JP6947286B2 - Manufacturing method of peeling film and manufacturing method of ceramic parts sheet - Google Patents

Description

The present disclosure relates to a peeling film, a ceramic component sheet, a method for manufacturing a peeling film, a method for manufacturing a ceramic component sheet, and a method for manufacturing a multilayer ceramic capacitor.

As a method for manufacturing a multilayer ceramic capacitor, a manufacturing method including peeling a ceramic green sheet formed on a peeling film from the peeling film and laminating with a plurality of similarly obtained ceramic green sheets is known (). For example, Patent Document 1). With the demand for miniaturization of multilayer ceramic capacitors, thinning of ceramic green sheets is required. Along with this, the peeling film used for forming the ceramic green sheet is required to have a smooth surface with sufficiently reduced unevenness and to have excellent peeling property.

As a peeling film having excellent peeling property, for example, Patent Document 2 describes a peeling film including a base film and a polymer layer provided on one surface of the base film, and the polymer layer is (meth). The silicone polymer component comprises a layer containing a cured product of the 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. A release film which is a polymer of a modified silicone oil modified with a (meth) acryloyl group and / or a vinyl group has been proposed.

Japanese Unexamined Patent Publication No. 2003-203822 Japanese Unexamined Patent Publication No. 2010-105384

In order to cope with the further miniaturization of multilayer ceramic capacitors in recent years, it is required to form a thinner ceramic green sheet or the like. In order to produce such a thin-film ceramic green sheet, it is desired to further improve the peeling property of the peeling film. However, if the content of the silicone polymer component in the peeling layer is increased in order to improve the peeling property, the silicone polymer component and other components are easily phase-separated. There are concerns that preparation will be difficult, that the prepared slurry will be difficult to apply to the substrate, and that defects will occur due to aggregation of the silicone polymer, making it difficult to obtain a peeling layer with sufficient smoothness. ..

Therefore, an object of the present disclosure is to provide a peeling film having excellent peelability and sufficient smoothness, and a method for producing the same. It is also an object of the present disclosure to provide a ceramic component sheet having the above-mentioned peeling film and capable of producing a thin-film green sheet, and a method for producing the same. A further object of the present disclosure is to provide a method for manufacturing a multilayer ceramic capacitor using a peeling film as described above.

One aspect of the present disclosure is a peeling film having a base material and a peeling layer provided on the base material, and the peeling layer is a silicone resin having a reactive functional group and other polymerizable components. It is a cured product of the composition containing . When the peak intensity of silicon at 1 nm is Y and the peak intensity of silicon measured when a silicone resin layer containing 90% or more of polydimethylsiloxane is formed is Z, X is larger than Y and Z. Provided is a peeling film in which the ratio of X to Z is 40% or more and the ratio of Y to Z is 5 to 50%.

The peeling film has a ratio of X to Z of 40% or more with respect to the peak intensity of silicon measured by XPS, and Y (peak intensity of silicon at a depth of 4.1 nm from the surface of the peeling layer). Is smaller than X (peak intensity on the surface of the peeling layer). Therefore, the resin component derived from the silicone resin having a reactive functional group is more in the surface layer portion of the peeling layer, and the peeling property on the surface of the peeling layer is excellent. Further, since the Y is 5 to 50% with respect to Z (the peak strength of silicon when the layer made of the silicone resin is formed), the other is at a depth of 4.1 nm from the surface of the release layer. Since the resin component derived from the polymerizable component is appropriately present, the aggregation of the resin component derived from the silicone resin is sufficiently reduced, and the peeling layer has few defects and is sufficiently excellent in smoothness.

The ratio of Y to X may be 70% or less.

The peeling layer may be a cured product of a composition containing a silicone resin having a reactive functional group, a (meth) acrylate having a reactive functional group, and an acrylic silicone graft polymer having a reactive functional group. When the peeling layer is a cured product formed by using the above composition, in the above composition, the acrylic silicone graft polymer having a reactive functional group is a silicone resin and (meth) acrylate (or a polymer thereof). Since it works to suppress the phase separation of the silicone resin and the aggregation of the silicone resin, it is possible to contain a larger amount of the silicone resin as compared with the conventional peeling layer, and the peeling property and smoothness of the resulting peeling layer are obtained. Can be compatible at a higher level.

The content of the acrylic silicone graft polymer may be 10 to 600% by mass based on the total amount of the (meth) acrylate. When the content of the acrylic silicone graft polymer is within the above range, the phase separation between the silicone resin and the (meth) acrylate (or a polymer thereof) and the aggregation of the silicone resin are more sufficiently suppressed, and the peeling layer is peeled off. It is possible to achieve both property and smoothness at a higher level.

The content of the silicone resin may be 0.5% by mass or more. By setting the content of the silicone resin within the above range, the content of the silicone resin on the surface of the peeling layer can be increased, so that the peeling property of the peeling layer can be further improved.

One aspect of the present disclosure is a ceramic comprising the peeling film described above and at least one green sheet selected from the group consisting of a ceramic green sheet and an electrode green sheet provided on the surface of the peeling layer. Provide parts sheet.

Since the ceramic component sheet has a peeling film having excellent peeling property and sufficient smoothness, the occurrence of pinholes and the variation in thickness of the green sheet provided on the peeling film are sufficiently suppressed. ing. Further, since the ceramic component sheet has a peeling film having excellent peeling property, it is also useful for producing a thin-film green sheet.

One aspect of the present disclosure is a method for producing a peeling film having a base material and a peeling layer provided on the base material, which has a silicone resin having a reactive functional group and a reactive functional group ( A step of coating a slurry containing a composition containing a meta) acrylate and an acrylic silicone graft polymer having a reactive functional group and a solvent on the substrate, and reducing the content of the solvent in the slurry. Provided is a method for producing a peeling film having a step of providing a photosensitive layer and a step of forming a peeling layer composed of a cured product of the above composition by exposing the photosensitive layer.

The method for producing a peeling film uses a composition containing a silicone resin having a reactive functional group, a (meth) acrylate having a reactive functional group, and an acrylic silicone graft polymer having a reactive functional group. The acrylic silicone graft polymer works to suppress the phase separation between the silicone resin and the (meth) acrylate (or the (meth) acrylate polymer produced during the curing reaction) and the aggregation of the silicone resin, and increases the amount of the silicone resin. Can be included. Further, in the process of removing the solvent and reducing the content of the solvent, the (meth) acrylate moves to the base material side due to the specific gravity of each component, the surface energy, etc., and the silicone resin moves to the side opposite to the base material. Moving. By exposing the photosensitive layer in a state where the above-mentioned movement has occurred in the photosensitive layer, the functional groups in each component react with each other to fix the distribution state of the components in the photosensitive layer. Due to such an action, the surface of the peeling layer opposite to the base material side (the surface on which the ceramic green sheet or the like is formed) has excellent peelability, and the occurrence of defects due to aggregation of the silicone resin is suppressed and smooth. It is possible to produce a peeling film having excellent properties.

Further, there may be a step of preparing the composition so that the content of the acrylic silicone graft polymer is 10 to 600% by mass based on the total amount of the (meth) acrylate. By preparing the composition so that the content of the acrylic silicone graft polymer is within the above range, the silicone resin and the (meth) acrylate (or the (meth) acrylate polymer produced during the curing reaction) are phase-separated. And, the aggregation of the silicone resin can be suppressed more sufficiently, and the occurrence of defects in the peeling layer can be further reduced. As a result, it is possible to produce a peeling film in which the peeling property and smoothness of the peeling layer are compatible at a higher level.

A step of preparing the composition so that the content of the silicone resin is 0.5% by mass or more may be further included. By preparing the composition so that the content of the silicone resin is within the above range, it is possible to produce a peeling film in which the peeling property of the peeling layer is further improved.

The reactive functional group is at least one functional group selected from the group consisting of a (meth) acryloyl group and a vinyl group, and the composition may further contain a photopolymerization initiator.

One aspect of the present disclosure is also a ceramic green sheet and an electrode green sheet provided on a base material, a peeling layer provided on the base material, and a surface of the peeling layer opposite to the base material side. A method for producing a ceramic component sheet, comprising at least one green sheet selected from the group consisting of, a silicone resin having a reactive functional group, a (meth) acrylate having a reactive functional group, and a reactivity. A step of coating a slurry containing a composition containing an acrylic silicone graft polymer having a functional group and a solvent on the base material, and a step of reducing the content of the solvent in the slurry to provide a photosensitive layer. The step of forming a peeling layer composed of a cured product of the above composition by exposing the photosensitive layer, and the surface of the peeling layer opposite to the base material side are composed of a ceramic powder and an electrode material. It comprises a step of applying a paste containing at least one selected from the group and removing the solvent to form at least one green sheet selected from the group consisting of a ceramic green sheet and an electrode green sheet. , Provide a method for manufacturing a ceramic component sheet.

In the method for producing a ceramic component sheet, since a peeling layer having excellent peelability and sufficient smoothness is prepared and used, the occurrence of pinholes in the green sheet and the variation in thickness can be sufficiently suppressed. By using the ceramic component sheet obtained by the above-mentioned method for manufacturing a ceramic component sheet, the yield of ceramic products such as multilayer ceramic capacitors can be improved.

One aspect of the present disclosure is a method for manufacturing a multilayer ceramic capacitor, which is a step of preparing a plurality of the ceramic component sheets described above, and peeling the peeling sheet from the ceramic component sheet, laminating the green sheet, and a plurality of layers. Provided is a method for manufacturing a multilayer ceramic capacitor, comprising a step of obtaining a laminate having the green sheet and a step of sintering the laminate to obtain a sintered body.

Since the above-mentioned ceramic component sheet is used in the method for manufacturing the multilayer ceramic capacitor, the ceramic component can be manufactured with a high yield.

According to the present disclosure, it is possible to provide a peeling film having excellent peelability and sufficient smoothness, and a method for producing the same. According to the present disclosure, it is also possible to provide a ceramic component sheet having the above-mentioned peeling film and capable of producing a thin-film green sheet, and a method for producing the same. According to the present disclosure, it is possible to further provide a method for manufacturing a multilayer ceramic capacitor using the peeling film as described above.

FIG. 1 is a schematic cross-sectional view showing an example of a peeling film. FIG. 2 is a schematic cross-sectional view showing an example of a ceramic component sheet. FIG. 3 is a schematic cross-sectional view showing an example of a ceramic component. FIG. 4 is a graph showing the result of the depth direction analysis of the peeling layer by XPS measurement in the example. FIG. 5 is a photograph of the appearance of the peeling film prepared in Example 3 and Comparative Example 6.

Hereinafter, embodiments of the present disclosure will be described with reference to the drawings as the case may be. However, the following embodiments are examples for explaining the present disclosure, and are not intended to limit the present disclosure to the following contents. Further, in the description, the same reference numerals are used for elements having the same structure or the same function, and duplicate description may be omitted in some cases. In addition, the positional relationship such as up, down, left, and right shall be based on the positional relationship shown in the drawings unless otherwise specified. Furthermore, the dimensional ratio of each element is not limited to the ratio shown in the drawings.

FIG. 1 is a schematic cross-sectional view showing an example of a peeling film. The peeling film 10 has a base film 12 and a peeling layer 14 provided on the base film 12. The peeling film 10 can be used, for example, for manufacturing a green sheet used for manufacturing a multilayer ceramic capacitor.

As the base film 12, for example, a synthetic resin film or the like is used. Examples of the synthetic resin include polyester; polyolefins such as polyethylene and polypropylene; polylactic acid; acrylic resins such as polymethacrylate and polymethylmethacrylate; polyamides such as nylon 6 and 6; polyvinyl chloride; polyurethane; polystyrene; polycarbonate; polyphenylene sulfide. In addition, fluororesins such as polytetrafluoroethylene can be mentioned. The synthetic resin preferably contains polyester, more preferably polyethylene terephthalate. Polyethylene terephthalate film is relatively inexpensive and has excellent mechanical properties and transparency.

The base film 12 may contain a filler. When the base film 12 contains a filler, the mechanical strength of the peeling film 10 can be sufficiently increased. The content of the filler in the base film 12 is not particularly limited, but it is preferably such that the transparency is not deteriorated. Examples of the filler include calcium carbonate, calcium phosphate, titanium oxide, silica, fumed silica, kaolin, talc, alumina, organic particles and the like.

The thickness s of the base film 12 is preferably 10 to 100 μm, more preferably 20 to 50 μm. By setting the thickness s of the base film 12 to 10 μm or more, the physical characteristics such as the dimensional stability of the peeling film 10 are more excellent. By setting the thickness s of the base film 12 to 100 μm or less, the manufacturing cost per unit area of the peeling film 10 can be further reduced.

The peeling layer 14 is composed of a cured product of a composition containing a silicone resin having a reactive functional group and other polymerizable components. In the peeling layer 14, the silicone resin has a specific distribution along the depth direction of the peeling layer 14. The distribution can be measured by XPS. The distribution can be controlled by adjusting the composition and blending ratio of the composition, adjusting the production conditions of the production method described later, and the like.

The distribution measurement of the silicone resin along the depth direction of the peeling layer 14 by XPS (X-ray photoelectron spectroscopy) includes the composition analysis of the peeling layer surface by XPS measurement and the etching of the peeling layer surface by sputtering using argon ions. Can be performed in combination with. The peeled layer is scraped from the surface by spatter, and the composition analysis on the exposed surface is performed by XPS while gradually exposing the inside. There is a correlation between the etching time due to sputtering and the distance (depth) in the thickness direction of the peeling layer. Therefore, the measurement result by XPS can be graphed as the distribution of the silicone resin with respect to the depth from the surface of the peeling layer. In the present specification, the measurement is performed assuming that the etching rate is 0.05 nm / sec.

In the peeling layer 14, the peak intensity of silicon on the surface of the peeling layer 14 opposite to the base material (base film 12) side measured by XPS is set to X, and the depth from the surface of the peeling layer 14 is defined as X. When the peak intensity of silicon at 4.1 nm is Y and the peak intensity of silicon measured when a silicone resin layer containing 90% or more of polydimethylsiloxane is formed is Z, X is larger than Y. The ratio of X to Z is 40% or more, and the ratio of Y to Z is 5 to 50%.

The peak intensity X with respect to the peak intensity Z may be, for example, 43% or more, 45% or more, or 50% or more, and may be 90% or less. When the peak intensity X is within the above range, the peeling property of the peeling layer 14 can be further enhanced, and the load required for peeling the green sheet after forming the green sheet on the peeling layer 14 is reduced. Can be done. The peak intensity Y with respect to the peak intensity Z may be, for example, 5 to 40%, 5 to 30%, 10 to 30%, or 10 to 25%. When the peak strength Y is within the above range, the resin component derived from other polymerizable components appropriately coexists with the resin component derived from the silicone resin, sufficiently suppresses the aggregation of the silicone resin, and the peeling layer 14 The smoothness of the resin can be further improved.

The ratio of the peak intensity Y to the peak intensity X is preferably 70% or less, more preferably 60% or less, and further preferably 50% or less. When the ratio of the peak intensity Y to the peak intensity X is within the above range, the silicone component on the base film 12 side can be sufficiently reduced, the coating film formability can be improved, and the coating film can be cured. Destruction at the interface between the peeling layer and the substrate, which is obtained later, can be suppressed more sufficiently.

The thickness t of the peeling layer 14 is preferably 0.5 to 3 μm, more preferably 1 to 2 μm, and even more preferably 1 to 1.5 μm. By setting the thickness t of the peeling layer 14 to 0.5 μm or more, the influence of the unevenness of the surface of the base film 12 can be more sufficiently reduced, and the surface of the peeling layer 14 opposite to the base film can be reduced. The smoothness on (the peeling surface 14a) can be made more sufficient. By setting the thickness t of the peeling layer 14 to 3 μm or less, it is possible to prevent the peeling film 10 from warping due to shrinkage of the photosensitive layer due to a curing reaction during the formation of the peeling layer.

The micro-roughness Sp of the surface of the peeling layer 14 opposite to the base film 12 side (peeling surface 14a) may be 100 nm or less, and may be 50 nm or less, 40 nm or less, 35 nm or less, or 30 nm or less. .. When the minute roughness Sp of the peeling surface 14a is within the above range, the occurrence of pinholes and the like can be more sufficiently suppressed in the ceramic green sheet and the electrode green sheet formed by using the peeling film 10. The variation in thickness of the ceramic green sheet and the electrode green sheet can be sufficiently reduced to improve the smoothness. The micro-roughness Sp can be measured by using the Micromap System (optical interferometry three-dimensional non-contact surface shape measuring system) of Ryoka System Co., Ltd. in accordance with the method described in JIS B 0601: 2013.

The peeling film 10 described above can be produced, for example, by the following production method. One embodiment of the method for producing a peeling film includes a step of coating a slurry containing a composition containing a silicone resin having a reactive functional group and a solvent on a substrate (coating step), and a step (coating step) in the slurry. A step of reducing the content of the solvent to provide a photosensitive layer (solvent reduction step) and a step of exposing the photosensitive layer to form a peeling layer composed of a cured product of the composition (exposure step). Has.

The coating step in the method for producing a peeling film is a step of coating a slurry on a substrate to form a coating film containing the above composition. As a coating method for forming a coating film, for example, a bar coating method, a Meyer bar coating method, a reverse coating method, a gravure coating method, a rod coating method, a die coating method, a spray coating method and the like can be used.

As the solvent contained in the slurry, a solvent capable of dissolving the silicone resin having a reactive functional group and other components is used. Examples of the solvent include toluene, xylene, methyl ethyl ketone (MEK), isopropyl alcohol (IPA), propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PEGMA) and the like. One of these solvents may be used alone, or two or more of these solvents may be used in combination.

The composition containing a silicone resin having a reactive functional group contains a silicone resin having a reactive functional group, a (meth) acrylate having a reactive functional group, and an acrylic silicone graft polymer having a reactive functional group. May be good. Reactive functional groups include at least one functional group selected from the group consisting of vinyl groups and (meth) acryloyl groups. The plurality of reactive functional groups may be the same or different from each other. As used herein, "(meth) acrylate" means acrylate and methacrylate, and "(meth) acryloyl group" refers to an acryloyl group and a methacryloyl group.

The silicone resin having a reactive functional group (hereinafter, also referred to as the component (A)) may be, for example, a modified silicone oil modified with a reactive functional group. Examples of the modified silicone oil include one-terminal (meth) acrylate-modified silicone oil, both-terminal (meth) acrylate-modified silicone oil, side chain (meth) acrylate-modified silicone oil, and both-terminal side chain (meth) acrylate-modified silicone oil. Examples thereof include one-terminal vinyl-modified silicone oil, both-terminal vinyl-modified silicone oil, side-chain vinyl-modified silicone oil, and both-terminal side-chain vinyl-modified silicone oil. One of these modified silicone oils may be used alone, or two or more thereof may be used in combination.

As the modified silicone oil, for example, those represented by the following general formula (1) or the following general formula (2) may be used.

In the above general formula (1), R ¹ and R ² represent a single bond or a divalent hydrocarbon group independently of each other. m represents an integer of 1 or more. R ¹ and R ² are preferably a polymethylene group having about 1 to 10 carbon atoms or an alkylene group having 1 to 10 carbon atoms. m is preferably about 10 to 1000.

In the above general formula (2), R ³ and R ⁴ represent a single bond or a divalent hydrocarbon group independently of each other. n 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. Further, n is preferably about 10 to 1000.

The (meth) acrylate having a reactive functional group (hereinafter, also referred to as the component (B)) preferably has two or more reactive functional groups, even if it has three or more reactive functional groups. good. The (meth) acrylate having a reactive functional group has, for example, an alkylenediol di (meth) acrylate, a (meth) acrylate having a trimethylolpropane skeleton, a (meth) acrylate having a pentaerythritol skeleton, and a dipentaerythritol skeleton. Examples include (meth) acrylate. These (meth) acrylates may be used alone or in combination of two or more.

Examples of the alkylenediol di (meth) acrylate include nonanediol di (meth) acrylate, decanediol di (meth) acrylate, and butylpropanediol diacrylate. Examples of the (meth) acrylate having a trimethylolpropane skeleton include trimethylolpropane di (meth) acrylate and trimethylolpropane tri (meth) acrylate. Examples of the (meth) acrylate having a pentaerythritol skeleton include pentaerythritol tetra (meth) acrylate. Examples of the (meth) acrylate having a dipentaerythritol skeleton include dipentaerythritol hexa (meth) acrylate.

The acrylic silicone graft polymer having a reactive functional group (hereinafter, also referred to as the component (C)) is a polymer of a monomer containing (meth) acrylic acid and / or (meth) acrylic acid ester with respect to an acrylic polymer. It is a polymer in which a silicone macromonomer has been introduced. As the acrylic silicone graft polymer having a reactive functional group, one type may be used alone, or two or more types may be used in combination. An acrylic silicone graft polymer having a reactive functional group preferably has one reactive functional group. The silicone as the graft portion has a polysiloxane structure, preferably a polydimethylsiloxane structure. It is preferable that a plurality of polysiloxane structures in the acrylic silicone graft polymer having a reactive functional group are introduced. The content ratio of the polysiloxane structure may be, for example, 3% by mass or more based on the total amount of the acrylic silicone graft polymer.

As used herein, the "acrylic silicone graft polymer having a reactive functional group" includes an oligomer having a relatively small molecular weight. That is, the "acrylic silicone graft polymer having a reactive functional group" includes an acrylic silicone graft oligomer having a reactive functional group. The weight average molecular weight of the acrylic polymer portion constituting the main chain of the acrylic silicone graft polymer having a reactive functional group may be, for example, 5000 to 20000000, 30000 to 1000000, or 100,000 to 400000. You can do it. In the present specification, "weight average molecular weight" means a value measured by gel permeation chromatography and is expressed as a polystyrene-equivalent value.

As the acrylic silicone graft polymer having a reactive functional group, a commercially available one may be used, or a separately synthesized one may be used. Examples of the acrylic silicone graft polymer having a reactive functional group include KP-500 series manufactured by Shin-Etsu Chemical Co., Ltd., Cymac series manufactured by Toa Synthetic Co., Ltd. (Simac is a registered trademark), and Taisei Fine Chemical Co., Ltd. 8SS (UV curable silicone acrylic polymer) series and the like can be used.

The acrylic silicone graft polymer having a reactive functional group can be prepared, for example, by the following preparation method. As an example of the preparation method, for example, a silicone macromonomer is introduced into a polymer (linear acrylic polymer) of a monomer such as (meth) acrylic acid and (meth) acrylate by a polymer reaction, and then a silicone macromonomer is introduced. , A method for preparing an acrylic silicone graft polymer having a reactive functional group by reacting a (meth) acrylate having a glycidyl group with a carboxyl group derived from acrylic acid and introducing a reactive functional group. Can be mentioned.

In addition to the above methods, the method for preparing an acrylic silicone graft polymer having a reactive functional group includes a monomer such as (meth) acrylic acid and (meth) acrylate and a monomer having a glycidyl group such as glycidyl (meth) acrylate. A silicone macromonomer was introduced by a polymer reaction into a linear acrylic polymer obtained by copolymerizing the above, and then (meth) acrylic acid was introduced into the glycidyl group introduced into the acrylic polymer. Reactive functional groups (here, (meth)) are reacted by reacting (meth) acrylic acid chloride, (meth) acrylamide, and (meth) acrylate having a hydroxyl group (for example, 2-hydroxyethyl (meth) acrylate, etc.). It may be a method of preparing an acrylic silicone graft polymer having a reactive functional group by introducing an acryloyl group). The above-mentioned method of copolymerizing a monomer having a glycidyl group includes a method of reacting an isocyanate compound having a (meth) acryloyl group with the hydroxyl group after copolymerizing a monomer having a hydroxyl group, and a monomer having a phenolic hydroxyl group. Alternatively, a method may be used in which a monomer having a thiol group is copolymerized and then a (meth) acrylate having a glycidyl group is reacted with the phenolic hydroxyl group or the thiol group.

In addition to the above method, the acrylic silicone graft polymer having a reactive functional group contains a polysiloxane having one vinyl group or a (meth) acryloyl group, a monomer such as (meth) acrylic acid and (meth) acrylate, and glycidyl (. It can also be prepared by a method of copolymerizing with a monomer having a glycidyl group such as a meta) acrylate and introducing a reactive functional group into an acrylic polymer having a silicone graft as described above.

Further, there may be a step of preparing the composition so that the content of the component (C) is 10 to 600% by mass based on the total amount of the component (B). The content of the component (C) may be, for example, 5 to 400% by mass, 12 to 300% by mass, and 15 to 100% by mass based on the total amount of the component (B). When the content of the component (C) is within the above range, the content of the component (A) in the slurry can be increased, and the peelability and smoothness of the peeling layer 14 are compatible at a higher level. can do.

Further, there may be a step of preparing the composition so that the content of the component (A) is 0.5% by mass or more. The content of the component (A) may be, for example, 0.8% by mass or more, 1.0% by mass or more, or 1.2% by mass or more based on the total amount of the composition. When the content of the component (A) is within the above range, a peeling film having further improved peeling property of the peeling layer can be produced.

As the component (A) and the component (B), it is preferable to select a component having a small compatibility with each other. By selecting a component that is difficult to be compatible with each other as the component (A) and the component (B), the phase is appropriately phased inside the coating film in the process of reducing the solvent content from the coating film in the solvent removing step described later. Separation can occur. Therefore, in the obtained photosensitive layer, a gradient of the concentration of the component (A) and the component (B) can be more easily provided in the depth direction thereof. Here, this concentration gradient can be adjusted by blending the component (C). As used herein, the terms "incompatible with each other" and "difficult to be compatible with each other" mean that when the respective components are mixed, phase separation occurs or the solution becomes cloudy, resulting in a uniform solution. ..

The composition containing the silicone resin having a reactive functional group may contain other components in addition to the component (A), the component (B) and the component (C). Examples of other components include a photopolymerization initiator and a filler.

As the photopolymerization initiator, a compound that generates radicals by irradiation with active light can be used. Examples of the photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, and 2-hydroxy-1- {4- [4- [4- [4-]. (2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one and other α-hydroxyalkylphenones, as well as 2-methyl-1- (4-methylthiophenyl) -2- Examples thereof include α-aminoalkylphenone such as morpholinopropan-1-one. As the photopolymerization initiator, for example, IRGACURE184, IRGACURE127, IRGACURE907, IRGACURE379, DAROCURE1173 (all manufactured by Ciba Specialty Chemicals Co., Ltd., trade name) and the like can be used.

The solvent reduction step in the method for producing a peeling film is a step of reducing the content of the solvent and providing a photosensitive layer containing the composition. The solvent reduction step is preferably a step of removing the solvent and providing a photosensitive layer made of the composition. The solvent may be removed by heating and drying at a temperature of 50 to 150 ° C. for 10 seconds to 10 minutes.

The specific gravity of the component (B) contained in the slurry is usually about 0.95 to 1.5, and the specific density of the component (A) is usually about 0.95 to 1.5. That is, the specific densities of the component (B) and the component (A) tend to be almost the same, or the component (A) tends to be slightly lighter. Further, the component (A) has a lower surface energy than the component (B). Here, in the case of a slurry containing a plurality of types of components that are incompatible with each other, each component moves so as to lower the energy state. In the slurry of the present embodiment, as described above, the component (A) has a lighter specific gravity and a lower surface energy, so that the solvent is reduced from the coating film provided on the base film 12 in the solvent removing step. In the process, the component (A) is more likely to move to the surface (the surface that becomes the peeling surface 14a) on the side opposite to the base film 12 side.

In the exposure step in the method for producing a peeling film, the reactive functionality of the components (A), (B) and (C) is performed by irradiating the photosensitive layer formed by reducing the content of the solvent with active light rays. This is a step of reacting the groups and curing the composition to form a peeling layer. The irradiation amount of the active light can be adjusted according to the thickness of the photosensitive layer and the like. The exposure step may be performed in a nitrogen atmosphere. By performing the exposure step in a nitrogen atmosphere, deactivation of radically active species due to oxygen can be suppressed, and insufficient curing of the photosensitive layer can be further suppressed. The active ray is preferably ultraviolet light. As the light source of ultraviolet rays, for example, a mercury lamp, a metal halide lamp, or the like can be used.

One embodiment of the ceramic component sheet is a ceramic green sheet and an electrode green provided on a base material, a peeling layer provided on the base material, and a surface of the peeling layer opposite to the base material side. It has at least one green sheet selected from the group consisting of sheets. As the ceramic component sheet, the above-mentioned peeling film 10 may be used as a peeling film having a base material and a peeling layer provided on the base material.

FIG. 2 is a schematic cross-sectional view showing an example of a ceramic component sheet. The ceramic component sheet 20 has a peeling film 10, a ceramic green sheet 22 on the peeling surface 14a of the peeling 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 may be, for example, 0.03 to 5 μm, or 0.1 to 1 μm. The ceramic green sheet 22 is peeled from the peeling film 10 and then fired to become a dielectric containing, for example, at least one selected from the group consisting of calcium titanate, strontium titanate and barium titanate.

The electrode green sheet 24 is peeled from the peeling film 10 and then fired to become an electrode containing at least one selected from the group consisting of, for example, copper, nickel and alloys thereof.

The ceramic parts sheet described above can be manufactured, for example, by the following manufacturing method. One embodiment of a method for producing a ceramic component sheet is a composition and solvent containing a silicone resin having a reactive functional group, a (meth) acrylate having a reactive functional group, and an acrylic silicone graft polymer having a reactive functional group. A step of coating a slurry containing the above-mentioned on a base material (coating step), a step of reducing the content of the solvent in the slurry to provide a photosensitive layer (solvent reduction step), and exposing the photosensitive layer. A step of forming a peeling layer composed of a cured product of the above composition (exposure step) and a group consisting of a ceramic powder and an electrode material on the surface of the peeling layer opposite to the base material side. A step of forming at least one green sheet selected from the group consisting of a ceramic green sheet and an electrode green sheet by applying a paste containing at least one selected and removing the solvent (sheet forming step). , Have.

The coating step, the solvent reducing step, and the exposure step are common to the above-mentioned manufacturing method of the peeling film 10, and the above-mentioned description can be applied. In the method for producing a ceramic component sheet, the coating step, the solvent reduction step, and the exposure step may be omitted by using the peeling film 10 described above.

In the sheet forming step, a paste containing ceramic powder (ceramic paste) and a paste containing an electrode material (electrode paste) are each applied on the surface 14a of the peeling film 10 on the side opposite to the base film 12 side.

The ceramic paste contains, for example, a dielectric material (ceramic powder) and an organic vehicle. As the dielectric raw material, various compounds that become composite oxides or oxides by firing, for example, carbonates, nitrates, hydroxides, organic metal compounds, and the like can be appropriately selected and used. The average particle size of the dielectric raw material is preferably 0.4 μm or less, more preferably 0.1 to 3.0 μm. The ceramic paste may further contain a dispersant, a plasticizer, a charge remover, a dielectric, a glass frit, an insulator and the like, if necessary.

The electrode paste is selected from the group consisting of, for example, conductive materials such as various conductive metals and alloys, and materials that become conductive materials after firing with various oxides, organic metal compounds, and resinates. Contains one and an organic vehicle. Examples of the conductor material include nickel metals, nickel alloys, and mixtures thereof. The electrode paste may further contain a plasticizer. When the electrode paste contains a plasticizer, the wettability of the electrode paste to the peeling layer can be further improved. Examples of the plasticizer include phthalates such as benzyl butyl phthalate (BBP), adipic acid, phosphoric acid esters, glycols and the like.

As the organic vehicle contained in the ceramic paste and the electrode paste, a binder resin dissolved in an organic solvent can be used. Examples of the binder resin include ethyl cellulose, acrylic resin, butyral resin, polyvinyl acetal, polyvinyl alcohol, polyolefin, polyurethane, polystyrene, and copolymers thereof. The binder resin preferably contains a butyral resin, specifically a polyvinyl butyral resin. By using a butyral resin as the binder resin, the mechanical strength of the ceramic green sheet 22 and the electrode green sheet 24 can be increased. The degree of polymerization of the polyvinyl butyral resin is preferably 1000 to 1700, and more preferably 1400 to 1700. When a butyral resin is used as the binder resin, the peelability of the ceramic green sheet 22 and the electrode green sheet 24 is further improved by using an alkylenediol di (meth) acrylate monomer as a raw material for the peeling layer 14. be able to.

Examples of the organic solvent used in the organic vehicle include terpineol, alcohol, butyl carbitol, acetone, toluene, xylene, benzyl acetate and the like. One of these organic solvents may be used alone, or two or more of these organic solvents may be used in combination. Examples of the alcohol include methanol, ethanol, propanol, butanol and the like.

The above-mentioned ceramic paste is applied onto the surface 14a of the peeling film 10 by, for example, a doctor blade device or the like. Then, the applied ceramic paste is heat-dried in a commercially available drying device 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 5 to 25% as compared to before drying.

Next, the electrode paste is printed on the surface 22a of the formed ceramic green sheet 22 using, for example, a screen printing device so as to have a predetermined pattern. Then, the applied electrode paste is heated and dried in a commercially available drying device at a temperature of, for example, 50 to 100 ° C. for 1 to 20 minutes to form an electrode green sheet 24. As a result, the ceramic component sheet 20 in which the peeling 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 by using the peeling film 10 having the peeling layer 14, the green sheet 26 composed of the ceramic green sheet 22 and the electrode green sheet 24 is sufficiently excellent in peeling property, and the green sheet 26 is sufficiently excellent in peeling property. The peeling residue can be sufficiently reduced. Therefore, the variation in the thickness of the green sheet 26 is sufficiently reduced, and the occurrence of pinholes can be sufficiently suppressed.

Further, when the electrode paste or the ceramic paste is applied to the surface 14a of the peeling layer 14, the generation of repelling is sufficiently suppressed, so that the green sheet 26 with less variation in pinholes and thickness can be easily formed. Can be done. This makes it easier to manufacture the monolithic ceramic capacitor.

A method for manufacturing a multilayer ceramic capacitor, which is an embodiment of a method for manufacturing ceramic parts, will be described below.

One embodiment of the method for manufacturing a multilayer ceramic capacitor includes a step of preparing a plurality of ceramic component sheets (preparation step), a lamination step of laminating a plurality of green sheets of ceramic component sheets to obtain a laminate, and firing the laminate. It has a firing step of obtaining a sintered body and an electrode forming step of forming a terminal electrode on the sintered body to obtain a monolithic ceramic capacitor.

In the preparatory step, a plurality of ceramic component sheets 20 manufactured by the above-mentioned method for manufacturing ceramic component sheets are prepared. Next, in the laminating step, the green sheets 26 of the plurality of ceramic component sheets 20 are laminated to obtain a laminated body in which the plurality of green sheets 26 are laminated.

An example of the laminating process will be described in detail. First, the peeling film 10 of the ceramic component sheet 20 is peeled off to obtain a 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. After that, the peeling film 10 is peeled off from the laminated ceramic component sheet 20. By repeating such a procedure and laminating the green sheet 26, a laminated body can be obtained. That is, in this laminating step, a laminated body is formed by laminating the ceramic component sheet 20 on the green sheet 26 and then repeating the procedure of peeling the peeling film 10 a plurality of times.

Another example of the laminating 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 peeling film 10 has been peeled off face each other. By repeating such a procedure and sequentially laminating the green sheets 26, a laminated body can be obtained. That is, in this laminating step, a laminated body is formed by repeating the procedure of laminating the green sheet 26 from which the peeling film 10 has been peeled off a plurality of times.

The number of laminated green sheets in the laminated body is not particularly limited, and may be, for example, tens to hundreds of layers. 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 laminated body. After forming the laminate, the laminate may be cut to obtain green chips.

In the firing step, the laminated body (green chips) obtained in the laminating step is fired to obtain a sintered body. The firing conditions are 1100 to 1300 ° C., and it is preferable to carry out the firing in an atmosphere such as a mixed gas of humidified nitrogen and hydrogen. However, the partial pressure of oxygen in the atmosphere at the time of firing is preferably ^10-2 Pa or less, more preferably ^10-2 to ^10-8 Pa. Before firing, it is preferable to perform a binder removal treatment on the laminated body. The binder removal process can be performed under normal conditions. When a base metal such as nickel or nickel alloy is used as the conductor material of the internal electrode layer (electrode green sheet 24), the temperature is preferably 200 to 600 ° C.

After firing, heat treatment may be performed to reoxidize the dielectric layer constituting the sintered body. The holding temperature or the maximum temperature in the heat treatment is preferably 1000 to 1100 ° C. Oxygen partial pressure during the heat treatment is preferably higher oxygen partial pressure than the reducing atmosphere at firing, and more preferably ¹⁰ -2 Pa~1Pa. It is preferable that the sintered body thus obtained is subjected to end face polishing by, for example, barrel polishing, sandblasting, or the like.

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

In the method for manufacturing ceramic parts of the present embodiment, since the above-mentioned ceramic parts sheet is used, it is possible to sufficiently suppress the occurrence of pinholes in the obtained ceramic parts, that is, the multilayer ceramic capacitor. Therefore, a monolithic ceramic capacitor can be formed with a high yield.

FIG. 3 is a schematic cross-sectional view showing an example of a ceramic component. The multilayer ceramic capacitor 100 shown in FIG. 3 includes an interior portion 40 and a pair of exterior portions 50 that sandwich the interior portion 40 in the stacking direction. The multilayer ceramic capacitor 100 of the present embodiment has a terminal electrode 60 on the side surface.

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

The exterior portion 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.

Although some embodiments have been described above, the present disclosure is not limited to the above embodiments.

Hereinafter, the contents of the present disclosure will be described in more detail with reference to Examples and Comparative Examples. However, the present disclosure is not limited to the following examples.

(Example 1)
In the reaction vessel, as the component (A), in the following general formula (1), m is 10 to 100, R ¹ and R ² are propyl groups, 0.5 parts by mass of a silicone resin, and the component (B) is used. 85 parts by mass of trimethylpropan triacrylate, 15 parts by mass of acrylic silicone graft polymer having an acryloyl group as component (C), 20 parts by mass of propylene glycol monomethyl ether as a solvent, and methyl ethyl ketone (MEK) and isopropyl alcohol (IPA). ) (A solution in which MEK and IPA were mixed in a volume ratio of 1: 1) was measured by 400 parts by mass, and a colorless and transparent solution was obtained by stirring and mixing.

A coating liquid (slurry) was prepared by adding 2.5 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone as a photopolymerization initiator to the above solution. Using a bar coater, the prepared coating liquid is applied to a biaxially stretched polyethylene terephthalate (PET) film (base film, thickness: 38 μm) and dried with hot air at a heating temperature of 80 ° C. for 30 seconds to evaporate the solvent. The photosensitive layer was formed on the PET film. The formed photosensitive layer was irradiated with ultraviolet rays in a nitrogen atmosphere having an oxygen concentration of 100 ppm to obtain a peeling film having a peeling layer having a thickness of 1016 nm. For the irradiation of ultraviolet rays, the integrated light intensity was set to 250 mJ / cm ² . The thickness of the peeling layer was measured using a spectrophotometer (manufactured by JASCO Corporation, trade name: V-670).

The peeling film obtained by the above method was subjected to XPS measurement, appearance, and peelability evaluation for the peeling layer according to the method shown below. The results are shown in Table 1 below.

<XPS measurement (measurement of element distribution of peeling layer by X-ray photoelectron spectroscopy, analysis in depth direction)>
XPS measurement (depth analysis) was performed on the peeled layer of the obtained peeled film. More specifically, the composition analysis of the surface of the peeling layer by XPS measurement and the etching of the surface of the peeling layer by sputtering using argon ions are used in combination to gradually expose the inside of the peeling layer on each surface. Composition analysis was performed.

Instead of the above solution, a solution in which polydimethylsiloxane was dissolved in a mixed solvent of toluene, MEK and IPA was used to form a peeling layer on the PET film in the same manner as in Example 1, and XPS measurement (depth) was performed. Direction analysis) was performed. In the example using only polydimethylsiloxane, the peak intensity of silicon was 30,000 (average value) regardless of the depth direction.

FIG. 4 is a graph showing the results of the depth direction analysis of the peeling layer by XPS measurement. In the graph, the vertical axis shows the peak intensity of silicon atoms (value converted to a value based on the measured value in the peeling layer composed of polydimethylsiloxane), and the horizontal axis shows the depth from the peeling layer surface (etching time). The value converted to the depth from the peeled layer surface) is shown. That is, the graph shows the distribution of silicon atoms along the depth direction of the peeling layer. In FIG. 4, the results of the examples are shown by solid lines, and the results of the comparative examples are shown by broken lines.

<Evaluation of minute roughness Sp>
The micro-roughness Sp of the peeling layer in the obtained peeling film conforms to the method described in JIS B 0601: 2013 with respect to the surface (the surface to be the peeling surface) opposite to the base film of the peeling layer. Then, the measurement was performed and determined using the Micromap System (optical interferometry type three-dimensional non-contact surface shape measurement system) of Ryoka System Co., Ltd.

<Evaluation of appearance>
The appearance of the peeling layer in the obtained peeling film was visually observed and evaluated according to the following criteria A to D.
A: No defects were observed in the area of 20 cm x 20 cm, and it was mirror-shaped.
B: In the region of 20 cm × 20 cm, the number of observed defects is 5 or less, and interference fringes are generated around the defects (with fluctuation in thickness).
C: There are 5 or more defects observed in the area of 20 cm × 20 cm, or it is difficult to count the number of defects and there is no gloss.
D: In the region of 20 cm × 20 cm, the number of observed defects is 10 or more, and the diameter of at least one of the observed defects is 1 mm or more.

For reference, a photograph of the appearance of the peeling film prepared in Example 3 and Comparative Example 6 is shown in FIG. FIG. 5A shows the appearance of the peeling film prepared in Example 3, and FIG. 5B shows the appearance of the peeling film prepared in Comparative Example 6. As shown in FIG. 5 (a), in the release film prepared in Example 3, the reflection of the fluorescent lamp on the release film was observed, and no defect was observed on the surface of the peeling layer, which was mirror-like. It was confirmed that On the other hand, in the peeling film prepared in Comparative Example 6, as shown in FIG. 5 (b), the image of the fluorescent lamp reflected on the peeling film was not clear, and innumerable defects were observed on the surface of the peeling layer. It was confirmed that the appearance was inferior.

<Evaluation of peelability>
The peeling property of the peeling layer in the obtained peeling film is based on the "Adhesive strength test method for peeling the peeling liner from the tape adhesive surface" described in ISO 29862: 2007 (JIS Z 0237: 2009) 180 ° peeling. The measurement was carried out as follows. A peeling tester (manufactured by Shimadzu Corporation, product name: Autograph AG-X (load cell SBL-10N, load: 10N)) was used for the measurement.

First, the obtained peeling film was placed on the washed plate glass so that the base film was in contact with the base film. Next, the adhesive surface of the 1-inch wide adhesive tape (manufactured by Nitto Denko Corporation, trade name: 31B) was adhered using a rubber roller so as to be in contact with the peeling layer of the peeling film so as not to allow air to enter. .. After bonding, the base film side of the peeling film was attached to the test plate of the peeling tester. As a gripping allowance, the adhesive tape was bent 180 ° and connected upward to a gripping jig connected to the load cell. One minute after the adhesive tape was adhered to the peeling film, the average value of the load detected by the load cell was obtained when the adhesive tape was pulled up at a load speed of 300 mm / min. By converting the obtained average value into the case where an adhesive tape having a width of 10 mm was used, the peeling property of the peeling film was obtained.

(Examples 2 to 12, Comparative Examples 1 to 7)
A peeling film was obtained in the same manner as in Example 1 except that the raw material and the charging ratio (mass ratio) were changed as shown in Table 1. The obtained peeling film was evaluated for the thickness of the peeling layer, XPS measurement for the peeling layer, appearance, and peeling property. The results are shown in Table 1 below.

In Table 1, the following compounds were used as the components (A), (B) and (C).
Component (A): Silicone resin having a reactive functional group a1: Dimethylpolysiloxane having acryloyl groups at both ends (compound represented by the formula (X))
a2: Polydimethylsiloxane having an acryloyl group in the side chain (manufactured by Big Chemie Co., Ltd., trade name: BYK-3500)
(B) component: (meth) acrylate having a reactive functional group b1: trimethylolpropane triacrylate b2: dipentaerythritol hexaacrylate (C) component: acrylic silicone graft polymer having a reactive functional group Acryloyl silicone having an acryloyl group Graft polymer

According to the present disclosure, it is possible to provide a peeling film having excellent peelability and sufficient smoothness, and a method for producing the same. According to the present disclosure, it is also possible to provide a ceramic component sheet having the above-mentioned peeling film and capable of producing a thin-film green sheet, and a method for producing the same. According to the present disclosure, it is possible to further provide a method for manufacturing a multilayer ceramic capacitor using the peeling film as described above.

10 ... peeling film, 12 ... base film, 14 ... peeling layer, 14a ... surface (peeling surface), 20 ... ceramic parts sheet, 22 ... ceramic green sheet, 22a ... surface, 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.

Claims (5)

A method for producing a peeling film having a base material and a peeling layer provided on the base material.
A slurry containing a composition containing a silicone resin having a reactive functional group, a (meth) acrylate having a reactive functional group, and an acrylic silicone graft polymer having a reactive functional group and a solvent is applied onto the substrate. And the process to do
A step of reducing the content of the solvent in the slurry to provide a photosensitive layer, and
A method for producing a peeling film, comprising a step of forming a peeling layer composed of a cured product of the composition by exposing the photosensitive layer. The content of the acrylic silicone graft polymer, wherein, based on the total amount of the (meth) acrylate, further comprising a step of preparing the composition such that 10 to 600 mass%, the peeling film according to claim 1 Production method. The method for producing a peeling film according to claim 1 or 2 , further comprising a step of preparing the composition so that the content of the silicone resin is 0.5% by mass or more. The reactive functional group is at least one functional group selected from the group consisting of a (meth) acryloyl group and a vinyl group.
The method for producing a peeling film according to any one of claims 1 to 3 , wherein the composition further contains a photopolymerization initiator. It is selected from the group consisting of a base material, a peeling layer provided on the base material, and a ceramic green sheet and an electrode green sheet provided on the surface of the peeling layer opposite to the base material side. A method for manufacturing a ceramic component sheet having at least one green sheet.
A slurry containing a composition containing a silicone resin having a reactive functional group, a (meth) acrylate having a reactive functional group, and an acrylic silicone graft polymer having a reactive functional group and a solvent is applied onto the substrate. And the process to do
A step of reducing the content of the solvent in the slurry to provide a photosensitive layer, and
A step of forming a peeling layer composed of a cured product of the composition by exposing the photosensitive layer, and
A ceramic green sheet and a ceramic green sheet and a paste containing at least one selected from the group consisting of ceramic powder and an electrode material are applied to the surface of the peeling layer opposite to the base material side to remove the solvent. A step of forming at least one green sheet selected from the group consisting of electrode green sheets, and
A method for manufacturing a ceramic parts sheet.

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