Manufacturing method for ceramic green sheets

Abstract

Provided is a method which is for manufacturing a ceramic green sheet using a ceramic green sheet-manufacturing release film having a substrate and a release agent layer, and by which the green sheet is easily released, the change in easy releasability over time is small, and excellent easy releasability can be stably achieved even after a long period of time has elapsed since green sheet coating. The problem is solved by a method for manufacturing a ceramic green sheet, the method comprising: a) a step for applying a ceramic slurry onto a ceramic green sheet-manufacturing release film; b) a step for forming a ceramic green sheet from the ceramic slurry applied in the a) step; and c) a step for releasing the ceramic green sheet formed in the b) step from the ceramic green sheet-manufacturing release film, wherein the ceramic green sheet-manufacturing release film has a substrate and a release agent layer provided on at least one side of the substrate, the Si amount Si0 on the surface on the reverse side of the release agent layer from the substrate before the a) step is at least 0.003 g / m2, and the difference between the Si amount Sic on the surface on the reverse side of the release agent layer from the substrate after the step c) and Si0, that is, δSi=Sic-Si0, is at least -0.00027 g / m2.

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing ceramic green sheets, and more specifically, to a method for manufacturing ceramic green sheets that allows for easy peeling of the green sheet, exhibits minimal change in peelability over time, and stably achieves excellent peelability even after a long period of time has elapsed since slurry coating during green sheet manufacturing, and is particularly suitable for use in the manufacture of various ceramic products such as multilayer ceramic capacitors and multilayer ceramic substrates. [Background technology]

[0002] In the manufacturing of sheet-like ceramic components, a method of manufacturing ceramic green sheets using release films for ceramic green sheet manufacturing has been conventionally employed. For example, to manufacture multilayer ceramic products such as multilayer ceramic capacitors and multilayer ceramic substrates, ceramic green sheets are formed on release films for ceramic green sheet manufacturing, and multiple sheets of the resulting ceramic green sheets are stacked and fired. In recent years, with the miniaturization and performance improvement of electronic devices, multilayer ceramic capacitors and multilayer ceramic substrates have been miniaturized and multilayered. To achieve multilayering, ceramic green sheets need to be made thinner, and from the viewpoint of preventing defects such as pinholes and thickness variations in thinned ceramic green sheets and effectively suppressing breakage when peeling the thinned ceramic green sheet from the release film, a release film for manufacturing ceramic green sheets has been proposed, which has a substrate and a release agent layer of a specific component, wherein the arithmetic mean roughness (Ra) and maximum protrusion height (Rp) on the side of the release agent layer opposite the substrate are each below a predetermined value, and the arithmetic mean roughness (Ra) and maximum protrusion height (Rp) on the side of the substrate opposite the release agent layer are each within a predetermined numerical range (see, for example, Patent Document 1).

[0003] In the manufacturing of various ceramic products such as multilayer ceramic capacitors and multilayer ceramic substrates, it is required that the ceramic green sheet formed on the release film for manufacturing ceramic green sheets be easily peeled off, from the standpoint of quality and productivity of the ceramic products. However, in conventional methods for manufacturing ceramic green sheets, even if peeling is easy immediately after forming the ceramic green sheet by coating it with slurry, the ease of peeling may decrease if stored for about a week after coating. This can lead to heavy peeling during storage, or the ceramic green sheet may break when peeled after storage, and improvements have been needed. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Release 2013 / 145865 A1 Pamphlet [Overview of the project] [Problems that the invention aims to solve]

[0005] In view of the above technical background, the present invention aims to provide a method for manufacturing a ceramic green sheet using a release film for manufacturing ceramic green sheets having a base material and a release agent layer, wherein the green sheet is easy to peel off, the ease of peeling does not change much over time, and excellent ease of peeling can be stably achieved even after a long period of time has elapsed since the green sheet coating. [Means for solving the problem]

[0006] As a result of intensive studies, the inventors of the present invention have found that in a method for producing a ceramic green sheet using a release film for producing a ceramic green sheet having a base material and a release agent layer provided on at least one of the base materials, the amount of Si on the surface of the release agent layer, and the changes in the amount of Si before and after ceramic slurry coating, green sheet formation, and release are each within a predetermined numerical range, thereby exceeding the limitations of the prior art and achieving high-level easy peelability that can be stabilized over time. The present invention has been completed based on this finding. That is, the present invention relates to [1] a) a step of coating a ceramic slurry on a release film for producing a ceramic green sheet, b) a step of forming a ceramic green sheet from the ceramic slurry coated in the step a), and c) a step of peeling the ceramic green sheet formed in the step b) from the release film for producing a ceramic green sheet, A method for producing a ceramic green sheet having The release film for producing a ceramic green sheet has a base material and a release agent layer provided on at least one of the base materials, The amount of Si, Si0, on the surface of the release agent layer opposite to the base material before the step a) is 0.003 g / m c or more, The amount of Si, Si c on the surface of the release agent layer opposite to the base material after performing the step c), and the difference, δSi = Si c - Si0, is -0.00027 g / m 2 or more, Relates to the method for producing a ceramic green sheet described above.

[0007] <00s0092>Hereinafter, [2] to [6] are all preferred embodiments or one embodiment of the present invention. [2] The method for producing a ceramic green sheet according to [1], wherein the ceramic slurry contains polyvinyl butyral having a hydroxyl value of 20 mol% or more. [3] The method for manufacturing a ceramic green sheet according to [1] or [2], comprising a step of printing an internal electrode on the ceramic green sheet between step b) and step c). [4] The method for manufacturing a ceramic product, comprising a step of manufacturing a ceramic green sheet by the method for manufacturing a ceramic green sheet according to any one of [1] to [3]. [5] The method for manufacturing a ceramic product according to [4], further comprising a step of firing the ceramic green sheet. [6] The method for manufacturing a ceramic product according to [4] or [5], wherein the ceramic product is a multilayer ceramic capacitor or a multilayer ceramic substrate.

[0008] Furthermore, the following, from [1'] to [6'], are all examples of a release film for manufacturing a ceramic green sheet preferably used in the manufacturing method of the present invention. [1'] A release film for manufacturing a ceramic green sheet, comprising a base material and a release agent layer provided on at least one of the base materials, where the amount of Si, Si1, on the surface of the release agent layer opposite to the base material is 0.003 g / m 2 or more, and the difference, δSi = Si2 - Si1, between the amount of Si, Si2, after peeling after applying and drying a ceramic slurry having the following composition on the surface of the release agent layer opposite to the base material and storing it for 1 week in a constant temperature and humidity environment of 23 ± 2°C × 50 ± 5% RH and the above Si1 is -0.00027 g / m 2 or more. The above release film for the ceramic green sheet manufacturing method: A) 45% by mass of barium titanate particles, B) 3.6% by mass of polyvinyl butyral, C) 0.9% by mass of dibutyl phthalate, D) 25% by mass of toluene, and E) 25% by mass of ethanol. A ceramic slurry. [2'] The release film for manufacturing ceramic green sheets according to [1'], wherein the amount of ceramic slurry coated is 50 μm in thickness before drying, the drying conditions are 70°C for 2 minutes, and the peeling is performed at an angle of 180°. [3'] The release film for manufacturing ceramic green sheets according to [1'] or [2'], characterized in that the release agent layer contains a cured product of a curable composition, the curable composition contains at least one reactive compound (a) having at least one reactive functional group selected from the group consisting of a (meth)acryloyl group, a hydroxyl group, and an epoxy group, and the total amount of the reactive compound (a) is 50% or more by mass ratio of the release agent layer. [4'] The release film for manufacturing ceramic green sheets according to [3'], wherein the curable composition comprises, as the reactive compound (a), at least one reactive silicone (a1) having at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups, and a siloxane skeleton, and at least one reactive compound (a2) having the same reactive functional group as the reactive silicone (a1) and having a reactive functional group equivalent of 2000 g / mol or less. [5'] The release film for manufacturing ceramic green sheets according to [4'], wherein the curable composition further contains a film-forming compound (a3) ​​having two or more (meth)acryloyl groups in one molecule. [6'] A release film for manufacturing ceramic green sheets according to any one of [1'] to [5'], wherein the arithmetic mean roughness (Ra) of the surface of the substrate on the release agent layer side is 1 to 70 nm. [Effects of the Invention]

[0009] The manufacturing method of the ceramic green sheet of the present invention is such that the peeling of the ceramic green sheet formed on the peeling film for manufacturing the ceramic green sheet is easy, the change with time of the easy peeling property is small, and excellent easy peeling property can be stably realized even when a long time has passed since the green sheet coating. It realizes technical effects with high practical value at a high level exceeding the limits of the prior art and can be suitably used for the manufacture of various ceramic products. For example, it is possible to significantly improve the productivity of various ceramic products such as multilayer ceramic capacitors and multilayer ceramic substrates, and it can be particularly suitably used in the manufacture thereof.

Brief Description of the Drawings

[0010] [Figure 1] It is a schematic diagram showing an example of the peeling film for manufacturing a ceramic green sheet used in the manufacturing method of the present invention.

Embodiments for Carrying Out the Invention

[0011] The present invention a) A step of coating a ceramic slurry on a peeling film for manufacturing a ceramic green sheet, b) A step of forming a ceramic green sheet from the ceramic slurry coated in the step a), and c) A step of peeling the ceramic green sheet formed in the step b) from the peeling film for manufacturing the ceramic green sheet, which is a manufacturing method of a ceramic green sheet having the peeling film for manufacturing the ceramic green sheet has a base material and a peeling agent layer provided on at least one side of the base material, the amount of Si, Si0, on the surface of the peeling agent layer opposite to the base material before the step a) is 0.003 g / m 2 or more, the amount of Si, Si c on the surface of the peeling agent layer opposite to the base material after performing the step c), and the difference from the above Si0, δSi = Si c-Si0 is -0.00027 g / m 2 That's all. This is a method for manufacturing the ceramic green sheet described above.

[0012] In other words, the present invention provides a method for manufacturing a ceramic green sheet, comprising the steps of: a) coating a ceramic slurry onto a release film for manufacturing ceramic green sheets; b) forming a ceramic green sheet from the ceramic slurry coated in step a); and c) peeling the ceramic green sheet formed in step b) from the release film for manufacturing ceramic green sheets, wherein the amount of Si on the side of the release agent layer of the release film for manufacturing ceramic green sheets that is opposite to the substrate satisfies the following conditions i) and ii). i) The amount of Si (initial Si amount) Si0 on the side of the release agent layer opposite to the substrate prior to step a) is 0.003 g / m 2 That's all. ii) The amount of Si on the side of the release agent layer opposite to the substrate after step c) (amount of Si after release) c And the difference with the above Si0, δSi = Si c -Si0 is -0.00027 g / m 2 That's all.

[0013] Since the initial Si content Si0 and the Si content change δSi are both within the above numerical ranges, and in combination with other technical features of the present invention, the manufacturing method of the present invention using the above-mentioned release film for manufacturing ceramic green sheets allows for easy peeling of the formed ceramic green sheet, exhibits minimal change in peelability over time, and stably achieves excellent easy peelability even after a long period of time has elapsed since the green sheet coating. This enables the realization of technical effects with high practical value at a level that surpasses the limitations of conventional technology. The mechanism by which the above-mentioned numerical ranges for Si0 and δSi enable excellent peelability of the ceramic green sheet and suppression of its deterioration over time is not entirely clear, but Si0 being within the above ranges is 0.003 g / m². 2As a result of the above, the release force of the release film can be stably maintained, and the δSi is -0.00027 g / m² 2 Based on the above, it can be inferred that even after a long period of time has elapsed since the green sheet coating, the amount of Si present on the surface of the release film after peeling remains almost unchanged from the initial amount and is stable over time.

[0014] The Si content of the release film for manufacturing ceramic green sheets used in the manufacturing method of the present invention, on the side opposite the substrate of the release agent layer, is Si0 and Si c This can be measured by methods conventionally known in the art, such as by X-ray fluorescence analysis. More specifically, it can be measured by the method described in the examples of this specification. The change in Si content δSi is obtained by measuring SiO and Si as described above. c Therefore, the equation δSi = Si c -This can be calculated according to Si0.

[0015] The initial Si content (Si0) on the side of the release agent layer opposite the substrate of the release film for manufacturing ceramic green sheets used in the manufacturing method of the present invention is 0.005 to 0.200 g / m². 2 Preferably, it is 0.010 to 0.150 g / m². 2 It is more preferable that the amount be 0.015 to 0.100 g / m². 2 It is particularly preferable that this be the case. The change in Si content δSi on the side of the release agent layer opposite the substrate of the release film used in the manufacturing method of the present invention is from -0.00026 to 0.0025 g / m². 2 Preferably, the value is between -0.00025 and 0.0020 g / m². 2 It is more preferable that the value is between -0.00024 and 0.0017 g / m². 2 It is particularly preferable that this be the case.

[0016] The initial Si amount Si0 on the side of the release agent layer opposite to the substrate, and the Si amount Si after step c) in the manufacturing method of the present invention having steps a) to c) above. cThe change in Si content, δSi, can be appropriately adjusted by adjusting the type and amount of material constituting the release agent layer, the amount of coating of the release agent layer, the drying temperature, the amount of active energy ray irradiation, and other curing conditions. In particular, it can be appropriately adjusted by adjusting the equivalent amount and amount of reactive functional groups of a reactive compound (a) having at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups, a reactive compound (a2) having the same reactive functional group as reactive silicone (a1) and having a reactive functional group equivalent of 2000 g / mol or less, and a film-forming compound (a3) ​​having two or more (meth)acryloyl groups in one molecule.

[0017] As described above, the release film for manufacturing ceramic green sheets used in the manufacturing method of the present invention has a base material and a release agent layer. The release film for manufacturing ceramic green sheets used in the manufacturing method of the present invention only needs to have a base material and a release agent layer, and may or may not have other layers. Therefore, as shown in Figure 1, the release film for manufacturing ceramic green sheets used in the manufacturing method of the present invention may consist only of a base material (13) and a release agent layer (12), or it may have other layers such as an antistatic layer in addition to the base material and release agent layer. The following explains each of the above layers.

[0018] Base material There are no particular restrictions on the base material that constitutes the release film for manufacturing ceramic green sheets used in the method for manufacturing ceramic green sheets of the present invention. Any base material that is conventionally known in the art can be appropriately selected and used. Examples of such base materials include films made of polyester such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polypropylene and polymethylpentene, polycarbonate, and plastics such as ethylene-vinyl acetate copolymer. These may be single layers or multilayer films of two or more layers of the same or different types. Among these, polyester films are preferred, polyethylene terephthalate films are particularly preferred, and biaxially oriented polyethylene terephthalate films are even more preferred. Polyethylene terephthalate films are less likely to generate dust during processing and use, so they can effectively prevent defects in ceramic slurry coating caused by dust, for example.

[0019] Furthermore, to improve adhesion with the release agent layer provided on at least one surface of this substrate, surface treatments such as oxidation or primer treatments can be applied. Examples of oxidation methods include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone treatment, and ultraviolet irradiation treatment. These surface treatment methods are appropriately selected depending on the type of substrate film, but corona discharge treatment is generally preferred in terms of effectiveness and ease of operation. There are no particular restrictions on the thickness of the substrate; the thickness can be set appropriately based on mechanical strength, ease of handling during manufacturing and use, etc. However, it is usually 10 to 300 μm, preferably 12 to 200 μm, and particularly preferably 15 to 125 μm.

[0020] The arithmetic mean roughness (Ra) of the surface of the substrate on the side with the release agent layer is preferably 0.1 to 70 nm, and more preferably 1 to 60 nm. A substrate with an arithmetic mean roughness (Ra) of 0.1 to 70 nm on the surface side of the release agent layer is preferable in terms of substrate handling and suppression of poor conductivity. Furthermore, substrates with an arithmetic mean roughness (Ra) of 1 to 70 nm are relatively easy and inexpensive to obtain, which is also preferable from the viewpoint of the availability and manufacturing cost of the release film for manufacturing ceramic green sheets used in the manufacturing method of the present invention.

[0021] The arithmetic mean roughness (Ra) of the substrate surface opposite to the release agent layer side is preferably 5 to 70 nm, and particularly preferably 10 to 60 nm. By ensuring that the arithmetic mean roughness (Ra) of the substrate surface opposite to the release agent layer is equal to or greater than the lower limit, blocking during winding of the release film for manufacturing ceramic green sheets used in the manufacturing method of the present invention can be effectively suppressed. Furthermore, by ensuring that the Ra is equal to or less than the upper limit, it becomes easier to smooth the surface of the release agent layer.

[0022] Release agent layer There are no particular restrictions on the material of the release agent layer that constitutes the release film for manufacturing ceramic green sheets used in the manufacturing method of the present invention, and the Si content Si0 on the side of the release layer opposite the substrate before step a) is 0.003 g / m². 2 The above is true, and the amount of Si after step c) in the manufacturing method of the present invention having steps a) to c) above. c The difference between this and the above Si0, δSi = Si c -Si0 is -0.00027 g / m 2 Any material can be used as long as the above conditions are met. From the viewpoint of ease of manufacturing and appropriate control of Si content, etc., for the release film for manufacturing ceramic green sheets, it is preferable to form the release layer by coating a curable composition onto a substrate and curing it, and it is particularly preferable to form the release layer by coating and curing a photocurable and / or thermocurable curable composition. That is, it is preferable that the release layer in the release film for manufacturing ceramic green sheets used in the manufacturing method of the present invention contains a cured product of a curable composition.

[0023] curable composition In the release film for manufacturing ceramic green sheets used in the manufacturing method of the present invention, the curable composition preferably used for forming the release agent layer preferably contains at least one reactive compound (a) having at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups. By using a curable composition containing at least one reactive compound (a) having at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups, the release agent layer of the release film for manufacturing ceramic green sheets of this embodiment can be formed easily and with good control over the Si content, etc.

[0024] The above curable composition may contain only one type of reactive compound (a) having at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups, or it may contain two or more types of reactive compounds (a) having at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups. From the viewpoint of controlling various properties such as the curability, peelability, and Si content of the release agent layer, it is preferable to use two or more types of reactive compounds (a) in combination, and in particular, it is preferable to use a combination of the reactive silicone (a1) and the crosslinking compound (a2) described later, and it is even preferable to combine it with the film-forming compound (a3) ​​described later.

[0025] The above curable composition may consist only of a reactive compound (a) having at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups, and may also contain other components such as solvents, radical initiators, cationic initiators, leveling agents, antistatic agents, dyes, and pigments. The amount of reactive compound (a) having at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups is preferably 50% by mass or more of the mass of the release agent layer, and particularly preferably 60 to 96% by mass.

[0026] Reactive compound (a) The reactive compound (a) preferably used in forming the release agent layer in the release film for manufacturing ceramic green sheets used in the manufacturing method of the present invention has at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups. By having at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups, photocurability and / or thermocurability can be imparted to the curable composition.

[0027] The reactive compound (a) may have one or more reactive functional groups, but from the viewpoint of photocurability and / or thermosetting properties, it is preferable to have two or more reactive functional groups, more preferably 2 to 15 reactive functional groups, and particularly preferable 2 to 10 reactive functional groups. When the reactive compound (a) has two or more reactive functional groups, it may have two or more of the same type of reactive functional group, or it may have a total of two or more combinations of different types of reactive functional groups. From the viewpoint of curability, the reactive compound (a) preferably has a (meth)acryloyl group when using active energy rays, and when using thermosetting in combination, a material containing a hydroxyl group or an epoxy group can be appropriately selected.

[0028] Preferred examples of the reactive compound (a) include a reactive silicone (a1) having at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups, and a siloxane skeleton; a reactive compound (a2) having the same reactive functional groups as the reactive silicone (a1) and having a reactive functional group equivalent of 2000 or less; and a film-forming compound (a3) ​​having two or more (meth)acryloyl groups in one molecule. In the curable composition, it is preferable to use a combination of reactive silicone (a1) and reactive compound (a2), and it is even more preferable to use a combination of these.

[0029] Reactive silicone (a1) The above curable composition preferably contains a reactive silicone (a1) having at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups, as the reactive compound (a), and a siloxane skeleton. By using reactive silicone (a1), the desired peelability can be imparted to the surface of the release agent layer, making it even easier to peel off the ceramic green sheet. Furthermore, the amount of Si and its changes can be appropriately controlled. The reactive silicone (a1) may have at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups, and may have a siloxane skeleton; no other restrictions are imposed. By having at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups, the reactive functional group reacts upon irradiation with active energy rays or through a separate reaction step (e.g., a heating step), incorporating the siloxane skeleton into a crosslinked structure and fixing it in place. This allows for more effective control of the peelability of the release agent layer, the Si content, and changes therein. Epoxy groups are particularly preferred as the reactive functional group.

[0030] The reactive functional group may be introduced at one end of the siloxane skeleton, at both ends, or in the side chain. Preferably, at least one reactive functional group selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups is introduced in two or more molecules of reactive silicone (a1). If there are two or more reactive functional groups, there may be two or more of the same type of reactive functional group, or there may be a total of two or more combinations of different reactive functional groups. In addition to reactive functional groups selected from the group consisting of (meth)acryloyl groups, hydroxyl groups, and epoxy groups, the material may further contain vinyl groups, maleimide groups, carboxyl groups, isocyanate groups, and the like.

[0031] There are no particular restrictions on the molecular weight of the reactive silicone (a1), but from the viewpoint of appropriate exfoliation properties and controllability of Si content and its changes, it is preferably 5,000 to 100,000, and particularly preferably 10,000 to 70,000.

[0032] In the above curable composition, the reactive silicone (a1) may be used alone or in combination of two or more types. There are no particular restrictions on the content of reactive silicone (a1) in the above curable composition, but it is preferably 0.1 to 20% by mass, and particularly preferably 0.2 to 15% by mass, based on the total mass of the release agent layer.

[0033] Reactive compound (a2) (crosslinking compound (a2)) The above curable composition preferably contains, as the reactive compound (a), a reactive compound (a2) having the same reactive functional groups as the reactive silicone (a1) and having a reactive functional group equivalent of 2000 g / mol or less. It is particularly preferable to use the reactive compound (a2) in combination with the reactive silicone (a1). The reactive compound (a2) functions as a crosslinking agent for reactive silicone (a1), etc., promoting the effect of the curable composition and allowing the reactive silicone (a1), etc., to be incorporated into and fixed in the crosslinked structure. This further improves the stain prevention and other performance of the ceramic green sheet. In view of its function as a crosslinking agent, the reactive compound (a2) is also referred to as "crosslinkable compound (a2)" in this specification.

[0034] The reactive functional group equivalent of reactive compound (a2) is 2000 g / mol or less, preferably 1800 g / mol or less, and particularly preferably 1700 g / mol or less. By having a reactive functional group equivalent of 2000 g / mol or less, the material will have a sufficient number of (meth)acryloyl groups, hydroxyl groups, and / or epoxy groups to achieve appropriate crosslinking performance. The reactive compound (a2) preferably has a total of one or more reactive functional groups ((meth)acryloyl groups, hydroxyl groups, and / or epoxy groups), preferably 2 to 15, and particularly preferably 2 to 6. Having the number of reactive functional groups within the above range allows for even more appropriate crosslinking performance.

[0035] There are no particular restrictions on the molecular weight of the crosslinkable compound (a2), but from the viewpoint of crosslinking performance, it is preferably between 150 and 4000, and particularly preferably between 150 and 3000. The crosslinkable compound (a2) may have a siloxane skeleton, and in this case, by introducing a sufficient siloxane skeleton into the release agent layer along with the siloxane skeleton of the reactive silicone (a1), even more desirable release performance can be achieved.

[0036] In the above curable composition, the crosslinking compound (a2) may be used alone or in combination of two or more types. There are no particular restrictions on the content of the crosslinking compound (a2) in the above curable composition, but it is preferably 0.08 to 99% by mass, more preferably 0.4 to 50% by mass, even more preferably 0.7 to 30% by mass, and particularly preferably 1.0 to 15% by mass, based on the total mass of the release agent layer. Furthermore, based on the amount of reactive silicone (a1) used, it is preferably 81 to 9900 parts by mass, and particularly preferably 85 to 1000 parts by mass, per 100 parts by mass of reactive silicone (a1).

[0037] It is also preferable to use a compound with excellent film-forming properties as the reactive compound (a) in the above curable composition. The compound with excellent film-forming properties may be either a compound having a (meth)acryloyl group or a compound having a hydroxyl group, but it is preferable to use a film-forming compound (a3) ​​having two or more (meth)acryloyl groups in one molecule. Film-forming compound (a3) The above curable composition preferably contains, as the reactive compound (a), a film-forming compound (a3) ​​having two or more (meth)acryloyl groups in one molecule. By including a film-forming compound (a3) ​​having two or more (meth)acryloyl groups in one molecule, the curable composition can be cured by irradiation with active energy rays. The film-forming compound (a3) ​​may be a monomer, oligomer, or polymer, or a mixture thereof. Preferably, the film-forming compound (a3) ​​is a (meth)acrylic acid ester. Here, (meth)acrylic acid ester means both acrylic acid esters and methacrylic acid esters. The same applies to other similar terms.

[0038] The (meth)acrylic acid ester is preferably at least one selected from polyfunctional (meth)acrylate monomers and (meth)acrylate oligomers, and more preferably at least one selected from bifunctional or more (meth)acrylate monomers and (meth)acrylate oligomers, and even more preferably a trifunctional or more (meth)acrylate monomer. Being bifunctional or more, and more preferably trifunctional or more, results in excellent curability of the curable composition and also better peelability of the surface of the resulting release agent layer.

[0039] There are no particular restrictions on the (meth)acryloyl group equivalent of the film-forming compound (a3), and a wide range of film-forming compounds (a3) ​​having a (meth)acryloyl group equivalent can be used as long as they can satisfy the conditions for the amount of Si and its change specified in the present invention. From the viewpoint of achieving even better peelability and controllability of various properties such as Si content, the (meth)acryloyl group equivalent of the film-forming compound (a3) ​​is preferably 300 g / mol or less, and particularly preferably 260 g / mol or less.

[0040] Examples of polyfunctional (meth)acrylate monomers include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, ethylene oxide-modified phosphate di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, and isocyanurate di(meth)acrylate. Examples include trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris((meth)acryloxyethyl) isocyanurate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like. These can be used individually or in combination of two or more types.

[0041] Examples of polyfunctional (meth)acrylate oligomers include polyester acrylate oligomers, epoxy acrylate oligomers, urethane acrylate oligomers, polyether acrylate oligomers, polybutadiene acrylate oligomers, and silicone acrylate oligomers.

[0042] Polyester acrylate oligomers can be obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends, obtained by the condensation of a polycarboxylic acid and a polyhydric alcohol, with (meth)acrylic acid, or by esterifying the terminal hydroxyl groups of an oligomer obtained by adding an alkylene oxide to a polycarboxylic acid with (meth)acrylic acid.

[0043] Epoxyacrylate oligomers can be obtained, for example, by reacting (meth)acrylic acid with the oxirane ring of a relatively low molecular weight bisphenol-type epoxy resin or novolac-type epoxy resin to esterify it. Alternatively, carboxyl-modified epoxy acrylate oligomers, obtained by partially modifying epoxy acrylate oligomers with dibasic carboxylic acid anhydrides, can also be used.

[0044] Urethane acrylate oligomers can be obtained, for example, by esterifying polyurethane oligomers, which are obtained by the reaction of polyether polyols or polyester polyols with polyisocyanates, with (meth)acrylic acid.

[0045] Polyether acrylate oligomers can be obtained by esterifying the hydroxyl groups of polyether polyols with (meth)acrylic acid.

[0046] In the above curable composition, the film-forming compound (a3) ​​may be used alone or in combination of two or more types. There are no particular restrictions on the content of the film-forming compound (a3) ​​in the above curable composition, but it is preferably 50 to 90% by mass, and particularly preferably 60 to 85% by mass, based on the total mass of the release agent layer.

[0047] The release agent layer can be formed by coating at least one surface of the substrate with the raw material for the release agent layer, preferably the curable composition described above, drying it as necessary, and curing it by irradiation with active energy rays such as light. If the reactive functional group of reactive compound (a) reacts with heat, the reaction can be caused by drying at this time, and reactive compound (a) preferably having a siloxane skeleton can be incorporated into the crosslinked structure. There are no particular restrictions on the coating method of the curable composition, and for example, gravure coating, bar coating, spray coating, spin coating, knife coating, roll coating, die coating, etc. can be used.

[0048] Typically, ultraviolet light and electron beams are used as active energy rays. The irradiation dose of active energy rays varies depending on the type of energy ray, but for example, in the case of ultraviolet light, it ranges from 10 to 1000 mJ / cm². 2 Preferably, 20 to 500 mJ / cm² is preferred, and especially 20 to 500 mJ / cm². 2 This is preferable. In the case of electron beams, a dose of approximately 0.1 to 50 kGy is preferable.

[0049] The thickness of the release agent layer is preferably 0.05 to 2 μm, and particularly preferably 0.2 to 1.5 μm. A release agent layer thickness of 0.05 μm or more is preferable from the viewpoint of smoothness of the surface of the release agent layer and suppression of pinholes and thickness unevenness in the ceramic green sheet. A release agent layer thickness of 2 μm or less is preferable from the viewpoint of suppressing curling due to curing shrinkage of the release agent layer. It is also preferable from the viewpoint of suppressing blocking and static charge.

[0050] Other layers The release film for manufacturing ceramic green sheets used in the manufacturing method of the present invention may have layers other than the above-mentioned substrate and release agent layer, such as a protective layer, adhesive layer, antistatic layer, etc. The substrate and the release agent layer may be directly laminated together, or they may be laminated together via other layers such as an adhesive layer.

[0051] Release film for manufacturing ceramic green sheets In the method for manufacturing ceramic green sheets of the present invention, it is preferable to use the various release films for manufacturing ceramic green sheets described in detail above as appropriate. However, the release films that can be used in the manufacturing method of the present invention are not limited to these, and the Si content Si0 on the side of the release agent layer opposite to the substrate before step a) is 0.003 g / m². 2 The above is true, and the amount of Si on the side of the release agent layer opposite to the substrate after step c) is also Si c And the difference with the above Si0, δSi = Si c -Si0 to -0.00027g / m 2 Various types of release films can be used as appropriate, to the extent that the above conditions can be met.

[0052] Manufacturing method for ceramic green sheets The present invention provides a method for manufacturing ceramic green sheets, comprising the following steps a) to c). a) Process of coating a ceramic slurry onto a release film for manufacturing ceramic green sheets. b) A step of forming a ceramic green sheet from the ceramic slurry coated in step a) above. c) A step of peeling the ceramic green sheet formed in step b) above from the ceramic green sheet manufacturing release film. The process includes the above-described specific steps a) to c), and the Si content Si0 on the side of the release agent layer opposite the substrate before step a) is 0.003 g / m 2 The above is true, and the amount of Si on the side of the release agent layer opposite to the substrate after step c) is also Si c And the difference with the above Si0, δSi = Si c -Si0 is -0.00027 g / m³ 2 As a result of the above, the method for manufacturing ceramic green sheets of the present invention makes it easy to peel the ceramic green sheet from the release film, and the ease of peeling changes little over time. Furthermore, it is possible to stably achieve excellent easy peeling even after a long period of time has elapsed since the green sheet coating. These technical effects have high practical value and can be achieved at a level that surpasses the limitations of conventional technology.

[0053] a) Coating of ceramic slurry In step a) of the method for manufacturing the ceramic green sheet of the present invention, for example, conventional techniques used in the art for coating a ceramic slurry onto a release film for manufacturing ceramic green sheets can be used as appropriate, and for example, the following techniques can be used.

[0054] Ceramic slurry There are no particular restrictions on the ceramic slurry used in step a) of the present invention; for example, a ceramic slurry that has been conventionally used in the manufacture of ceramic green sheets in the art can be used as appropriate.

[0055] The ceramic slurry preferably contains ceramic particles and a solvent, and it is preferable that the ceramic particles are dispersed in the solvent. As the ceramic particles mentioned above, inorganic compound particles capable of forming ceramics by sintering can be used. Examples of inorganic compounds include oxides, nitrides, oxynitrides, and borides of metals or metalloids. More specific examples of inorganic compounds include perovskite-type compounds such as barium titanate (BaTiO3), calcium titanate (CaTiO3), strontium titanate (SrTiO3), or calcium zirconate (CaZrO3) and strontium zirconate (SrZrO3). When these inorganic compounds are used as the main component in ceramic particles, minor components such as Mn, Mg, Si, Co, Ni, or rare earth elements may be included in lower amounts than the main component.

[0056] The particle size of the ceramic particles should preferably be 1 μm or less for the primary particles.

[0057] The solvent may be an organic solvent or an inorganic solvent such as an aqueous solvent, but an organic solvent is preferred from the viewpoint of ease of solvent removal when forming the ceramic green sheet in step b) described below. As an organic solvent, a general type can be used and can be appropriately selected depending on the drying temperature during green sheet formation and the type of binder used. Generally, aromatic, alcohol, ester, ketone, and hydrocarbon solvents are used, and it is also possible to use a mixture of these. There are no particular restrictions on the boiling point of the solvent, but it is preferably between 60 and 130°C, and particularly preferably between 70 and 130°C.

[0058] From the viewpoint of ease of handling of the ceramic green sheet, it is preferable that the ceramic slurry contains a binder in addition to ceramic particles and a solvent. As the binder mentioned above, various binders conventionally used in the manufacture of ceramic green sheets in this art can be used as appropriate. For example, polyvinyl butyral, urethane resin, polyvinyl acetate resin, acrylic resin, cellulose resin, etc., can be used as appropriate. Among these, polyvinyl butyral and acrylic can be used particularly preferably. It is especially preferable to use polyvinyl butyral with a hydroxyl value of 20 mol% or more. There are no particular restrictions on the amount of binder used, but it is preferably 3 to 20 parts by mass, and particularly preferably 5 to 15 parts by mass, per 100 parts by mass of ceramic particles.

[0059] In addition to the ceramic particles, solvent, and optional binder, the ceramic slurry may also contain other components such as plasticizers, surfactants, dispersion stabilizers, and antistatic agents. Examples of suitable plasticizers include dibutyl phthalate and fatty acid esters.

[0060] A ceramic slurry can be produced by stirring and mixing the aforementioned ceramic particles, an organic solvent, and optionally other components such as a binder and a plasticizer. There are no particular restrictions on the method of stirring and mixing; methods and equipment conventionally used in the manufacture of ceramic slurries in this technology can be used as appropriate. For example, stirring and mixing can be done using a ball mill. Using a ball mill allows for simultaneous adjustment of the particle size of the ceramic particles.

[0061] In step a), the method for applying the ceramic slurry can be appropriately selected depending on the viscosity of the ceramic slurry and the type and thickness of the ceramic green sheet to be formed in step b). For example, applicators, on-roll die coaters, reduced-pressure die coaters, off-roll die coaters, slit coaters, curtain coaters, pull-up coaters, knife coaters, cast coaters, reverse roll coaters, blade coaters, screen printing methods, etc., can be used as appropriate.

[0062] b) Green sheet formation process, In step a), a ceramic green sheet can be formed on a release film by removing the solvent from the coated ceramic slurry in step b) through drying or other means. There are no particular restrictions on the temperature and time when drying is performed in step b), but drying can usually be performed at 60 to 100°C, preferably 70 to 100°C, for 30 to 300 seconds, preferably 30 to 200 seconds.

[0063] By ensuring a drying time of 30 seconds or more in step b), the particles within the sheet can be uniformly and densely arranged by the time drying is complete, thereby reducing voids within the green sheet. By keeping the drying time in step b) to 200 seconds or less, the production efficiency in the manufacturing process of ceramic green sheets can be improved.

[0064] By setting the drying temperature in step b) to 70°C or higher, virtually no solvent remains in the ceramic green sheet, preventing the formation of voids in the ceramic during the firing process. Alternatively, by setting the drying temperature to 100°C or lower, the occurrence of blistering and dents on the surface of the green sheet due to rapid evaporation of the solvent can be suppressed. Furthermore, multiple drying zones may be used, with different temperatures for each zone.

[0065] c) Peeling process In step c), the ceramic green sheet formed in step b) is peeled off the release film for manufacturing the ceramic green sheet. There are no particular restrictions on the peeling method in step c), and it can be appropriately selected depending on the material and properties of the ceramic green sheet and subsequent processes. For example, the ceramic green sheet can be peeled off by cutting the ceramic green sheet portion on the release film and then heating it, or by deforming the release film. In the method for manufacturing ceramic green sheets of the present invention, by using the specific release film detailed above, the peeling force in step c) can be reduced (light peeling). This effectively reduces damage to the ceramic green sheet. The peeling force in the peeling process is preferably 5 to 100 (mN / 50mm), and particularly preferably 10 to 50 (mN / 50mm).

[0066] In the method for manufacturing ceramic green sheets of the present invention, by using the specific release film described in detail above, it is possible to maintain a peel force that does not change much from the initial green sheet peel force, even if a long time has passed between steps a) and b) and step c). For example, even after storing the material at room temperature for one week following steps a) and b), the peel force in step c) is preferably 115% or less of the peel force obtained when step c) is performed immediately after steps a) and b), and particularly preferably 110% or less. By having a peel force of 115% or less in step c) after storing the material at room temperature for one week following step b), defects such as green sheet breakage can be suppressed even more effectively.

[0067] Electrode printing process, half-cutting process, die-cutting process In addition to steps a) to c) described above, the method for manufacturing a ceramic green sheet of the present invention may further include steps of electrode printing, half-cutting and / or punching, performed after step b) and before step c).

[0068] By firing the ceramic green sheet obtained by the manufacturing method of the present invention, various ceramic products can be manufactured. According to the above embodiment, which has an electrode printing step before step b) and subsequent step c), after electrode printing, multilayer ceramic capacitors and multilayer ceramic substrates can be manufactured by going through step c) (peeling), lamination and compression, cutting and separation, firing, and external electrode formation steps.

[0069] By firing the ceramic green sheet obtained by the above manufacturing method, various ceramic products can be manufactured. In the manufacturing of multilayer ceramic capacitors, a step of printing internal electrodes onto a green sheet can be included between step b) and step c) above. Subsequently, the multilayer ceramic capacitor can be manufactured through the steps of step c) (peeling), lamination and compression, cutting and separation, firing, and external electrode formation. [Examples]

[0070] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

[0071] In the following examples / comparative examples, the physical properties / characteristics were evaluated using the methods described below. (Si content) Using an X-ray fluorescence analyzer (manufactured by Rigaku Corporation, product name: ZSXPrimusII), the intensity of the specific X-ray Kα of silicon was measured under the following conditions, and the amount of silicon (Si) on the surface of the release agent layer of the release film sample was determined. Analysis area: 30mmφ Analysis element: Si Analytical crystal: PET Output: 50kV, 60mA According to the calibration curve, the specific X-ray Kα intensity of silicon at 1.0 kcps corresponds to a silicon content of 0.003 g / m². 2 It was determined that this corresponds to the silicon content (g / m²), and based on this, the strength (kcps) was determined to be the silicon content (g / m²). 2 It was converted to ).

[0072] (Peeling force) 1) Preparation of ceramic slurry A ceramic slurry, which will be used as a raw material for ceramic green sheets, was prepared by mixing barium titanate (manufactured by Sakai Chemical Industry Co., Ltd., BT-01), polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., S-Rec BH-S), dibutyl phthalate, toluene, and ethanol in a mass ratio of 45:3.6:0.9:25:25. 2) Formation of ceramic green sheet A ceramic slurry prepared in 1) above was applied to the release agent layer side of a release film sample for manufacturing ceramic green sheets to a thickness of 50 μm using an applicator, and dried at 70°C for 2 minutes to form a ceramic green sheet with a thickness of 10 μm. 3) Measurement of the peeling force of the green sheet The release film sample and the ceramic green sheet formed on it in step 2) above were cut into strips measuring 50 mm x 200 mm. The green sheet was peeled from the release film at a 180° angle using a Tensilon (A&D Company, Limited: RTG-1210), and its peel strength was measured.

[0073] The details of each component, such as the resin used in the release agent layer in the examples / comparative examples are as follows. (a3) Polyfunctional acrylate 1 Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Product name: NK Ester A-9300 Tris-(2-acryloxyethyl)isocyanurate (number of functional groups: 3) Acrylic equivalent: 141 g / mol (a3) Polyfunctional acrylate 2 Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Product name: NK Ester A-TMM-3LM-N Pentaerythritol tri and tetraacrylate (number of functional groups: 3 and 4) Acrylic equivalent: 93.7 g / mol (a3) Polyfunctional acrylate 3 Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Product name: NK Ester A-DCP Tricyclodecanedimethanol diacrylate (Number of functional groups: 2) Acrylic equivalent: 304 g / mol (a3) Polyfunctional acrylate 4 Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Product name: NK Ester A-GLY-9E Ethoxylated glycerin triacrylate (number of functional groups: 3) Acrylic equivalent: 217 g / mol (a3) Polyfunctional acrylate 5 Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., Product name: NK Ester A-HD-N 1,6-Hexanediol diacrylate (Number of functional groups: 2) Acrylic equivalent: 113 g / mol (a1) Epoxy-modified silicone 1 Manufactured by Arakawa Chemical Industries, Ltd., Product name: Silikolease UV POLY201 Dimethyl silicon, alicyclic epoxy silicon block copolymer (a2) Epoxy-modified silicone 2 Manufactured by Shin-Etsu Chemical Co., Ltd., Product name: Shin-Etsu Silicone KR-470 A cycloaliphatic epoxy group-containing cyclic siloxane tetrafunctional oligomer Epoxy equivalent: 200 g / mol (a2) Epoxy-modified silicone 3 Manufactured by Shin-Etsu Chemical Co., Ltd., Product name: Shin-Etsu Silicone X-22-169AS Bi-terminal / alicyclic epoxy-modified silicone oil Epoxy equivalent: 500 g / mol (a2) Epoxy-modified silicone 4 Manufactured by Shin-Etsu Chemical Co., Ltd., Product name: Shin-Etsu Silicone X-22-169B Bi-terminal / alicyclic epoxy-modified silicone oil Epoxy equivalent: 1700 g / mol Epoxy-modified silicone 5 Manufactured by Shin-Etsu Chemical Co., Ltd., Product name: Shin-Etsu Silicone KF-102 Side-chain / alicyclic epoxy-modified silicone oil Epoxy equivalent: 3600 g / mol • Cationic initiator 1 Manufactured by Sanshin Chemical Industry Co., Ltd. Product name: San-Aid SI-100 • Radical initiator 1 Product name: Esacure ONE (manufactured by IGM RESINS) α-hydroxyketone type photopolymerization initiator

[0074] [Example 1] A curable composition for the release agent layer was prepared by blending polyfunctional acrylate 1, epoxy-modified silicone 1, epoxy-modified silicone 2, cationic initiator 1, and radical initiator 1 in the mass ratios shown in Table 1. A polyethylene terephthalate film with a thickness of approximately 30 μm and a surface arithmetic mean roughness (Ra) of approximately 20 nm was used as the substrate. The curable composition prepared above was coated onto one surface of the substrate, dried at 100°C for 15 seconds, and then irradiated with ultraviolet light using a high-pressure mercury lamp (cumulative light intensity: approximately 40 mJ / cm²). 2A release agent layer was formed by curing the material, and a release film was manufactured having a substrate and a release agent layer provided on one side of the substrate. The Si content was measured on the surface of the release layer of the manufactured release film using the method described above, and the initial Si content Si0 was obtained. Next, using the method described above, 1) a ceramic slurry was prepared, and 2) a ceramic green sheet was formed. Then, 3) the peeling force of the green sheet was measured to obtain the initial sheet peeling force. Using a separate, unused release film sample and the ceramic slurry obtained in step 1) above, the ceramic green sheet described in step 2) above was formed. After being stored for one week in a constant temperature and humidity environment of 23±2℃ × 50±5%RH, the peeling force of the green sheet described in step 3) above was measured, and the sheet peeling force was obtained after one week. Furthermore, after measuring the sheet peeling force one week later (after peeling the green sheet), the amount of Si on the surface of the release layer of the release film was measured using the method described above. c I obtained it. The results are shown in Table 1.

[0075] [Examples 2 to 4, and Comparative Examples 1 to 4] The release film was manufactured and evaluated in the same manner as in Example 1, except that the formulation of the curing agent composition for the release layer was changed to that shown in Table 1. The results are shown in Table 1.

[0076] [Table 1] [Industrial applicability]

[0077] The present invention provides a highly practical and beneficial technical effect that surpasses the limitations of conventional technologies. This effect includes easy peeling of the ceramic green sheet formed on a release film, minimal change in peelability over time, and stable and excellent peelability even after a long period of time has elapsed since the green sheet coating. It can be suitably used in the manufacture of various ceramic products. For example, it can significantly improve the productivity of various ceramic products such as multilayer ceramic capacitors and multilayer ceramic substrates, and can be particularly suitable for use in their manufacture. [Explanation of Symbols]

[0078] 11: Release film for manufacturing ceramic green sheets 12: Release agent layer 13: Base material

Claims

1. a) A step of coating a ceramic slurry onto a release film for manufacturing ceramic green sheets, b) A step of forming a ceramic green sheet from the ceramic slurry coated in step a), and c) A step of peeling the ceramic green sheet formed in step b) from the release film for manufacturing the ceramic green sheet, A method for manufacturing a ceramic green sheet having the following characteristics: The aforementioned release film for manufacturing ceramic green sheets comprises a base material and a release agent layer provided on at least one of the base material. The amount of Si on the side of the release agent layer opposite to the substrate before step a) ０ However, 0.003 g / m ２ That's all. The amount of Si on the side of the release agent layer opposite to the substrate after step c) is performed. ｃ And, the above Si ０ The difference between δSi and Si is δSi = Si ｃ -Si ０ However, -0.00027 g / m³ ２ That's all. The above method for manufacturing a ceramic green sheet, The ceramic slurry contains ceramic particles containing barium titanate (BaTiO3), calcium titanate (CaTiO3), strontium titanate (SrTiO3), calcium zirconate (CaZrO3), or strontium zirconate (SrZrO3), and 3 to 20 parts by mass of a binder per 100 parts by mass of the ceramic particles. The release agent layer contains a cured product of a curable composition, and the curable composition contains an epoxy-modified silicone having epoxy groups and a siloxane skeleton, and a polyfunctional (meth)acrylate. A method for manufacturing the above-mentioned ceramic green sheet.

2. The method for producing a ceramic green sheet according to claim 1, wherein the ceramic particles further contain Mn, Mg, Si, Co, Ni, or a rare earth element.

3. The method for producing a ceramic green sheet according to Claim 1, wherein the binder contains at least one selected from the group consisting of polyvinyl butyral, urethane resin, polyvinyl acetate resin, acrylic resin, and cellulose resin.

4. The method for producing a ceramic green sheet according to claim 3, wherein the binder contains polyvinyl butyral with a hydroxyl value of 20 mol% or more.

5. A method for manufacturing a ceramic green sheet according to any one of claims 1 to 4, comprising a step of printing internal electrodes onto the ceramic green sheet between step b) and step c).

6. A method for manufacturing a ceramic product, comprising the step of manufacturing a ceramic green sheet by the method for manufacturing a ceramic green sheet described in any one of claims 1 to 4.

7. A method for manufacturing a ceramic product according to claim 6, further comprising the step of firing the ceramic green sheet.

8. The method for manufacturing a ceramic product according to claim 6, wherein the ceramic product is a multilayer ceramic capacitor or a multilayer ceramic substrate.

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