JP2019009266A - Method of manufacturing multilayer ceramic electronic component, and, multilayer ceramic electronic component - Google Patents

Abstract

To provide a manufacturing method enabling a compact large capacity multilayer ceramic electronic component to be efficiently manufactured.SOLUTION: The method of manufacturing a multilayer ceramic electronic component comprises: a step of fabricating a laminated sheet body including internal electrode patterns arranged at an interface between a plurality of ceramic green sheets and having first and second main faces opposed to each other; a step of cutting a part of the laminated sheet body from a first main surface along a first cutting line, thereby forming a gap along the first cutting line, and exposing a plurality of internal electrodes to the appearing cutting side surface; a step of disposing a laminated resin sheet 41 in which a first resin sheet 51 containing a first resin component and an inorganic material and a second resin sheet 52 containing a second resin component are laminated on the first main surface of the laminated sheet body; a step of obtaining a mother block 36 in which the laminated resin sheet is recessed in a gap and the cutting side surface is covered with a first resin sheet, by applying thermocompression bonding to the laminated sheet body in the laminating direction; and a step of removing the second resin sheet after obtaining the mother block.SELECTED DRAWING: Figure 10

Description

The present invention relates to a method for manufacturing a multilayer ceramic electronic component and a multilayer ceramic electronic component.

The multilayer ceramic capacitor is a chip type ceramic capacitor in which a large number of dielectric layers such as titanium oxide and barium titanate and internal electrode layers are stacked. Multilayer ceramic capacitors are used in a wide range of electronic circuits because they can realize a small size and a large capacity while taking advantage of the excellent high frequency characteristics of ceramics.

The multilayer ceramic capacitor is manufactured, for example, by the following method. First, a plurality of sheets obtained by applying a conductive paste serving as an internal electrode on the surface of a ceramic green sheet by screen printing or the like are alternately stacked and heat-pressed to form a laminated sheet body. Next, the laminated sheet body is cut to form a chip-formed laminated body. After firing the multilayer body, a multilayer ceramic capacitor is obtained by forming terminal electrodes (see, for example, Patent Document 1).

International Publication No. 2017/073621

In order to realize a small-sized and large-capacity multilayer ceramic capacitor, it is effective to increase the effective area of the internal electrodes occupying the ceramic green sheet, that is, the area of the internal electrodes facing each other.

However, in the method described in Patent Document 1, it is necessary to secure a large margin for cutting in consideration of printing deviation and stacking deviation of internal electrodes. Therefore, it is disadvantageous for manufacturing a small and large capacity multilayer ceramic electronic component.

The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a method for manufacturing a multilayer ceramic electronic component capable of efficiently manufacturing a small-sized and large-capacity multilayer ceramic electronic component. Another object of the present invention is to provide a multilayer ceramic electronic component obtained by the above method.

The method for manufacturing a multilayer ceramic electronic component of the present invention includes a plurality of laminated ceramic green sheets and internal electrode patterns respectively disposed along a plurality of interfaces between the ceramic green sheets, and is opposed to the stacking direction. A step of producing a laminated sheet body having a first principal surface and a second principal surface, and at least a part of the laminated sheet body from the first principal surface along a first cutting line in a first direction; By cutting, a gap along the first cutting line is formed, and a plurality of internal electrodes in an unfired state are exposed on a cut side surface that appears by cutting along the first cutting line. A laminate in which a first resin sheet containing a first resin component and an inorganic substance and a second resin sheet containing a second resin component are laminated on the first main surface of the laminated sheet body after the step of cutting The step of arranging the fat sheet so that the first resin sheet is in contact with the first main surface, and by thermocompression bonding the laminated sheet body on which the laminated resin sheet is arranged in the laminating direction, A step of obtaining a mother block in which the laminated resin sheet is inserted into the gap along the first cutting line and the cut side surface is covered with the first resin sheet together with the first main surface; And a step of removing the second resin sheet after obtaining the block.

In the method for manufacturing a multilayer ceramic electronic component of the present invention, in the step of removing the second resin sheet, the second resin sheet may be peeled off, or the second resin sheet may be decomposed and removed by heat treatment. .

In the method for producing a multilayer ceramic electronic component of the present invention, the multilayer resin sheet has a viscosity of V1 [kPa · s], the viscosity of the first resin sheet under the conditions of a temperature of 80 ° C. and a shear rate of 7.6 s ⁻¹ . When the viscosity of the second resin sheet is V2 [kPa · s], it is preferable that Log (V2) / Log (V1) is 0.7 or more and 1.4 or less.

In the method for manufacturing a multilayer ceramic electronic component of the present invention, it is preferable that the viscosity V2 of the second resin sheet is 1500 kPa · s or less.

In the manufacturing method of the multilayer ceramic electronic component of the present invention, it is preferable that the viscosity V1 of the first resin sheet is 1500 kPa · s or less.

In the method for producing a multilayer ceramic electronic component of the present invention, the melting point or glass transition temperature of the first resin component contained in the first resin sheet is less than 100 ° C., and the inorganic material in the first resin sheet The content is preferably 40% by volume or more.

In the method for producing a multilayer ceramic electronic component of the present invention, the first resin component contained in the first resin sheet is an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic acid copolymer, an ethylene- It is preferable to include one or two or more ethylene copolymers selected from the group consisting of a (meth) methyl acrylate copolymer and an ethylene-ethyl acrylate copolymer.

In the method for manufacturing a multilayer ceramic electronic component of the present invention, the inorganic substance contained in the first resin sheet is at least one of Ba, Ca, Sr, and Pb and at least one of Ti, Zr, and Hf. It is preferable to contain the perovskite type | mold ceramic composition containing these.

In the method for manufacturing a multilayer ceramic electronic component according to the present invention, the thickness of the first resin sheet is preferably 10 μm or more and 200 μm or less.

In the method for manufacturing a multilayer ceramic electronic component of the present invention, the thickness of the second resin sheet is preferably 20 μm or more and 1000 μm or less.

In the method for manufacturing a multilayer ceramic electronic component of the present invention, the multilayer resin sheet further includes a third resin sheet laminated on the opposite side of the second resin sheet from the side on which the first resin sheet is laminated. You may have.

The multilayer ceramic electronic component of the present invention includes a plurality of ceramic layers and a plurality of internal electrodes arranged in the stacking direction, the first main surface and the second main surface facing the stacking direction, and the stacking direction A component body having a first side surface and a second side surface opposite to each other in a width direction orthogonal to the first direction, and a first end surface and a second end surface opposite to each other in a length direction orthogonal to the stacking direction and the width direction; A multilayer ceramic electronic component comprising: a first external electrode provided on the first end surface of the component main body; and a second external electrode provided on the second end surface of the component main body. The ceramic constituting the first side surface and the second side surface of the component main body has the same composition as the ceramic constituting the first main surface of the component main body. 2 different sets of ceramics that constitute the main surface And characterized in that.

According to the present invention, a small-sized and large-capacity multilayer ceramic electronic component can be efficiently manufactured.

FIG. 1 is a perspective view schematically showing an example of a multilayer ceramic capacitor obtained by the method for manufacturing a multilayer ceramic electronic component of the present invention. 2 is a cross-sectional view of the multilayer ceramic capacitor shown in FIG. 1 taken along the line II-II. 3 is a cross-sectional view of the multilayer ceramic capacitor shown in FIG. 1 taken along line III-III. FIG. 4 is a plan view schematically showing an example of a ceramic green sheet on which an internal electrode pattern is formed. Fig.5 (a) is a perspective view which shows typically an example of the method of laminating | stacking a ceramic green sheet. FIG. 5B and FIG. 5C are plan views schematically showing an example of a method for laminating ceramic green sheets. FIG. 6 is a perspective view schematically showing an example of a laminated sheet body. FIG. 7 is a perspective view schematically showing an example of the laminated sheet body after being cut. FIG. 8 is a perspective view schematically showing an example of a laminated sheet body in which laminated resin sheets are arranged. FIG. 9 is a perspective view schematically showing another example of a laminated sheet body in which laminated resin sheets are arranged. FIG. 10 is a perspective view schematically showing an example of a mother block. FIG. 11 is a perspective view schematically showing an example of the mother block after the second resin sheet is removed. FIG. 12 is a perspective view schematically showing an example of the mother block after being cut. FIG. 13 is a perspective view schematically showing another example of the mother block after being cut.

Hereinafter, the manufacturing method of the multilayer ceramic electronic component of the present invention will be described.
However, the present invention is not limited to the following configurations, and can be applied with appropriate modifications without departing from the scope of the present invention. A combination of two or more desirable configurations described below is also the present invention.

As an embodiment of the method for manufacturing a multilayer ceramic electronic component of the present invention, a method for manufacturing a multilayer ceramic capacitor will be described as an example. In addition, the manufacturing method of this invention is applicable also to multilayer ceramic electronic components other than a multilayer ceramic capacitor.

First, a multilayer ceramic capacitor obtained by the method for producing a multilayer ceramic electronic component of the present invention will be described.
FIG. 1 is a perspective view schematically showing an example of a multilayer ceramic capacitor obtained by the method for manufacturing a multilayer ceramic electronic component of the present invention. 2 is a cross-sectional view of the multilayer ceramic capacitor shown in FIG. 1 taken along the line II-II. 3 is a cross-sectional view of the multilayer ceramic capacitor shown in FIG. 1 taken along line III-III.

In this specification, the lamination direction, the width direction, and the length direction of the multilayer ceramic capacitor are defined by arrows T, W, and L in the multilayer ceramic capacitor 11 shown in FIGS. 1, 2, and 3, respectively. Here, the stacking direction, the width direction, and the length direction are orthogonal to each other. The stacking direction is a direction in which a plurality of ceramic layers 21 and a plurality of pairs of internal electrodes 22 and 23 are stacked.

A multilayer ceramic capacitor 11 shown in FIG. 1 includes a component body 12. As shown in FIGS. 1, 2, and 3, the component main body 12 has a rectangular parallelepiped shape or a substantially rectangular parallelepiped shape, and includes a first main surface 13 and a second main surface 14 that are opposed to the stacking direction T; The first side surface 15 and the second side surface 16 that are opposed to the width direction W perpendicular to the stacking direction T, and the first end surface 17 and the second side surface that are opposed to the length direction L orthogonal to the stacking direction T and the width direction W. End face 18.

As shown in FIGS. 2 and 3, the component body 12 extends in the direction of the first main surface 13 and the second main surface 14 and is orthogonal to the first main surface 13 and the second main surface 14. And a plurality of pairs of internal electrodes 22 and 23 formed along the interface between the ceramic layers 21.

As will be described later, the component main body 12 is obtained by producing a mother block and then cutting the mother block into pieces into a plurality of green chips. In order to produce a mother block, first, a laminated sheet body is produced by laminating a predetermined number of ceramic green sheets having a conductive paste printed on the surface, and at least a part of the laminated sheet body is a first main sheet. By cutting from the surface, the internal electrode is exposed on the cut side surface. By placing a laminated resin sheet in which the first resin sheet and the second resin sheet are laminated on the first main surface of the laminated sheet body after being cut and thermocompression bonded, the cut side surface together with the first main surface is provided. A mother block covered with the first resin sheet can be produced.

As shown in FIGS. 2 and 3, the internal electrode 22 and the internal electrode 23 face each other with the ceramic layer 21 interposed therebetween. When the internal electrode 22 and the internal electrode 23 face each other, electrical characteristics are exhibited. That is, a capacitance is formed in the multilayer ceramic capacitor 11 shown in FIG.

The internal electrode 22 has an exposed end exposed at the first end surface 17 of the component main body 12, and the internal electrode 23 has an exposed end exposed at the second end surface 18 of the component main body 12. On the other hand, the internal electrodes 22 and 23 are not exposed on the first side surface 15 and the second side surface 16 of the component main body 12.

As shown in FIGS. 1, 2, and 3, the multilayer ceramic capacitor 11 further includes a first end face of the component body 12 so as to be electrically connected to the exposed ends of the internal electrodes 22 and 23, respectively. 17 and a second external electrode 25 provided on the second end face 18 of the component main body 12.

The first external electrode 24 and the second external electrode 25 are formed on the first end surface 17 and the second end surface 18 of the component main body 12, respectively. In FIG. The main surface 14 of the second side and the first side surface 15 and the second side surface 16 have portions that wrap around each part.

There is no restriction | limiting in particular in the external shape and dimension of a component main body, According to a use, it can set suitably. When the outer shape of the component main body is a rectangular parallelepiped shape or a substantially rectangular parallelepiped shape, the length dimension (the length in the L direction in FIG. 1) that is the dimension in the end face direction of the component main body is usually 0.4 mm or more and 5.6 mm or less. The width dimension (the length in the W direction in FIG. 1) that is the dimension in the side surface direction of the component body is 0.2 mm or greater and 5.0 mm or less, and the thickness dimension that is the dimension in the stacking direction of the component body ( In FIG. 1, the length in the T direction is 0.2 mm or more and 1.9 mm or less.

As a ceramic material constituting the ceramic layer, for example, a dielectric ceramic mainly composed of barium titanate, calcium titanate, strontium titanate, calcium zirconate, or the like can be used.

As described above, the manufacturing method of the present invention can be applied to multilayer ceramic electronic components other than multilayer ceramic capacitors. For example, when the multilayer ceramic electronic component is a piezoelectric component, a piezoelectric ceramic such as a PZT ceramic is used, and when the thermistor is a semiconductor ceramic such as a spinel ceramic.

The thickness of the ceramic layer is not particularly limited, but is preferably 3 μm or less.

As the conductive material constituting the internal electrode, for example, a metal material such as Ni, Cu, Ag, Pd, Ag—Pd alloy, Au, or the like can be used.

The thickness of the internal electrode is not particularly limited, but is preferably 1.5 μm or less.

The external electrode is preferably composed of a base layer and a plating layer formed on the base layer. For example, Cu, Ni, Ag, Pd, an Ag—Pd alloy, Au, or the like can be used as the conductive material constituting the base layer. The underlayer may be formed by applying a co-fire method in which a conductive paste is applied onto an unfired component body and simultaneously fired with the component body, and the conductive paste is applied onto the fired component body. It may be formed by applying a post-fire method. Alternatively, the underlayer may be formed by direct plating, or may be formed by curing a conductive resin including a thermosetting resin.

The plating layer formed on the base layer preferably has a two-layer structure of Ni plating and Sn plating thereon.

The thickness of the external electrode is not particularly limited, but is usually 10 μm or more and 50 μm or less.

Next, a method for manufacturing the multilayer ceramic capacitor 11 shown in FIG. 1 will be described as an example of the method for manufacturing the multilayer ceramic electronic component of the present invention.

First, a ceramic green sheet to be a ceramic layer is prepared. For example, a ceramic slurry containing a ceramic powder, a binder and a solvent is prepared, and the ceramic slurry is formed into a sheet using a die coater, a gravure coater, a micro gravure coater, etc. on a carrier film, thereby producing a ceramic green sheet. Can be produced.

The thickness of the ceramic green sheet is preferably 3 μm or less.

Next, an electrode layer (internal electrode pattern) having a predetermined pattern to be an internal electrode is formed on the ceramic green sheet. The method for forming the internal electrode pattern is not particularly limited as long as the electrode layer can be uniformly formed. For example, a screen printing method using a conductive paste is used.

FIG. 4 is a plan view schematically showing an example of a ceramic green sheet on which an internal electrode pattern is formed.
As shown in FIG. 4, an internal electrode pattern 32 to be each of the internal electrodes 22 and 23 is formed by printing a conductive paste with a predetermined pattern on the ceramic green sheet 31 to be the ceramic layer 21. Is done. Specifically, a plurality of strip-like internal electrode patterns 32 are formed on the ceramic green sheet 31.

The thickness of the internal electrode pattern is preferably 1.5 μm or less.

Thereafter, a predetermined number of layers are laminated while shifting the ceramic green sheets on which the internal electrode patterns are formed, and a predetermined number of ceramic green sheets on which the internal electrode patterns are not formed are stacked on top and bottom thereof to produce a laminated sheet body. If necessary, the laminated sheet body is pressed in the laminating direction by means such as isostatic pressing.

Fig.5 (a) is a perspective view which shows typically an example of the method of laminating | stacking a ceramic green sheet.
As shown in FIG. 5A, the ceramic green sheet 31 on which the internal electrode pattern 32 is formed is placed at a predetermined interval along the width direction of the internal electrode pattern 32 (the x direction in FIG. 5A), that is, the internal electrode. A predetermined number of layers are stacked while shifting by half the width direction dimension of the pattern 32. Further, a predetermined number of ceramic green sheets on which no internal electrode pattern is formed are stacked above and below.

FIG. 5B and FIG. 5C are plan views schematically showing an example of a method for laminating ceramic green sheets. FIGS. 5B and 5C are enlarged views of the first and second ceramic green sheets, respectively.
5 (b) and 5 (c), a cutting line 33 in a first direction (x direction in FIGS. 5 (b) and 5 (c)) orthogonal to the direction in which the strip-shaped internal electrode pattern 32 extends. And each part of the cutting line 34 of the 2nd direction (y direction in FIG.5 (b) and FIG.5 (c)) orthogonal to this is shown. The strip-shaped internal electrode pattern 32 has a shape in which two internal electrodes 22 and 23 are connected at the respective leading portions and are continuous along the first direction (x direction). 5B and 5C, the cutting lines 33 and 34 are shown in common.

FIG. 6 is a perspective view schematically showing an example of a laminated sheet body.
A laminated sheet body 35 shown in FIG. 6 includes a plurality of laminated ceramic green sheets 31 and internal electrode patterns 32 arranged along a plurality of interfaces between the ceramic green sheets 31 and are opposed to the lamination direction. It has the 1st main surface 35a and the 2nd main surface 35b.

A gap along the first cutting line is formed by cutting at least part of the laminated sheet body manufactured as described above from the first main surface along the first cutting line in the first direction. At the same time, a plurality of internal electrodes in an unfired state are exposed on the cut side surface that appears by cutting along the first cutting line. For the cutting of the laminated sheet body, for example, a method such as pressing using a blade, dicing using a dicer, laser cutting using a laser, or the like is applied.

FIG. 7 is a perspective view schematically showing an example of the laminated sheet body after being cut.
In FIG. 7, the laminated sheet body 35 is cut from the first main surface 35a along the cutting line 33 in the first direction, and a plurality of green block bodies 19 arranged in the row direction are obtained. In FIG. 7, three green block bodies 19 are taken out from one laminated sheet body 35, but actually a larger number of green block bodies 19 are taken out.

Between the individual green block bodies 19, there are gaps generated by cutting. The size of the gap, that is, the distance between the green block bodies 19 is a size corresponding to the thickness of the blade of the blade, and is, for example, about 100 μm to 200 μm.

Each green block 19 includes a plurality of unfired ceramic layers (ceramic green sheets 31 to be ceramic layers 21) and a plurality of internal electrodes (internal electrode patterns 32 to be internal electrodes 22 and 23). It has the laminated structure comprised by these.

The internal electrode patterns 32 to be the internal electrodes 22 and 23 are exposed on the cut side surfaces 19 a and 19 b of the green block body 19 that appear by cutting along the cutting line 33 in the first direction.

In addition, as shown in FIG. 7, it is preferable to cut | disconnect the laminated sheet body 35 in the state affixed on the adhesive sheet 38 so that the green block bodies 19 may be arranged in a row direction. As an adhesive sheet, a general dicing sheet, a dicing tape, etc. can be used, for example.

In FIG. 7, the laminated sheet body 35 is separated into a plurality of green block bodies 19 by completely cutting the laminated sheet body 35 in the laminating direction. If it can be exposed, the entire laminated sheet body may be cut so that the laminated sheet body is separated, or a part of the laminated sheet body may be cut so that the laminated sheet body is not separated.

Subsequently, a laminated resin sheet in which the first resin sheet and the second resin sheet are laminated is disposed on the first main surface of the cut laminated sheet body. At this time, the laminated resin sheet is disposed so that the first resin sheet is in contact with the first main surface.

Examples of the method of arranging the laminated resin sheet on the first main surface of the laminated sheet body include a method of superimposing the laminated resin sheet on the laminated sheet body.

FIG. 8 is a perspective view schematically showing an example of a laminated sheet body in which laminated resin sheets are arranged.
In FIG. 8, a laminated resin sheet 41 in which a first resin sheet 51 and a second resin sheet 52 are laminated in this order is disposed on the first main surface of the laminated sheet body 35 after cutting. The laminated resin sheet 41 is disposed on the first main surface of the laminated sheet body 35 such that the first resin sheet 51 is in contact with the first main surface.

<Laminated resin sheet>
Hereinafter, an embodiment of the laminated resin sheet used in the present invention will be described.
The laminated resin sheet of the present embodiment is configured by laminating a first resin sheet containing a first resin component and an inorganic substance and a second resin sheet containing a second resin component.

(First resin sheet)
The first resin sheet contains a first resin component and an inorganic substance.

Although the 1st resin component contained in a 1st resin sheet is not specifically limited, What has melting | fusing point or glass transition temperature is less than 100 degreeC is preferable. The melting point or glass transition temperature of the first resin component is preferably 99 ° C. or lower, and more preferably 95 ° C. or lower. When the melting point or glass transition temperature of the first resin component is less than 100 ° C., the cut side surface can be easily covered with the first resin sheet.

On the other hand, the melting point or glass transition temperature of the first resin component is preferably 40 ° C. or higher, and more preferably 50 ° C. or higher. When the melting point or glass transition temperature of the first resin component is 40 ° C. or higher, deformation of the first resin sheet during the production of the laminated resin sheet can be suppressed.

In addition, melting | fusing point or glass transition temperature of resin components, such as a 1st resin component, is measured with a differential scanning calorimetry (DSC) apparatus. The glass transition temperature is measured according to JIS K 7121-1987.

The first resin component preferably contains an ethylene-based copolymer (ethylene-based elastomer), and the ethylene-based copolymer and other resins (referred to as “arbitrary first resin” in the present specification). May be included) or only an ethylene-based copolymer may be used.
In the present specification, “ethylene copolymer” means a copolymer having structural units derived from ethylene.

The ethylene-based copolymer is a copolymer having a structural unit derived from ethylene and a structural unit derived from ethylene having at least a polar group as a substituent for replacing a hydrogen atom (hereinafter referred to as “polar”). It may be referred to as an “ethylene-based copolymer having a group”.
Since the ethylene-based copolymer having a polar group has a high affinity for metals, by using such an ethylene-based copolymer, the first resin composition described later has a higher degree of inorganic dispersion. The first resin sheet formed from such a first resin composition similarly has higher inorganic dispersion and higher strength.

Examples of the polar group in ethylene having at least the polar group described above include alkylcarbonyloxy groups such as acetyloxy group; carboxy groups; alkoxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups.
Examples of the substituent other than the polar group in the ethylene having at least the polar group described above include an alkyl group such as a methyl group.

Examples of ethylene having at least a polar group include vinyl acetate; isopropenyl acetate; (meth) acrylic acid; salts of (meth) acrylic acid; methyl acrylate, ethyl acrylate, n-propyl acrylate, and acrylic acid. Isopropyl, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, (Meth) acrylic acid esters such as n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate; maleic acid; maleic anhydride ; Maleate; maleate ester and the like.
In this specification, “(meth) acrylic acid” is a concept including both “acrylic acid” and “methacrylic acid”.

The ethylene-based copolymer having the polar group is within the range not impairing the effects of the present invention, in addition to the structural unit derived from ethylene and the structural unit derived from ethylene having at least the polar group described above. You may have the other structural unit which does not correspond to either.

Examples of the monomer for deriving other structural units include α-olefins other than ethylene such as propylene, n-butene and isobutylene; acrylamide; N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetone. Acrylamide derivatives such as acrylamide, acrylamide propane sulfonic acid and salts thereof, dimethylaminopropyl acrylamide, dimethylaminopropyl acrylamide salts, quaternary salts of dimethylaminopropyl acrylamide, N-methylol acrylamide and derivatives thereof; methacrylamide; N-methyl Methacrylamide, N-ethylmethacrylamide, methacrylamidepropanesulfonic acid and its salts, N- (3-dimethylaminopropyl) methacrylamide, N- (3- Methacrylamide derivatives such as methylaminopropyl) methacrylamide acid salt, quaternary salt of N- (3-dimethylaminopropyl) methacrylamide, N-methylolmethacrylamide and derivatives thereof; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether , Vinyl ethers such as isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether; nitriles such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride and vinyl fluoride; vinylidene chloride; Vinylidene halides such as vinylidene fluoride; allyls such as allyl acetate (2-propenyl acetate) and allyl chloride (3-chloro-1-propene) Compound (compound having an allyl group (2-propenyl group)); vinylsilyl compound such as vinyltrimethoxysilane (silyl compound having a vinyl group (ethenyl group)); and the like.

In the present specification, the “derivative” means a compound having a structure in which one or more hydrogen atoms of the original compound are substituted with a group other than a hydrogen atom. Further, the “group” includes not only an atomic group formed by bonding a plurality of atoms but also one atom.

In the ethylene-based copolymer having the polar group, the proportion of the structural unit derived from ethylene having at least the polar group is preferably 5% by mass or more and 50% by mass or less in all the structural units. More preferably, it is 10 mass% or more and 45 mass% or less. The said 1st resin sheet can contain sufficient quantity of an inorganic substance because the said ratio is 5 mass% or more. Moreover, the effect which suppresses blocking of a 1st resin sheet becomes higher because the said ratio is 50 mass% or less.

In the ethylene-based copolymer having the polar group, the proportion of other structural units is preferably 10% by mass or less, and may be 0% by mass in all the structural units. When the ratio is 10% by mass or less, the cut side surface can be easily covered with the first resin sheet.

Preferred examples of the ethylene copolymer having the polar group include an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic acid copolymer, an ethylene- (meth) acrylic acid methyl copolymer, and And ethylene-ethyl acrylate copolymer.
Among these, the ethylene copolymer having the above polar group is an ethylene-vinyl acetate copolymer (EVA), an ethylene-methyl acrylate copolymer (EMA), or an ethylene-methyl methacrylate copolymer (EMMA). Alternatively, ethylene-ethyl acrylate copolymer (EEA) is more preferable, and ethylene-methyl acrylate copolymer (EMA) or ethylene-methyl methacrylate copolymer (EMMA) is particularly preferable.

The ethylene-based copolymer has a functional group such as a hydroxyl group, a carboxy group, an acid anhydride group, an amino group, or a trimethoxysilyl group in the molecular chain or at the molecular chain end within a range not impairing the effects of the present invention. You may have.

The molecular weight of the ethylene copolymer is not particularly limited.
However, the weight average molecular weight of the ethylene copolymer is preferably 1 × 10 ⁴ or more and 2 × 10 ⁶ or less in that the moldability of the first resin sheet becomes better.
In the present specification, “weight average molecular weight” is a polystyrene equivalent value measured by gel permeation chromatography (GPC) method unless otherwise specified.

The molecular weight dispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the ethylene copolymer is not particularly limited, but in terms of reducing the stickiness of the first resin sheet and improving the appearance, It is preferably 1.0 or more and 3.5 or less, and more preferably 1.1 or more and 3.0 or less.

The first resin component contained in the first resin sheet may be only one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected according to the purpose.

The first resin component is selected from the group consisting of ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid methyl copolymer, and ethylene-ethyl acrylate copolymer. It is preferable to include one or two or more kinds of ethylene copolymers, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid methyl copolymer And only one or two or more ethylene copolymers selected from the group consisting of ethylene-ethyl acrylate copolymers may be used. By using such a first resin component, the cut side surface can be easily covered with the first resin sheet.

The content of the ethylene copolymer in the first resin component is preferably 20% by mass or more, more preferably 40% by mass or more, and may be 100% by mass. The mechanical strength of a 1st resin sheet improves more because content of an ethylene-type copolymer is 20 mass% or more.
In addition, content (mass%) of the ethylene-type copolymer in the 1st resin component in a 1st resin sheet is content of the ethylene-type copolymer in the 1st resin component in the 1st resin composition mentioned later. It is the same as the amount (% by mass).

As said arbitrary 1st resin, a modified polyolefin polymer etc. are mentioned, for example.
Examples of the modified polyolefin polymer include one selected from the group consisting of an epoxy group, a carboxy group, an acid anhydride group, an amino group, an amide group, an oxazoline group, a hydroxyl group, a mercapto group, a ureido group, and an isocyanate group. Examples thereof include a modified polyolefin polymer having two or more kinds of functional groups in one molecule.
Examples of the modified polyolefin polymer include a copolymer of an olefin monomer and another vinyl monomer other than the olefin monomer and a vinyl monomer having a functional group, and a hydrogenated copolymer thereof, and Examples thereof also include copolymers having a structure in which one or two or more hydrogen atoms of these copolymers are substituted with the above functional groups.

When the arbitrary first resin is a copolymer, its molecular structure is not particularly limited, and may be any of a random copolymer, a block copolymer, a graft copolymer, A block copolymer or a graft copolymer is preferred.

The arbitrary first resin contained in the first resin sheet may be one kind or two or more kinds. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected according to the purpose.

The content of any first resin in the first resin component is preferably 50% by mass or less, more preferably 30% by mass or less, and may be 0% by mass. When the content of the arbitrary first resin is 50% by mass or less, the cut side surface can be easily covered with the first resin sheet.
In addition, content (mass%) of arbitrary 1st resin in the 1st resin component in a 1st resin sheet is content of arbitrary 1st resin in the 1st resin component in the 1st resin composition mentioned later. It is the same as the amount (% by mass).

The content of the first resin component in the first resin sheet is preferably 6% by mass or more and 20% by mass or less, and more preferably 9% by mass or more and 14% by mass or less. When the content of the first resin component in the first resin sheet is within the above range, the first resin sheet has high strength.

The inorganic substance contained in the first resin sheet may be a known one and is not particularly limited. Examples of preferable inorganic materials include insulators such as glass, mica, and ceramic. By using these inorganic substances, a short circuit between the electrodes can be prevented.

Although the said ceramic is not specifically limited, As an preferable thing, an insulator ceramic is mentioned, for example. Examples of the insulator ceramic include perovskite-type ceramic compositions containing at least one of Ba, Ca, Sr, and Pb and at least one of Ti, Zr, and Hf. Specific examples include barium titanate, calcium titanate, strontium titanate, and lead zirconate titanate.

Although the said glass or mica is not specifically limited, As a preferable thing, the glass filler, glass flake, glass bead, silica, synthetic mica, the nano filler of synthetic mica etc. are mentioned, for example. By using glass or mica, the mechanical strength of the first resin sheet can be improved.

The shape of the inorganic substance is not particularly limited and can be arbitrarily selected according to the purpose.
For example, the inorganic material is preferably in the form of a particle such as a sphere in that the degree of dispersion of the inorganic material in the first resin sheet and the first resin composition described later is higher. Moreover, it is preferable that the shape of an inorganic substance is plate shape or scale shape at the point which the intensity | strength of a 1st resin sheet improves more.

The particle diameter of the inorganic substance is not particularly limited, but the weighted average particle diameter of the inorganic substance is preferably 0.05 μm or more and 1.2 μm or less, and more preferably 0.1 μm or more and 1.0 μm or less. When the weighted average particle diameter of the inorganic substance is 0.05 μm or more, the specific surface area of the inorganic substance is reduced, and the dispersibility of the inorganic substance in the first resin sheet and the first resin composition described later is further increased. Moreover, when the weighted average particle diameter of the inorganic substance is 1.2 μm or less, the gap between the inorganic substances becomes smaller, and the moisture resistance of the first resin sheet and the first resin composition described later is further improved.

In the present specification, the “weighted average particle diameter of the inorganic substance” means a value calculated by measuring the particle diameter of 100 inorganic substances through observation with a microscope. In the case of a non-particulate inorganic substance such as a plate or scale, the minor and major diameters of these non-particulate inorganic substances are measured to calculate the cross-sectional area of the inorganic substance and have the same cross-sectional area as the above cross-sectional area The diameter of the circle is calculated, and the weighted average particle diameter is calculated in the same manner as in the case of the particulate inorganic substance with this diameter as the particle diameter. As described above, the “weighted average particle diameter of the inorganic substance” includes not only the weighted average particle diameter of the particulate inorganic substance but also the weighted average particle diameter of the non-particulate inorganic substance.

Only 1 type may be sufficient as the inorganic substance which a 1st resin sheet contains, and 2 or more types may be sufficient as it. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected according to the purpose.

For example, the first resin sheet may be used in combination of two or more inorganic substances having different weighted average particle sizes. Thus, it becomes possible to increase more content of the inorganic substance of a 1st resin sheet by using an inorganic substance together. For example, when two groups of inorganic substances are used in combination, the weighted average particle diameter of one group of inorganic substances is 0.05 μm or more and 0.3 μm or less, and the inorganic substance is obtained from the point that the above-described effects can be obtained more remarkably. It is preferable that the weighted average particle diameter of the other group is 0.3 μm or more and 1.0 μm or less.

The content of the inorganic substance in the first resin sheet is preferably 40% by volume or more, more preferably 40% by volume or more and 70% by volume or less, and particularly preferably 45% by volume or more and 65% by volume or less. preferable. Since the content of the inorganic substance in the first resin sheet is within the above range, the first resin sheet is sufficiently high in flexibility and fluidity during heating, and even when the interval between the cut side surfaces is narrow, the first resin sheet. Can easily cover the cut side surface. Furthermore, since the content of the inorganic substance in the first resin sheet is 40% by volume or more, the volume of the first resin sheet before sintering, which will be described later, and a layer obtained by sintering (for example, a dielectric layer) ) And the volume are smaller, and such a layer can be formed more stably. Moreover, the mechanical strength of a 1st resin sheet improves more because content of the inorganic substance in a 1st resin sheet is 70 volume% or less.
In the present specification, the content (volume%) of the inorganic substance in the first resin sheet is preferably a content at normal temperature. Here, “normal temperature” means a temperature that is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 ° C. or more and 25 ° C. or less.

The inorganic material preferably includes a perovskite-type porcelain composition containing at least one of Ba, Ca, Sr, and Pb and at least one of Ti, Zr, and Hf. Barium titanate, calcium titanate It is more preferable to include one or more insulating ceramics selected from the group consisting of strontium titanate and lead zirconate titanate, barium titanate, calcium titanate, strontium titanate and titanate zirconate Only one or more insulating ceramics selected from the group consisting of lead may be used.

In the range which does not impair the effect of this invention, the 1st resin sheet may contain the other component other than the 1st resin component and the inorganic substance, and does not need to contain it.
Examples of other components include other resin components other than the first resin component, various additives, and the like.

The other component contained in the first resin sheet may be only one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected according to the purpose.

What is necessary is just to adjust suitably content of the other component in a 1st resin sheet according to the kind of other component, for example so that content of an inorganic substance may be 40 volume% or more.

Other resin components other than the first resin component are not particularly limited, and can be arbitrarily selected according to the purpose.

Examples of the additive include metal salt stabilizers such as copper chloride, cuprous iodide (copper iodide (I)), copper acetate, and cerium stearate; hindered amines, hindered phenols, and sulfur-containing compounds. Antioxidants or heat-resistant stabilizers such as acrylate-based and phosphorus-based organic compounds; UV absorbers or weathering agents such as benzophenone-based, salicylate-based, and benzotriazole-based; light stabilizers; mold release agents; lubricants; Viscosity modifiers; Colorants such as pigments and dyes; Fluorescent agents such as fluorescent pigments and fluorescent dyes; Surface treatment agents such as silane coupling agents; Coloring inhibitors; Red phosphorus, metal hydroxide flame retardants, and phosphorus-based flame retardants Flame retardants, silicone flame retardants, halogen flame retardants, flame retardants such as mixtures of the above halogen flame retardants and antimony trioxide; wood powder; rice bran powder; walnut powder; waste paper; phosphorescent pigment; borate glass, silver Antibacterial agent such as antibacterial agent or antifungal agent; Mold corrosion inhibitor such as hydrotalcite such as magnesium-aluminum hydroxyhydrate; Antistatic agent; Antiblocking agent; Surfactant; Deodorant; Plasticizer; Agents and the like.
The additive is preferably a plasticizer from the viewpoint of improving the flexibility of the first resin composition described later.

Examples of the plasticizer include aromatic carboxylic acid esters, aliphatic monocarboxylic acid esters, aliphatic dicarboxylic acid esters, aliphatic tricarboxylic acid esters, phosphoric acid triesters, petroleum resins, polyalkylene glycol plasticizers, and epoxy resins. Examples thereof include a plasticizer and a castor oil plasticizer.
More specifically, examples of the plasticizer include neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di (2-ethylbutyrate), polyoxyethylene diacetate, polyoxyethylene di (2-ethylhexa). Noate), polyoxypropylene monolaurate, polyoxypropylene monostearate, polyoxyethylene dibenzoate, polyol ester such as polyoxypropylene dibenzoate; aliphatic carboxylic acid ester such as butyl oleate; triethyl acetylcitrate; Oxyacid esters such as tributyl acetyl citrate, ethoxycarbonylmethyl dibutyl citrate, di (2-ethylhexyl) citrate, methyl acetyl ricinoleate, and butyl acetyl ricinoleate Soybean oil, soybean oil fatty acid, soybean oil fatty acid ester, epoxidized soybean oil, rapeseed oil, rapeseed oil fatty acid, rapeseed oil fatty acid ester, epoxidized rapeseed oil, linseed oil, linseed oil fatty acid, linseed oil fatty acid ester, epoxidized linseed oil, coconut oil, Vegetable oil-based compounds such as coconut oil fatty acid; pentaerythritol; sorbitol; polyacrylic acid ester; silicone oil;

In the first resin sheet, the ratio of the plasticizer content to the total content of components other than inorganic substances is preferably 70% by mass or less, more preferably 60% by mass or less, and 0% by mass. There may be. When the proportion of the plasticizer content is 70% by mass or less, the first resin sheet is improved in flexibility without impairing strength.

The first resin sheet may be composed of one layer (single layer) or may be composed of two or more layers. When the first resin sheet is composed of a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of these layers is not particularly limited as long as the effects of the present invention are not impaired.

In the present specification, not only the case of the first resin sheet, but “a plurality of layers may be the same or different from each other” means “all layers may be the same or all layers. May be different, and only some of the layers may be the same ”, and“ a plurality of layers are different from each other ”means that“ at least one of the constituent material and thickness of each layer is different from each other ” "Means.

The thickness of the first resin sheet is preferably 10 μm or more and 200 μm or less, and more preferably 50 μm or more and 150 μm or less. The intensity | strength of a 1st resin sheet improves more because the thickness of a 1st resin sheet is 10 micrometers or more. Further, since the thickness of the first resin sheet is 200 μm or less, the thickness of the first resin sheet does not become excessive, and even when the interval between the cut side surfaces is narrow, the first resin sheet can easily cut the side surface. Can be coated.
In the case where the first resin sheet is composed of a plurality of layers, the total thickness of the plurality of layers may be set to the thickness of the preferable first resin sheet.

(Second resin sheet)
The second resin sheet contains a second resin component.

Although the 2nd resin component contained in a 2nd resin sheet is not specifically limited, General purpose resin, such as a polyethylene (PE) type resin, a polypropylene (PP) type resin, a polyvinyl chloride (PVC) type resin, or a thermoplastic elastomer ( TPE) (hereinafter, these polymers may be collectively referred to as “second polymer”), and the second polymer and other resins (in this specification, “arbitrary” May be referred to as "second resin"), or only the second polymer may be included.

Among the second resin components, more specifically, as the general-purpose resin, for example, polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate copolymer. Polymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, styrene butadiene rubber, nitrile rubber, butadiene rubber, chloroprene rubber, ethylene propylene terpolymer, butyl rubber, isobutylene rubber, soft polyvinyl chloride, silicone resin Composition, ethylene propylene rubber, chlorinated polyethylene, acrylonitrile / butadiene / styrene (ABS) resin, acrylonitrile / acrylic rubber / styrene (AAS) resin, acrylonitrile / ethylene rubber / styrene (AES) resin, Meth) acrylic acid ester / styrene (MS) resin, styrene / butadiene / styrene (SBS) resin, and styrene / isoprene / butadiene / styrene (SIBS) resins.
Among the second resin components, more specifically, as the thermoplastic elastomer, for example, olefin elastomer (TPO), polyvinyl chloride elastomer (TPVC), styrene elastomer (SBC), urethane elastomer (TPU). ), Polyester elastomer (TPEE), polyamide elastomer (TPAE) and the like.

The molecular weight of the second polymer is not particularly limited.
However, the weight average molecular weight of the second polymer is preferably 1 × 10 ⁴ or more and 2 × 10 ⁶ or less in that the moldability of the second resin sheet becomes better.

The molecular weight dispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the second polymer is not particularly limited. However, in terms of reducing the stickiness of the second resin sheet and improving the appearance, 1 It is preferably from 0.0 to 3.5, more preferably from 1.1 to 3.0.

Only 1 type may be sufficient as the 2nd resin component which a 2nd resin sheet contains, and 2 or more types may be sufficient as it. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected according to the purpose.

The second resin component is polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic. Acid copolymer, styrene butadiene rubber, nitrile rubber, butadiene rubber, chloroprene rubber, ethylene propylene terpolymer, butyl rubber, isobutylene rubber, soft polyvinyl chloride, silicone resin composition, ethylene propylene rubber, chlorinated polyethylene, acrylonitrile / butadiene / Styrene (ABS) resin, acrylonitrile / acrylic rubber / styrene (AAS) resin, acrylonitrile / ethylene rubber / styrene (AES) resin, (meth) acrylic ester / styrene (MS) resin, Rene / butadiene / styrene (SBS) resin, styrene / isoprene / butadiene / styrene (SIBS) resin, olefin elastomer (TPO), polyvinyl chloride elastomer (TPVC), styrene elastomer (SBC), urethane elastomer (TPU) ), Polyester-based elastomer (TPEE) and polyamide-based elastomer (TPAE), preferably one or two or more second polymers selected from the group consisting of one or two or more second polymers. It may be only combined. By using such a second resin component, the cut side surface can be easily covered with the laminated resin sheet.

The content of the second polymer in the second resin component is preferably 20% by mass or more, more preferably 50% by mass or more, and may be 100% by mass. When the content of the second polymer is 20% by mass or more, the mechanical strength of the second resin sheet is further improved.
In addition, content (mass%) of the 2nd polymer in the 2nd resin component in a 2nd resin sheet is content (2% of the 2nd polymer in the 2nd resin component in the 2nd resin composition mentioned later). Mass%).

As said arbitrary 2nd resin, the same thing as said arbitrary 1st resin is mentioned, for example.

When the above optional second resin is a copolymer, its molecular structure is not particularly limited, and may be any of a random copolymer, a block copolymer, a graft copolymer, A block copolymer or a graft copolymer is preferred.

The arbitrary second resin contained in the second resin sheet may be one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected according to the purpose.

The content of the optional second resin in the second resin component is preferably 50% by mass or less, more preferably 30% by mass or less, and may be 0% by mass. When the content of the optional second resin is 50% by mass or less, the cut side surface can be easily covered with the first resin sheet.
In addition, content (mass%) of arbitrary 2nd resin in a 2nd resin component in a 2nd resin sheet is content of arbitrary 2nd resin in a 2nd resin component in the 2nd resin composition mentioned later. It is the same as the amount (% by mass).

The content of the second resin component in the second resin sheet is preferably 40% by mass or more and 100% by mass or less, and more preferably 60% by mass or more and 100% by mass or less. When the content of the second resin component in the second resin sheet is in the above range, the strength of the second resin sheet is further improved.

In the range which does not impair the effect of this invention, the 2nd resin sheet may contain the other component other than the 2nd resin component, and does not need to contain it.
Examples of other components include various additives.

The other component contained in the second resin sheet may be only one type or two or more types. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected according to the purpose.

What is necessary is just to adjust suitably content of the other component in a 2nd resin sheet according to the kind of other component.

Examples of the additive contained in the second resin sheet include the same additives as those contained in the first resin sheet.
The additive is preferably a plasticizer in terms of easy adjustment of the viscosity V2 of the second resin sheet.

When using the said plasticizer, it is preferable that they are 1 mass% or more and 60 mass% or less, and, as for content of the plasticizer in a 2nd resin sheet, it is more preferable that they are 5 mass% or more and 40 mass% or less. When the content of the plasticizer is 1% by mass or more, the effect obtained by using the plasticizer is more remarkably obtained. Moreover, the intensity | strength of a 2nd resin sheet improves more because content of a plasticizer is 60 mass% or less.

The second resin sheet may be composed of one layer (single layer) or may be composed of two or more layers. When the second resin sheet is composed of a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

The thickness of the second resin sheet is preferably 20 μm or more and 1000 μm or less, and more preferably 150 μm or more and 800 μm or less. When the thickness of the second resin sheet is 20 μm or more, the strength of the second resin sheet is further improved. Moreover, since the thickness of the 2nd resin sheet is 1000 micrometers or less, the thickness of the 2nd resin sheet does not become excess, but a handleability becomes favorable.
When the second resin sheet is composed of a plurality of layers, the total thickness of the plurality of layers may be set to the thickness of the preferable second resin sheet.

In the laminated resin sheet used in the present invention, the viscosity of the first resin sheet is V1 [kPa · s] and the viscosity of the second resin sheet is V2 [kPa] at a temperature of 80 ° C. and a shear rate of 7.6 s ^−1. When s], Log (V2) / Log (V1) (hereinafter, sometimes simply abbreviated as “logarithm ratio of viscosity”) is preferably 0.7 or more and 1.4 or less.
When the logarithmic ratio of the viscosity is in the above range, the laminated resin sheet easily enters into the gap along the first cutting line. Therefore, even when the interval between the cutting side surfaces is narrow, the cutting side surface can be easily formed with the first resin sheet. Can be coated.

In the laminated resin sheet, the logarithmic ratio of the viscosity is more preferably 0.72 or more and 1.37 or less from the viewpoint that it becomes easier to cover the cut side surface with the first resin sheet.

The viscosity V1 of the first resin sheet is not particularly limited, but is preferably 1500 kPa · s or less, more preferably 1200 kPa · s or less, and particularly preferably 1000 kPa · s or less. When V1 is 1500 kPa · s or less, it is easier to cover the cut side surface with the first resin sheet.

On the other hand, the viscosity V1 of the first resin sheet is preferably 1 kPa · s or more, more preferably 5 kPa · s or more, and particularly preferably 10 kPa · s or more. When V1 is 1 kPa · s or more, the strength of the first resin sheet is further improved, and deformation is further suppressed.

The viscosity V1 of the first resin sheet can be adjusted, for example, by adjusting the type or content of the components contained in the first resin sheet, the thickness of the first resin sheet, or the like.

The viscosity V2 of the second resin sheet is not particularly limited, but may be the same as or different from the viscosity V1 of the first resin sheet, but is preferably equal to or less than V1.

That is, the viscosity V2 of the second resin sheet is preferably 1500 kPa · s or less, more preferably 1200 kPa · s or less, and particularly preferably 900 kPa · s or less. When V2 is 1500 kPa · s or less, it is easier to cover the cut side surface with the first resin sheet.

On the other hand, the viscosity V2 of the second resin sheet is preferably 0.5 kPa · s or more, more preferably 1 kPa · s or more, and particularly preferably 5 kPa · s or more. When V2 is 0.5 kPa · s or more, the strength of the second resin sheet is further improved, and deformation is further suppressed.

The viscosity V2 of the second resin sheet can be adjusted, for example, by adjusting the type or content of the component contained in the second resin sheet, the thickness of the second resin sheet, or the like.

V1 and V2 can be measured by the following method using, for example, a viscosity measuring device (for example, “Capillograph” manufactured by Toyo Seiki Co., Ltd.).
(Measurement method of viscosity)
The heated cylinder is filled with the first resin sheet or the second resin sheet (hereinafter abbreviated as “resin pellet”) processed into a pellet, and after sufficiently preheating, it is fixed with a constant speed plunger. Resin pellets heated to 80 ° C. are extruded from an orifice (2 mmφ × 10 mmL) provided at the bottom of the cylinder, and the melt viscosity is calculated from the stress measured at that time. At this time, measurement is performed by changing the descending speed of the plunger, and the melt viscosity when the shear rate is 7.6 s ⁻¹ is obtained from the change curve of the melt viscosity with respect to the shear rate of the resin pellet. Adopted as V2.

In addition, when the 1st resin sheet and the 2nd resin sheet satisfy | fill the conditions of the above viscosity, respectively, the operating temperature of a 1st resin sheet and a 2nd resin sheet, ie, a laminated resin sheet, is limited to 80 degreeC. It is not a thing and can be arbitrarily set according to the purpose.

The laminated resin sheet used in the present invention is not limited to the above-described embodiment, and a part of the configuration may be changed, deleted, or added.

Specifically, the laminated resin sheet may have a layer (sheet) other than the first resin sheet and the second resin sheet. For example, the laminated resin sheet may have a third resin sheet laminated on the opposite side of the second resin sheet from the side on which the first resin sheet is laminated.

FIG. 9 is a perspective view schematically showing another example of a laminated sheet body in which laminated resin sheets are arranged.
In FIG. 9, a laminated resin sheet 42 in which a first resin sheet 51, a second resin sheet 52, and a third resin sheet 53 are laminated in this order is disposed on the first main surface of the laminated sheet body 35 after cutting. ing. The laminated resin sheet 42 is disposed on the first main surface of the laminated sheet body 35 so that the first resin sheet 51 is in contact with the first main surface.

The third resin sheet is not particularly limited as long as it contains a resin capable of maintaining a sheet-like shape, and can be arbitrarily set according to the purpose.
For example, the third resin sheet may contain only the resin component, or may contain both the resin component and other components. What is necessary is just to select the content component of a 3rd resin sheet suitably according to the objective.

The resin component contained in the 3rd resin sheet is not specifically limited, For example, it may be the same as the resin component quoted as a 1st resin component or a 2nd resin component, and may differ.

As for the resin component which a 3rd resin sheet contains, and other components, all may be only 1 type, and 2 or more types may be sufficient as them. In the case of two or more types, the combination and ratio thereof can be arbitrarily selected according to the purpose.

The third resin sheet may be surface-treated. Examples of such a third resin sheet include a release sheet in which one or both surfaces of the resin sheet are subjected to a release treatment.
Preferable resin components contained in the release sheet include, for example, polyethylene terephthalate (PET).
The release treatment of the release sheet can be performed using a known release treatment agent such as a silicone treatment agent.
When the third resin sheet is a release sheet, the third resin sheet is preferably arranged so that at least the release treatment surface is in contact with the second resin sheet.

The third resin sheet may be composed of one layer (single layer), or may be composed of two or more layers. When the third resin sheet is composed of a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of the plurality of layers is not particularly limited as long as the effects of the present invention are not impaired.

The thickness of the third resin sheet may be appropriately selected according to the type of the third resin sheet, but usually it is preferably 12 μm or more and 100 μm or less.

<Method for producing laminated resin sheet>
The laminated resin sheet used in the present invention can be produced, for example, by laminating a first resin sheet and a second resin sheet.
A 1st resin sheet can be manufactured by shape | molding the 1st resin component, an inorganic substance, and the 1st resin composition formed by mix | blending another component as needed to a sheet form.
Moreover, a 2nd resin sheet can be manufactured by shape | molding the 2nd resin component and the 2nd resin composition by which another component is mix | blended as needed into a sheet form.

In the first resin composition, the ratio of the content (parts by mass) of one specific component other than the solvent to the total content (parts by mass) of all components other than the solvent is the specific content in the first resin sheet. It becomes the same as the content (mass%) of one component.
Similarly, the ratio of the content (parts by mass) of a specific component other than the solvent to the total content (parts by mass) of all components other than the solvent in the second resin composition is specified in the second resin sheet. It becomes the same as the content (mass%) of one component.

The first resin composition is, for example, a resin component such as the first resin component is heated to a temperature equal to or higher than the melting point or glass transition temperature to be in a molten state (liquid state) or a rubber state. Depending on the above, it can be produced by adding non-resin components such as other components and kneading.
Similarly, for example, the second resin composition is prepared by heating a resin component such as the second resin component to a temperature equal to or higher than the melting point or the glass transition temperature to obtain a molten state (liquid state) or a rubber state. And it can manufacture by adding a non-resin component, such as another component, to this, and knead | mixing.

The method of heating the resin component until it reaches a temperature equal to or higher than the melting point or glass transition temperature is not particularly limited, and a known method can be applied, but it is a method of heating using a closed kneader, so-called internal mixer. Is preferred.
Further, the method of adding and kneading the non-resin component to the resin component in a molten state or rubber state is not particularly limited, and a known method can be applied, but an open roll, a single screw extruder, a twin screw kneader, A kneading method using a kneader such as a kneader or a Banbury mixer is preferred.

The 1st resin composition or 2nd resin composition obtained as a kneaded material after kneading | mixing can be made into a pellet form or a tablet form by performing further granulation, a cooling process, etc., for example.

In the production of the first resin sheet, the method of molding the first resin composition into a sheet is not particularly limited, but specific examples include a method of molding using an extrusion apparatus equipped with a T die. .
Similarly, the method of forming the second resin component or the second resin composition into a sheet shape during the production of the second resin sheet is not particularly limited, but as an example, an extrusion device equipped with a T die is used. And the like.

The first resin sheet and the second resin sheet may be laminated by a known method. For example, a laminated resin sheet can be obtained by laminating these sheets by thermal lamination or the like.

As the laminated resin sheet, one or more resins further on the opposite side of the second resin sheet from the side on which the first resin sheet is laminated, such as the one laminated with the third resin sheet as described above What laminated | stacked the sheet | seat can be manufactured with the following method, for example.
That is, first, one or more resin sheets (for example, a third resin sheet) are manufactured by the same method as that for the first resin sheet or the second resin sheet. At this time, one or more resin sheets (for example, the third resin sheet) are obtained by applying the resin composition (for example, the third resin composition) in the same manner as in the case of the first resin composition except that the blending components are different. It can manufacture by using this resin composition.
Next, the step of laminating one or more resin sheets on the side of the second resin sheet on the side where the first resin sheet is laminated or the side opposite to the side on which the first resin sheet is to be laminated, In addition, the objective laminated resin sheet can be manufactured by performing additionally at suitable timing. Or when laminating the 1st resin sheet and the 2nd resin sheet as mentioned above, the laminated resin sheet made into the object can also be manufactured by laminating one or more resin sheets simultaneously.

At the time of manufacturing the laminated resin sheet, the first resin sheet, the second resin sheet, and the third resin sheet can be laminated at any timing.

The laminated sheet body on which the above-described laminated resin sheet is disposed is heat-pressed in the laminating direction. Examples of the thermocompression bonding method include a method of pressing in the laminating direction by means such as a rigid press or an isostatic press. As a result, the laminated resin sheet is inserted into the gap along the first cutting line, and a mother block having the first main surface and the cut side surface covered with the first resin sheet is obtained.

As above-mentioned, since the 1st resin sheet contains an inorganic substance among laminated resin sheets, after the 1st resin component burns away, it functions as a ceramic layer. Therefore, since the ceramic layer can be formed on the cut side surface where the internal electrode is exposed, a small-sized and large-capacity multilayer ceramic electronic component can be efficiently manufactured.

FIG. 10 is a perspective view schematically showing an example of a mother block.
When the laminated sheet body 35 on which the laminated resin sheet 41 shown in FIG. 8 is disposed is heat-pressed in the lamination direction, like the mother block 36 shown in FIG. 10, the first resin sheet 51 in the laminated resin sheet 41 is A gap (see FIG. 8) along the cutting line 33 in the first direction is inserted, and the cutting side surface is covered together with the first main surface. When the first resin sheet 51 enters the gap, as shown in FIG. 10, the second resin sheet 52 also enters the gap without coming into contact with the cut side surface. Typically, the second resin sheet 52 is indented to a depth of half or more of the gap.

When the laminated sheet body on which the laminated resin sheet is arranged is heat-pressed, the buffer sheet is interposed on one or both of the upper surface of the laminated resin sheet and the second main surface of the laminated sheet body. Alternatively, a pressure plate for applying pressure may be disposed (laminated), and pressure may be applied by applying pressure to the pressure plate. The buffer sheet is for suppressing damage to the laminated resin sheet or the laminated sheet body during pressurization.

As described above, when the buffer sheet and the pressure plate are used, a release sheet may be further disposed (laminated) between the laminated resin sheet and the buffer sheet or between the laminated sheet body and the buffer sheet. Good. The release sheet is for preventing the buffer sheet from sticking, and examples thereof include one in which one surface or both surfaces of the resin film are subjected to a release treatment.
Examples of the resin film include a polyethylene terephthalate (PET) film. Moreover, as said mold release process, what is performed using well-known mold release processing agents, such as a silicone processing agent, etc. are mentioned, for example. Thus, as a release sheet, the same thing as what was demonstrated previously as a 3rd resin sheet is mentioned.
That is, the pressurization of the laminated resin sheet using the release sheet means the same as the pressurization of the laminated resin sheet when the third resin sheet is a release sheet.

The thermocompression bonding of the laminated sheet body in which the laminated resin sheet is arranged is preferably performed while heating at least the laminated resin sheet, and the whole laminated resin sheet or the whole laminated sheet body in which the laminated resin sheet is arranged is heated. You may go while. By doing in this way, a cutting | disconnection side surface can be more easily coat | covered with the 1st resin sheet in a laminated resin sheet.

The temperature at the time of thermocompression bonding may be appropriately adjusted in consideration of the melting point or glass transition temperature of the first resin component and the second resin component, but it is usually preferably 70 ° C. or higher and 100 ° C. or lower.

The pressure at the time of thermocompression bonding may be appropriately adjusted in consideration of the temperature at the time of thermocompression bonding, the type of the laminated resin sheet, etc., but it is usually preferably 50 kg / cm ² or more and 1000 kg / cm ² or less.
The time for thermocompression bonding may be appropriately adjusted in consideration of the temperature and pressure during thermocompression bonding, but it is usually preferably 1 minute or more and 30 minutes or less.

After obtaining the mother block as described above, the second resin sheet of the laminated resin sheet is removed.
The method for removing the second resin sheet is not particularly limited, and examples thereof include a method for peeling the second resin sheet, a method for decomposing and removing the second resin sheet by heat treatment, and the like. These methods may be combined.

As a 1st method of removing a 2nd resin sheet, the method of removing a 2nd resin sheet from a mother block is mentioned. For example, the second resin sheet may be peeled from the mother block, or the second resin sheet may be decomposed and removed by heat-treating the mother block.

FIG. 11 is a perspective view schematically showing an example of the mother block after the second resin sheet is removed.
In the mother block 36a shown in FIG. 11, the second resin sheet 52 is removed from the mother block 36 shown in FIG. 10, and the cut side surface is covered with the first resin sheet 51 together with the first main surface.

When removing the second resin sheet from the mother block, the mother block after the second resin sheet is removed is divided into a second cutting line in the first direction orthogonal to each other and a third cutting line in the second direction. A plurality of green chips are obtained by cutting along the line. Note that the cutting along the second cutting line in the first direction can be omitted. For the cutting of the mother block, for example, a cutting method using a blade, dicing using a dicer, guillotine cutting, laser cutting using a laser, or the like is applied.

FIG. 12 is a perspective view schematically showing an example of the mother block after being cut.
12, the mother block 36a shown in FIG. 11 is cut along a cutting line 33 in the first direction and a cutting line 34 in the second direction orthogonal to each other, and a plurality of green chips arranged in the row and column directions. 20a is obtained. At this time, the mother block is cut so that the cut side surface that appears by cutting along the cutting line 33 in the first direction is covered with the first resin sheet 51. For example, there is a method of making the thickness of the blade of the blade used for cutting the mother block 36a shown in FIG. 11 smaller than the thickness of the blade of the blade used for cutting the laminated sheet 35 shown in FIG. Can be mentioned. Note that cutting along the cutting line 33 in the first direction can be omitted. In FIG. 12, six green chips 20a are taken out from one mother block, but actually, a larger number of green chips 20a are taken out.

There is a gap generated by cutting between the individual green chips 20a. The size of the gap, that is, the distance between the green chips 20a is a size corresponding to the thickness of the blade of the blade and is not particularly limited, but is about 100 μm or less, for example.

The green chip 20a separated from the mother block is subjected to firing described later, and finally becomes a component main body 12 constituting the multilayer ceramic capacitor 11 shown in FIGS. Each green chip 20a includes a plurality of ceramic layers in an unfired state (ceramic green sheet 31 to be the ceramic layer 21) and a plurality of internal electrodes (internal electrode patterns 32 to be the internal electrodes 22 and 23). It has the laminated structure comprised by.

As in FIG. 2, the internal electrode patterns 32 to be the internal electrodes 22 and 23 are not exposed on both side surfaces of the green chip 20 a that appear by cutting along the cutting line 33 in the first direction. Further, only the internal electrode pattern 32 to be the internal electrode 22 is exposed on one end face of the green chip 20a that appears by cutting along the cutting line 34 in the second direction, and the internal electrode 23 is formed on the other end face. Only the power internal electrode pattern 32 is exposed.

In addition, as shown in FIG. 12, it is preferable to cut | disconnect in the state in which the mother block was affixed on the adhesive sheet 38 so that the green chip | tip 20a may be arranged in a row and column direction. As the pressure-sensitive adhesive sheet, for example, a general dicing sheet, a dicing tape, an expanded sheet that expands by heating, and the like can be used.

As a second method of removing the second resin sheet, there is a method of removing the second resin sheet from the green chip obtained by dividing the mother block into pieces. For example, the second resin sheet may be peeled from the green chip, or the second resin sheet may be decomposed and removed by heat treating the green chip. This heat treatment may be a heat treatment different from the firing treatment described later, or may be a firing treatment. That is, the removal of the second resin sheet and the firing of the green chip may be performed simultaneously by the firing treatment.

When removing the second resin sheet from the green chip, the mother block before the second resin sheet is removed is divided into a second cutting line in the first direction orthogonal to each other and a third cutting line in the second direction. A plurality of green chips are obtained by cutting along the line. Note that the cutting along the second cutting line in the first direction can be omitted. For the cutting of the mother block, for example, a cutting method using a blade, dicing using a dicer, guillotine cutting, laser cutting using a laser, or the like is applied.

FIG. 13 is a perspective view schematically showing another example of the mother block after being cut.
In FIG. 13, the mother block 36 shown in FIG. 10 is cut along a cutting line 33 in the first direction and a cutting line 34 in the second direction orthogonal to each other, and a plurality of green chips arranged in the row and column directions. 20 is obtained. At this time, the mother block is cut so that the cut side surface that appears by cutting along the cutting line 33 in the first direction is covered with the first resin sheet 51. For example, there is a method of making the thickness of the blade of the blade used for cutting the mother block 36 shown in FIG. 10 smaller than the thickness of the blade of the blade used for cutting the laminated sheet body 35 shown in FIG. Can be mentioned. Note that cutting along the cutting line 33 in the first direction can be omitted. In FIG. 13, six green chips 20 are taken out from one mother block, but actually, a larger number of green chips 20 are taken out.

A gap generated by cutting exists between the individual green chips 20. The size of the gap, that is, the distance between the green chips 20 is a size corresponding to the thickness of the blade of the blade and is not particularly limited, but is, for example, about 100 μm or less.

The green chip 20 separated from the mother block is subjected to the removal of the second resin sheet and the firing described later, and finally the components constituting the multilayer ceramic capacitor 11 shown in FIGS. 1, 2, and 3. It becomes the main body 12. Each green chip 20 includes a plurality of ceramic layers in an unfired state (ceramic green sheet 31 to be the ceramic layer 21) and a plurality of internal electrodes (internal electrode patterns 32 to be the internal electrodes 22 and 23). It has the laminated structure comprised by.

As in FIG. 2, the internal electrode patterns 32 to be the internal electrodes 22 and 23 are not exposed on both side surfaces of the green chip 20 that appear by cutting along the cutting line 33 in the first direction. Further, only the internal electrode pattern 32 to be the internal electrode 22 is exposed on one end face of the green chip 20 that appears by cutting along the cutting line 34 in the second direction, and the internal electrode 23 is formed on the other end face. Only the power internal electrode pattern 32 is exposed.

In addition, as shown in FIG. 13, it is preferable to cut | disconnect in the state in which the mother block was affixed on the adhesive sheet 38 so that the green chip 20 may be arranged in a row and column direction. As the pressure-sensitive adhesive sheet, for example, a general dicing sheet, a dicing tape, an expanded sheet that expands by heating, and the like can be used.

In each case of removing the second resin sheet from the mother block and removing the second resin sheet from the green chip, each green chip is fired. The firing temperature is, for example, in the range of 900 ° C. to 1300 ° C., although it depends on the ceramic material contained in the ceramic green sheet and the unfired protective layer and the metal material contained in the internal electrode.

For example, the green chip 20a shown in FIG. 12 becomes the component main body 12 constituting the multilayer ceramic capacitor 11 shown in FIGS. 1, 2, and 3 by being fired. The first resin sheet 51 becomes a part of the ceramic layer 21 together with the ceramic green sheet 31. Therefore, in the component main body 12 obtained by firing, the boundary between the portion derived from the first resin sheet 51 and the portion derived from the ceramic green 31 may not appear clearly.

In addition, you may perform a binder removal process with respect to each green chip | tip before baking. In this case, the second resin sheet can be decomposed and removed by the heat of the binder removal process.

As a third method for removing the second resin sheet, there is a method of firing the mother block before the second resin sheet is removed. In this case, the second resin sheet can be removed by heat during firing, and the mother block can be separated into green chips.

In addition, you may perform a binder removal process with respect to the mother block before baking. In this case, the second resin sheet can be decomposed and removed by the heat of the binder removal process.

In any method of removing the second resin sheet, heat treatment (annealing treatment) may be performed after firing.

Moreover, when the ceramic layer derived from the 1st resin sheet or the 2nd resin sheet is formed in the unnecessary part, you may remove an excess part suitably.

The first external electrode and the second external electrode are formed by applying a conductive paste to both end faces of the component main body obtained by firing, baking, and plating as necessary. The application of the conductive paste may be performed on the unfired component body, or the conductive paste may be baked simultaneously when firing the unfired component body.

From the above, the multilayer ceramic capacitor 11 shown in FIG. 1 is manufactured.
The multilayer ceramic capacitor manufactured in this way is mounted on a printed circuit board or the like by soldering or the like and used for various electronic devices.

As described above, the manufacturing method of the present invention is not limited to the method of manufacturing a multilayer ceramic capacitor, and can also be applied to a method of manufacturing a multilayer ceramic electronic component other than the multilayer ceramic capacitor.

In the manufacturing method of the multilayer ceramic electronic component of the present invention, not only the first main surface of the multilayer sheet body after cutting but also the cut side surface is covered with the first resin sheet. The ceramic contained in the first resin sheet may have the same composition as the ceramic contained in the ceramic green sheet for forming the ceramic layer, but may have a different composition. For example, as the ceramic contained in the first resin sheet, ceramic powder having a larger particle size than that of the ceramic contained in the ceramic green sheet can be used.

In addition, by setting the ceramic contained in the first resin sheet to a composition different from that of the ceramic contained in the ceramic green sheet, for example, a portion derived from the first resin sheet can have a different color from the other ceramic layers. . In this case, since it can be distinguished from other surfaces by the difference in color, the direction of the multilayer ceramic electronic component can be identified from the appearance.

Accordingly, a multilayer ceramic electronic component having the following characteristics is also one aspect of the present invention.
The multilayer ceramic electronic component of the present invention includes a plurality of ceramic layers and a plurality of internal electrodes arranged in the stacking direction, the first main surface and the second main surface facing the stacking direction, and the stacking direction A component body having a first side surface and a second side surface opposite to each other in a width direction orthogonal to the first direction, and a first end surface and a second end surface opposite to each other in a length direction orthogonal to the stacking direction and the width direction; A multilayer ceramic electronic component comprising: a first external electrode provided on the first end surface of the component main body; and a second external electrode provided on the second end surface of the component main body. The ceramic constituting the first side surface and the second side surface of the component main body has the same composition as the ceramic constituting the first main surface of the component main body. 2 different sets of ceramics that make up the main surface And characterized in that.

In this specification, “different composition” includes not only the case where the types of elements contained in the ceramic are different but also the case where the types of elements contained in the ceramic are the same, even if the content is different. It is. However, differences in the degree of variation in the manufacturing process are not included.

In the multilayer ceramic electronic component of the present invention, the dimension in the width direction may be shorter or longer than the dimension in the length direction.

Examples in which the method for producing a multilayer ceramic electronic component of the present invention is disclosed more specifically below. In addition, this invention is not limited only to these Examples.

1) Production of resin sheet <Production of first resin sheet>
[Reference Example 1]
Ethylene-methyl acrylate copolymer (“EB440H” manufactured by Nippon Polyethylene Co., Ltd., melting point 77 ° C., melt flow rate 18 g / 10 min), barium titanate (“BTC-4FA” manufactured by Nippon Chemical Industry Co., Ltd.), paraffin oil ( "PW90" manufactured by Idemitsu Kosan Co., Ltd.), the content of barium titanate at 23 ° C is 55% by volume, and the ratio of the content of paraffin oil to the total content of components other than barium titanate The 1st resin composition whose is 30 mass% was prepared. Next, a first resin sheet (thickness: 200 μm) was produced by hot pressing the first resin composition.
The obtained resin sheet had a viscosity V1 of 300 kPa · s. The results are shown in Table 1.

[Reference Example 2]
A first resin composition was prepared in the same manner as in Reference Example 1 except that the ratio of the content of paraffin oil to the total content of components other than barium titanate was 40% by mass instead of 30% by mass. And the 1st resin sheet (thickness 200 micrometers) was produced by the same method as the reference example 1 except the point which used this 1st resin composition.
The obtained resin sheet had a viscosity V1 of 130 kPa · s. The results are shown in Table 1.

[Reference Example 3]
The first resin composition was prepared in the same manner as in Reference Example 1 except that the ratio of the content of paraffin oil to the total content of components other than barium titanate was changed to 60% by mass instead of 30% by mass. And the 1st resin sheet (thickness 200 micrometers) was produced by the same method as the reference example 1 except the point which used this 1st resin composition.
The obtained resin sheet had a viscosity V1 of 20 kPa · s. The results are shown in Table 1.

[Reference Example 4]
Except that the content of barium titanate was changed to 70% by volume instead of 55% by volume, a first resin composition was prepared by the same method as in Reference Example 1, and this first resin composition was used. Produced a first resin sheet (thickness: 200 μm) in the same manner as in Reference Example 1.
The viscosity V1 of the obtained resin sheet was 2600 kPa · s. The results are shown in Table 1.

<Production of laminated resin sheet>
[Example 1]
(Production of first resin sheet and second resin sheet)
A first resin composition was prepared by the same method as in Reference Example 1, and this first resin composition was heated and pressed to produce a first resin sheet (thickness 80 μm).
Separately, a polyolefin elastomer (“8032NS” manufactured by Mitsui Chemicals, softening point 120 ° C.) is prepared as a second resin component, and a second resin sheet (thickness 200 μm) is produced by heating and pressing this. did.

The viscosity V1 of the first resin sheet was 300 kPa · s, the viscosity V2 of the second resin sheet was 60 kPa · s, and the logarithmic ratio of the viscosity (Log (V2) / Log (V1)) was 0.72. . The results are shown in Table 1.

(Production of laminated resin sheet)
Subsequently, the 1st resin sheet and the 2nd resin sheet which were obtained above were heat-pressed, and the laminated resin sheet by which the 1st resin sheet and the 2nd resin sheet were laminated | stacked was produced.

[Example 2]
The first resin composition was prepared by the same method as in Reference Example 2, and the first resin sheet (thickness 80 μm) and the second resin were the same as in Example 1 except that this first resin composition was used. A laminated resin sheet obtained by laminating sheets (thickness: 200 μm) was produced.
The viscosity V1 of the first resin sheet was 130 kPa · s, the viscosity V2 of the second resin sheet was 60 kPa · s, and the logarithmic ratio of viscosity (Log (V2) / Log (V1)) was 0.84. . The results are shown in Table 1.

[Example 3]
The first resin composition was prepared by the same method as in Reference Example 3, and the first resin sheet (thickness 80 μm) and the second resin were the same as in Example 1 except that this first resin composition was used. A laminated resin sheet obtained by laminating sheets (thickness: 200 μm) was produced.
The viscosity V1 of the first resin sheet was 20 kPa · s, the viscosity V2 of the second resin sheet was 60 kPa · s, and the logarithmic ratio of the viscosity (Log (V2) / Log (V1)) was 1.37. . The results are shown in Table 1.

[Example 4]
The first resin composition was prepared by the same method as in Reference Example 4, and the first resin sheet (thickness 80 μm) and the second resin were the same as in Example 1 except that this first resin composition was used. A laminated resin sheet obtained by laminating sheets (thickness: 200 μm) was produced.
The viscosity V1 of the first resin sheet was 2600 kPa · s, the viscosity V2 of the second resin sheet was 60 kPa · s, and the logarithmic ratio of viscosity (Log (V2) / Log (V1)) was 0.52. . The results are shown in Table 1.

[Example 5]
The first resin sheet (thickness 80 μm) and the second resin component were the same as in Example 2 except that polyethylene (“F522NH” manufactured by Ube Maruzen Polyethylene Co., Ltd.) was used instead of the polyolefin-based elastomer as the second resin component. A laminated resin sheet in which two resin sheets (thickness 200 μm) were laminated was produced.
The viscosity V1 of the first resin sheet was 130 kPa · s, the viscosity V2 of the second resin sheet was 3000 kPa · s, and the logarithmic ratio of viscosity (Log (V2) / Log (V1)) was 1.64. . The results are shown in Table 1.

2) Production of laminated block Polyvinyl butyral binder, a plasticizer and ethanol as an organic solvent were added to BaTiO ₃ as a ceramic raw material, and these were wet mixed by a ball mill to produce a ceramic slurry. Subsequently, this ceramic slurry was formed into a sheet by a lip method to obtain a rectangular ceramic sheet having a thickness of 4 μm. Next, a conductive paste containing Ni was screen-printed on the ceramic sheet to form a conductive film having a thickness of 1 μm to be an internal electrode containing Ni as a main component.

Next, 25 ceramic sheets on which no conductive film is formed are laminated, and 200 ceramic sheets on which the conductive film is formed are laminated so that the side from which the conductive film is drawn is staggered. Three ceramic sheets with no conductive film formed thereon were laminated to obtain an unfired laminated sheet body to be a capacitor component body.

The unfired laminated sheet was sandwiched with 0.2 mm rubber and heated and pressurized by a hydrostatic press under conditions of a temperature of 80 ° C. and a pressure of 1.0 ton / cm ² to obtain a laminated block.

The laminated block was cut in one direction by dicing to obtain a plurality of green block bodies as shown in FIG. Between the individual green block bodies, there were gaps generated by cutting, and the conductive film was exposed on the cut side surfaces that appeared by cutting.

The first resin sheet produced in each reference example or the laminated resin sheet produced in each example was placed on the upper surface of the green block body, and a rigid body press with a rigid plate temperature of 80 ° C. and a pressure of 1.0 ton / cm ² Was heated and pressurized to obtain a mother block. By filling the resin composition of each resin sheet into the gap, an unfired protective layer was formed not only on the upper surface of the mother block but also on the side surface.

3) Cutting the mother block and firing the chip The mother block was cut by dicing to obtain a green chip. About the reference example, the cutting | disconnection of 2 directions (1st direction and 2nd direction) was performed. About the Example, after peeling the 2nd resin sheet from the mother block, the cutting | disconnection of 1 direction (2nd direction) was performed.

The obtained green chip was heated at 250 ° C. in an N ₂ atmosphere to burn the binder, and then fired at 1200 ° C. in a reducing atmosphere containing H ₂ , N ₂ and H ₂ O gas. A tied part body was obtained. The dimension of the obtained component main body is 1.0 mm in the length direction (D _L ), 0.5 mm in the width direction (D _W ), and 0.5 mm in the height direction (D _T ).

4) Formation of external electrode An external electrode having a structure including a base electrode layer (baked layer) and a plating layer was formed on the component body after firing. The material for forming the base electrode layer (baked layer) contained Cu and glass and was baked at 850 ° C. Further, Cu plating was performed to form a plating layer.

<Evaluation of side coverage>
Each of the 20 fired component bodies was held using a thermosetting resin, then subjected to cross-sectional polishing, observed with a microscope, and side coverage was evaluated according to the following criteria. In the evaluation of the side coverage, it was determined whether the first and second side surfaces of the component body were formed with a uniform thickness.
A: The first and second side surfaces are uniformly formed in all cross sections.
○ Judgment: A part with insufficient side coverage is found on one component body.
[Delta] Judgment: Side cover insufficient portions are found in 2 or more and less than 20 component bodies.
X determination: All 20 parts are found to have insufficient side coverage.
It should be noted that if the yield is 1 or less, it is determined that there is no practical problem.

<Evaluation of interface peeling>
For each of the fired component bodies, an appearance inspection was performed on 20 pieces, peeling of the interface portion between the internal electrode and the protective layer was confirmed, and interface peeling was evaluated according to the following criteria.
◎ Judgment: No interface peeling.
○ Judgment: Interfacial peeling is observed in one component body.
Δ Judgment: Interfacial peeling is observed in 2 or more and less than 20 component bodies.
X Determination: Interfacial peeling is observed on all 20 component bodies.
It should be noted that if the yield is 1 or less, it is determined that there is no practical problem.

As described above, in Reference Examples 1 to 4, it was necessary to cut in two directions, whereas in Examples 1 to 5, cutting in one direction was sufficient, and the processing time was shortened.

Moreover, as shown in Table 1, in Examples 1-5, while being excellent in side surface coverage, peeling of the interface is suppressed, and this tendency is particularly good in Examples 1-3.

11 Multilayer ceramic capacitors (multilayer ceramic electronic components)
12 component main body 13 first main surface 14 second main surface 15 first side surface 16 second side surface 17 first end surface 18 second end surface 19 green block bodies 19a, 19b cut side surfaces 20, 20a green chip 21 Ceramic layers 22 and 23 Internal electrode 24 First external electrode 25 Second external electrode 31 Ceramic green sheet 32 Internal electrode pattern 33 Cutting line 34 in the first direction 34 Cutting line 35 in the second direction Laminated sheet body 35a Laminated sheet body First main surface 35b Second main surface 36, 36a of laminated sheet body Mother blocks 41, 42 Laminated resin sheet 51 First resin sheet 52 Second resin sheet 53 Third resin sheet

Claims (13)

Including a plurality of laminated ceramic green sheets and internal electrode patterns respectively disposed along a plurality of interfaces between the ceramic green sheets, the first principal surface and the second principal surface facing each other in the lamination direction; A step of producing a laminated sheet body,
By cutting at least a part of the laminated sheet body from the first main surface along a first cutting line in a first direction, a gap along the first cutting line is formed, and the first A step of exposing a plurality of internal electrodes in an unfired state to a cut side surface that appears by cutting along a cutting line of 1;
A laminated resin sheet in which a first resin sheet containing a first resin component and an inorganic substance and a second resin sheet containing a second resin component are laminated on the first main surface of the laminated sheet body after cutting. Arranging the first resin sheet so as to contact the first main surface;
The laminated resin sheet is inserted into the gap along the first cutting line by thermocompression bonding the laminated sheet body on which the laminated resin sheet is arranged in the laminating direction, and the first main surface And a step of obtaining a mother block, wherein the cut side surface is covered with the first resin sheet;
And a step of removing the second resin sheet after obtaining the mother block. The method for manufacturing a multilayer ceramic electronic component according to claim 1, wherein in the step of removing the second resin sheet, the second resin sheet is peeled off. The method for manufacturing a multilayer ceramic electronic component according to claim 1, wherein in the step of removing the second resin sheet, the second resin sheet is decomposed and removed by heat treatment. The laminated resin sheet has a first resin sheet viscosity of V1 [kPa · s] and a second resin sheet viscosity of V2 [kPa · s] at a temperature of 80 ° C. and a shear rate of 7.6 s ^−1. s], Log (V2) / Log (V1) is 0.7 or more and 1.4 or less, The manufacturing method of the multilayer ceramic electronic component of any one of Claims 1-3. The method for producing a multilayer ceramic electronic component according to claim 4, wherein the viscosity V2 of the second resin sheet is 1500 kPa · s or less. The method for producing a multilayer ceramic electronic component according to claim 4 or 5, wherein the first resin sheet has a viscosity V1 of 1500 kPa · s or less. The melting point or glass transition temperature of the first resin component contained in the first resin sheet is less than 100 ° C .;
The method for manufacturing a multilayer ceramic electronic component according to claim 1, wherein the content of the inorganic substance in the first resin sheet is 40% by volume or more. The first resin component contained in the first resin sheet includes an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic acid copolymer, an ethylene- (meth) acrylic acid methyl copolymer, and an ethylene-acrylic. The manufacturing method of the multilayer ceramic electronic component of any one of Claims 1-7 containing the 1 type, or 2 or more types of ethylene-type copolymer selected from the group which consists of an acid acid copolymer. The said inorganic substance contained in a said 1st resin sheet contains the perovskite type | mold ceramic composition containing at least 1 sort (s) among Ba, Ca, Sr, and Pb and at least 1 sort (s) among Ti, Zr, and Hf. The manufacturing method of the multilayer ceramic electronic component of any one of 1-8. The method for manufacturing a multilayer ceramic electronic component according to claim 1, wherein the first resin sheet has a thickness of 10 μm to 200 μm. The method for producing a multilayer ceramic electronic component according to claim 1, wherein the thickness of the second resin sheet is 20 μm or more and 1000 μm or less. The laminated resin sheet according to any one of claims 1 to 11, further comprising a third resin sheet laminated on a side of the second resin sheet opposite to a side on which the first resin sheet is laminated. The manufacturing method of the multilayer ceramic electronic component of description. A plurality of ceramic layers and a plurality of internal electrodes arranged in the stacking direction; a first main surface and a second main surface facing the stacking direction; and a first surface facing the width direction orthogonal to the stacking direction. A component main body having one side surface and a second side surface, and a first end surface and a second end surface facing each other in a length direction orthogonal to the stacking direction and the width direction;
A first external electrode provided on the first end face of the component body;
A multilayer ceramic electronic component comprising: a second external electrode provided on the second end surface of the component body;
The ceramic constituting the first side surface and the second side surface of the component body has the same composition as the ceramic constituting the first main surface of the component body, and the second side of the component body. A multilayer ceramic electronic component having a composition different from that of a ceramic constituting a main surface.

Images