts by mass of the acrylate monomer of the above formula (4), 0.138 parts by mass of the modified silicone oil of the above formula (5), 100 parts by mass of methyl ethyl ketone, 100 parts by mass of toluene, and a reaction initiator (IRGACURE127) 1.5 A part by mass was placed in a metal container and mixed with stirring to obtain a colorless and transparent coating solution.

Using the obtained coating liquid, a release film roll was obtained in the same manner as in Example 1. About the peeling film unrolled from the peeling film roll, it carried out similarly to Example 1, and measured the surface adhesion energy and contact angle of water. The surface adhesion energy was 6.5 mJ / m ² . Moreover, the contact angle of the peeling surface was 102 °, and the contact angle of the base film surface was 66 °. The measurement results are also shown in Table 1.

  Further, a dielectric sheet was formed on the surface of the polymer layer of the release film in the same manner as in Example 1, and the presence or absence of pinholes was evaluated in the same manner as in Example 1. As a result, no pinhole was detected.

  Furthermore, an electrode was formed on the dielectric sheet in the same manner as in Example 1 to obtain a lamination sheet. About the obtained sheet | seat for lamination | stacking, it carried out similarly to Example 1, and evaluated the peelability of the dielectric material sheet. As a result, the dielectric sheet could be peeled from the release film without tearing.

(Example 3)
With respect to 100 parts by mass of the acrylate monomer of the above formula (4), 0.069 parts by mass of the modified silicone oil of the above formula (5), 50 parts by mass of methyl ethyl ketone, 100 parts by mass of toluene, and a reaction initiator (IRGACURE127) 1.5 A part by mass was placed in a metal container and mixed with stirring to obtain a colorless and transparent coating solution.

Using the obtained coating liquid, a release film roll was obtained in the same manner as in Example 1. About the peeling film unrolled from the peeling film roll, it carried out similarly to Example 1, and measured the surface adhesion energy and contact angle of water. The surface adhesion energy was 7.6 mJ / m ² . Moreover, the contact angle of the peeling surface was 96 degrees, and the contact angle of the base film surface was 64 degrees. The measurement results are also shown in Table 1.

  Further, a dielectric sheet was formed on the surface of the polymer layer of the release film in the same manner as in Example 1, and the presence or absence of pinholes was evaluated in the same manner as in Example 1. As a result, no pinhole was detected.

  Furthermore, an electrode was formed on the dielectric sheet in the same manner as in Example 1 to obtain a lamination sheet. About the obtained sheet | seat for lamination | stacking, it carried out similarly to Example 1, and evaluated the peelability of the dielectric material sheet. As a result, the dielectric sheet could be peeled from the release film without tearing.

Example 4
With respect to 100 parts by mass of the acrylate monomer of the above formula (4), 0.046 parts by mass of the modified silicone oil of the above formula (5), 100 parts by mass of methyl ethyl ketone, 100 parts by mass of toluene, and a reaction initiator (IRGACURE127) 1.5 A part by mass was placed in a metal container and mixed with stirring to obtain a colorless and transparent coating solution.

Using the obtained coating liquid, a release film roll was obtained in the same manner as in Example 1. About the peeling film unrolled from the peeling film roll, it carried out similarly to Example 1, and measured the surface adhesion energy and contact angle of water. The surface adhesion energy was 9.8 mJ / m ² . Moreover, the contact angle of the peeling surface was 92 °, and the contact angle of the base film surface was 64 °. The measurement results are also shown in Table 1.

  Further, a dielectric sheet was formed on the surface of the polymer layer of the release film in the same manner as in Example 1, and the presence or absence of pinholes was evaluated in the same manner as in Example 1. As a result, no pinhole was detected.

  Furthermore, an electrode was formed on the dielectric sheet in the same manner as in Example 1 to obtain a lamination sheet. About the obtained sheet | seat for lamination | stacking, it carried out similarly to Example 1, and evaluated the peelability of the dielectric material sheet. As a result, the dielectric sheet could be peeled from the release film without tearing.

(Example 5)
With respect to 100 parts by mass of the acrylate monomer of the above formula (4), 0.138 parts by mass of the modified silicone oil of the above formula (5), 100 parts by mass of methyl ethyl ketone, 100 parts by mass of toluene, 1 part by mass of a reaction initiator (IRGACURE907) Was put in a metal container and mixed by stirring to obtain a colorless and transparent coating solution.

Using the obtained coating liquid, a release film roll was obtained in the same manner as in Example 1. About the peeling film unrolled from the peeling film roll, it carried out similarly to Example 1, and measured the surface adhesion energy and contact angle of water. The surface adhesion energy was 7.1 mJ / m ² . Moreover, the contact angle of the peeling surface was 102 °, and the contact angle of the base film surface was 66 °. The measurement results are also shown in Table 1.

  Further, a dielectric sheet was formed on the surface of the polymer layer of the release film in the same manner as in Example 1, and the presence or absence of pinholes was evaluated in the same manner as in Example 1. As a result, no pinhole was detected.

  Furthermore, an electrode was formed on the dielectric sheet in the same manner as in Example 1 to obtain a lamination sheet. About the obtained sheet | seat for lamination | stacking, it carried out similarly to Example 1, and evaluated the peelability of the dielectric material sheet. As a result, the dielectric sheet could be peeled from the release film without tearing.

(Comparative Example 1)
A coating solution was obtained in the same manner as in Example 1 except that the modified silicone oil of the above formula (5) was not added.

Using the obtained coating liquid, a release film roll was obtained in the same manner as in Example 1. About the peeling film unrolled from the peeling film roll, it carried out similarly to Example 1, and measured the surface adhesion energy and contact angle of water. The surface adhesion energy was 11 mJ / m ² . Moreover, the contact angle of the peeling surface was 72 °, and the contact angle of the base film surface was 63 °. The measurement results are also shown in Table 1.

  Further, a dielectric sheet was formed on the surface of the polymer layer of the release film in the same manner as in Example 1, and the presence or absence of pinholes was evaluated in the same manner as in Example 1. As a result, no pinhole was detected.

  Furthermore, an electrode was formed on the dielectric sheet in the same manner as in Example 1 to obtain a lamination sheet. About the obtained sheet | seat for lamination | stacking, it carried out similarly to Example 1, and evaluated the peelability of the dielectric material sheet. As a result, the dielectric sheet could not be peeled from the release film.

(Comparative Example 2)
With respect to 100 parts by mass of the acrylate monomer of the above formula (4), 0.138 parts by mass of the modified silicone oil of the above formula (5), 100 parts by mass of methyl ethyl ketone, 100 parts by mass of toluene, and 10 parts by mass of a reaction initiator (IRGACURE907). Was put in a metal container and mixed by stirring to obtain a colorless and transparent coating solution.

Using the obtained coating liquid, a release film roll was obtained in the same manner as in Example 1. About the peeling film unrolled from the peeling film roll, it carried out similarly to Example 1, and measured the surface adhesion energy and contact angle of water. The surface adhesion energy was 10.4 mJ / m ² . Moreover, the contact angle of the peeling surface was 101 °, and the contact angle of the base film surface was 65 °. The measurement results are also shown in Table 1.

  Further, a dielectric sheet was formed on the surface of the polymer layer of the release film in the same manner as in Example 1, and the presence or absence of pinholes was evaluated in the same manner as in Example 1. As a result, no pinhole was detected.

  Furthermore, an electrode was formed on the dielectric sheet in the same manner as in Example 1 to obtain a lamination sheet. About the obtained sheet | seat for lamination | stacking, it carried out similarly to Example 1, and evaluated the peelability of the dielectric material sheet. As a result, the dielectric sheet was torn and only a part of the dielectric sheet could be peeled from the release film.

(Comparative Example 3)
To 100 parts by mass of the acrylate monomer of the above formula (4), 50 parts by mass of methyl ethyl ketone, 100 parts by mass of toluene, and 1.5 parts by mass of a reaction initiator (IRGACURE127) are placed in a metal container, mixed with stirring, and colorless and transparent. A coating solution was obtained.

The obtained coating solution is applied to a biaxially stretched polyethylene terephthalate (PET) film (base film, thickness 38 μm) with a bar coater, dried with hot air at a heating temperature of 80 ° C. for 30 seconds to evaporate methyl ethyl ketone and toluene. Then, ultraviolet rays were irradiated in a nitrogen atmosphere with an oxygen concentration of 100 ppm to obtain a film in which a polymer layer having a thickness of 1 μm was formed on the base film. The thickness was measured using a spectrophotometer (trade name: V-670, manufactured by JASCO Corporation). Further, in the ultraviolet irradiation, the integrated light quantity was set to 250 mJ / cm ² .

  Subsequently, 10 parts by mass of addition polymerization type silicone KS-847 (manufactured by Shin-Etsu Chemical Co., Ltd.), 50 parts by mass of toluene, 50 parts by mass of methyl ethyl ketone, PL-50T, 0.1 parts by mass are put in a metal container and mixed by stirring. A colorless and transparent coating solution was obtained.

  The obtained coating solution was applied to the above film with a bar coater, cured while drying the solvent with hot air at 110 ° C. to obtain a release film, and a release film roll was obtained by winding the release film. . The coating thickness was 0.12 μm.

About the peeling film unrolled from the peeling film roll, it carried out similarly to Example 1, and measured the surface adhesion energy and contact angle of water. The surface adhesion energy was 7.8 mJ / m ² . Moreover, the contact angle of the peeling surface was 109 °, and the contact angle of the base film surface was 86 °. The measurement results are also shown in Table 1.

  Further, a dielectric sheet was formed on the surface of the polymer layer of the release film in the same manner as in Example 1, and the presence or absence of pinholes was evaluated in the same manner as in Example 1. As a result, 21 pinholes were detected.

  Furthermore, an electrode was formed on the dielectric sheet in the same manner as in Example 1 to obtain a lamination sheet. About the obtained sheet | seat for lamination | stacking, it carried out similarly to Example 1, and evaluated the peelability of the dielectric material sheet. As a result, the dielectric sheet could be peeled from the release film without tearing.

  From Table 1, when the surface adhesion energy of water on the surface of the polymer layer of the release film is within the range of the present invention, pinholes due to repellency such as paste are not detected, and the dielectric from the release film It was confirmed that the peelability of the body sheet was also good.

  Moreover, since the contact angle of the surface of the base film in the release films according to Examples 1 to 5 is within the scope of the present invention, even if the release film is wound and stored in a roll shape, the release film is peeled off. It was confirmed that the coating property on the surface was good.

  On the other hand, when the surface adhesion energy of water on the surface of the polymer layer of the release film is outside the range of the present invention, pinholes are not detected, but the contact angle of water is low (Comparative Example 1). Even if it was high (Comparative Example 2), it was confirmed that the peelability of the dielectric sheet from the release film was poor.

  Further, by comparing Example 5 and Comparative Example 2 and using a reaction initiator having a structure containing an amine, if the amount used is too large, the surface adhesion energy on the release surface becomes too large, It was confirmed that the peelability deteriorated.

  Furthermore, when a component different from the silicone polymer component of the present invention is used (Comparative Example 3), even if the surface adhesion energy of water on the surface of the polymer layer of the release film is within the range of the present invention, Pinholes were detected, and it was confirmed that there were many repels such as paste.

  DESCRIPTION OF SYMBOLS 10 ... Release film, 10a ... Lower end part, 10b ... Upper end part, 12 ... Base film, 12a ... Surface, 14 ... Polymer layer, 14a ... Surface (release surface), 16 ... Release film roll, 20 ... Ceramic component sheet 22 ... ceramic green sheet, 22a ... surface, 22b ... surface (peeling side), 24 ... electrode green sheet, 26 ... green sheet, 40 ... interior part, 42 ... ceramic layer, 44 ... internal electrode layer, 50 ... exterior Part, 60 ... terminal electrode, 100 ... multilayer ceramic capacitor, 200 ... droplet, 200a, 200b ... end.

Claims (4)

A release film comprising a base film and a polymer layer provided on one surface of the base film,
The polymer layer has a layer containing a cured product of a (meth) acrylate component, and a film containing a silicone polymer component that covers a part of the surface of the layer opposite to the base film side. ,
The silicone polymer component is a polymer of a modified silicone oil modified with a (meth) acryloyl group and / or a vinyl group,
A release film, wherein the surface adhesion energy of water is 10 mJ / m ² or less on the surface of the polymer layer. A release film roll formed by winding a release film into a roll,
The release film comprises a base film and a polymer layer provided on one surface of the base film,
The base film is made of a polyester resin,
The polymer layer has a layer containing a cured product of a (meth) acrylate component, and a film containing a silicone polymer component that covers a part of the surface of the layer opposite to the base film side. ,
The silicone polymer component is a polymer of a modified silicone oil modified with a (meth) acryloyl group and / or a vinyl group,
On the surface of the polymer layer, the surface adhesion energy of water is 10 mJ / m ² or less,
A release film roll, wherein a contact angle of water is 80 ° or less on a surface of the base film opposite to the polymer layer side.   A ceramic component sheet comprising the release film according to claim 1 and a green sheet comprising at least one of a ceramic green sheet and an electrode green sheet on the polymer layer of the release film. A preparation step of preparing a plurality of ceramic component sheets according to claim 3,
Lamination step of laminating the green sheets of the ceramic component sheet to obtain a laminate having a plurality of the green sheets;
A firing step of firing the laminate to obtain a sintered body.

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