JP6540913B2 - Resin sheet, laminated resin sheet, and resin composition - Google Patents

Description

The present invention relates to a resin sheet, a laminated resin sheet, and a resin composition.

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 be made small and have a large capacity while taking advantage of the excellent high frequency characteristics and the like possessed by ceramics.

The multilayer ceramic capacitor is manufactured, for example, by the following method. First, ceramic powder and a binder (resin component) are mixed to form a ceramic green sheet. Next, a conductive paste is applied by screen printing or the like to a plurality of regions on the surface of the ceramic green sheet to form an internal electrode, and a ceramic green sheet provided with the internal electrode is obtained. Next, a plurality of ceramic green sheets provided with internal electrodes are stacked and heat-pressed to form a laminated sheet. Then, the laminated sheet is cut to form a chipped laminated body. Thereafter, the formed laminate is heated to decompose and remove the binder. Further, after sintering the ceramic powder, a terminal electrode is formed to obtain a multilayer ceramic capacitor.

In the laminated sheet obtained by this method, the area in which the internal electrode is formed and the area in which the internal electrode is not formed are mixed on the surface of one ceramic green sheet. For this reason, one of the adjacent ceramic green sheets does not deform well corresponding to the shape of the other internal electrode, and the followability of the ceramic green sheets becomes insufficient, and a void is generated between the ceramic green sheets. There is. Then, patent document 1 discloses the method of suppressing generation | occurrence | production of such a void part in the said lamination sheet.

Further, when producing a ceramic green sheet, press molding, slip casting, sheet molding, extrusion molding, injection molding and the like are performed. Conventionally, when using a press forming method using water as a medium, it is water-soluble and excellent in the binder power to the inorganic powder, the strength of the obtained ceramic green sheet is high, and the workability before sintering (such as machinability) Vinyl alcohol polymers (hereinafter sometimes abbreviated as "PVA") are used because they are easy to handle, including. However, since PVA has high crystallinity and is hard, there is a problem that the pressing pressure has to be increased in press molding.

Patent Document 2 discloses an alkyl-modified vinyl alcohol-based polymer for obtaining a ceramic green sheet having high flexural strength and excellent in processability, flexibility and crack resistance in place of the PVA in order to improve the properties attributed to PVA. A ceramic green sheet using (hereinafter sometimes abbreviated as "alkyl-modified PVA") is disclosed.

Unexamined-Japanese-Patent No. 2000-223353 JP, 2013-170107, A

The laminate obtained by cutting the laminated sheet has a problem that the exposed end portion formed by the cutting is brittle.
Therefore, conventionally, in order to protect the end portion, a resin composition containing a ceramic such as a dielectric ceramic is applied to the surface of the end portion, that is, a cut surface (cut surface), A technique may be employed in which a ceramic layer is separately formed and protected by coating.
In this case, in the laminate to which the resin composition is to be applied, in addition to the above-described chipped one, for example, one cut from the laminated sheet before being chipped into one row (In the state where the chipping planned sites are connected in a line) is also included.
However, immediately after cutting, a large number of the laminates are aligned, and in the method described above, when the resin composition is applied to the cut surface, the cut surface facing sideways just after cutting is upward. It is necessary to change the orientation of the laminate so that the process is inefficient.
Further, the covering of the cut surface of the laminate is similar to the above-mentioned problem in the filling of the gaps between the ceramic green sheets in that the gaps are embedded, but the patent document 1 The method described in the above can not be applied to the coating of the cut surface of the laminate.

Furthermore, until now, a resin composition containing a ceramic is applied to the cut surface of the laminate, and after the voids between the laminates are embedded with the resin composition, the cut surface is covered with the ceramic layer by firing. However, the step of filling the groove like the void with a resin is not limited to the case of forming such a ceramic layer, and may be applied in various situations, and such a filling may be applied. It is extremely useful if it is easy (in other words, coating of the cutting surface).

The present invention has been made in view of the above circumstances, and it is possible to obtain a chip obtained in a state in which a plurality of ceramic green sheets and internal electrodes are alternately arranged by cutting a laminated sheet in which a large number of ceramic green sheets and internal electrodes are alternately stacked. It is an object of the present invention to provide a resin sheet capable of easily covering the exposed cut surface of a laminated body in which the laminated body or the laminated body in which a plurality of chips are connected.

By the way, when manufacturing the laminated ceramic capacitor, when the ceramic green sheet on which the internal electrode is printed is heat-pressed, the thickness is different depending on the density (presence or absence) of the internal electrode in the laminating direction, and unevenness occurs on the surface of the laminated sheet There was a problem. For this reason, when it was made into chips, there was a problem that local peeling occurred when the laminated sheet was cut. Moreover, when it was set as a product component by cutting, the surface of components became the curved state by the influence of the unevenness mentioned above, and there existed problems, such as position shift at the time of mounting. Therefore, it may be necessary to add a step of smoothing the surface of the laminated sheet before cutting the laminated sheet.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resin composition which can be laminated on a ceramic green sheet and is excellent in conformity to irregularities and smoothness of the surface, and a resin sheet. .

In order to solve the above-mentioned subject, the present invention adopts the following composition.
First Embodiment
(1) A laminated resin sheet which has a viscosity V5 of 1500 kPa · s or less under the conditions of a temperature of 80 ° C. and a shear rate of 7.6 s−1, and is for embedding a groove,
The groove has a depth / width ratio of 0.5 or more,
The resin sheet is disposed on the surface of the object to be treated so as to cover the groove, and the resin sheet is heated relative to the object under conditions of a temperature of 80 ° C. and a pressure of 92 kg / cm 2. When pressed, it is possible to indent the groove and embed the groove,
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;
Assuming that the viscosity of the first resin sheet is V1 kPa · s and the viscosity of the second resin sheet is V2 kPa · s under the conditions of a temperature of 80 ° C. and a shear rate of 7.6 s ⁻¹ , Log (V2) / Log ( V1) is 0.7 to 1.4,
The melting point or glass transition temperature of the first resin component is less than 100 ° C.,
The content of the inorganic substance in the first resin sheet is 40% by volume or more,
Said V2 is 1500 kPa * s or less,
Said V1 is 1500 kPa * s or less,
A laminated resin sheet , wherein the inorganic substance is a dielectric ceramic .
(2) The first resin component is selected from ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene-methyl (meth) acrylate copolymer and ethylene-ethyl acrylate copolymer The laminated resin sheet as described in said (1) containing 1 type, or 2 or more types of ethylene-type copolymers selected from the group which consists of.
(3) the dielectric ceramic, barium titanate, including one or more dielectric ceramic is selected from the group consisting of strontium titanate and lead zirconate titanate, wherein (1) or (2) The laminated resin sheet as described in.
(4) The laminated resin sheet according to any one of (1) to (3) , wherein the relative dielectric constant of the first resin sheet is 15 or more.
(5) The laminated resin sheet according to any one of (1) to (4) , wherein the thickness of the first resin sheet is 10 to 200 μm.
(6) The laminated resin sheet according to any one of (1) to (5) , wherein the thickness of the second resin sheet is 20 to 1000 μm.
(7) In any one of the above (1) to (6) , one or more resin sheets are further laminated on the side opposite to the side of the second resin sheet on which the first resin sheet is laminated. Laminated resin sheet as described.

Second Embodiment
(8) A resin composition for a resin sheet for embedding a groove , which contains a resin component having a melting point or a glass transition temperature of less than 100 ° C. and an inorganic substance, and the content of the inorganic substance is 40% by volume or more. ,
The inorganic substance is a dielectric ceramic,
A resin composition for a resin sheet for embedding treatment of grooves having a vibration frequency of 10 Hz and a storage elastic modulus at 80 ° C. of 1.0 × 10 ⁸ Pa or less in dynamic viscoelasticity (DMA) measurement.
(9) The resin composition for resin sheet for embedding the groove | channel as described in said (8) in which the said resin component contains an ethylene-type copolymer.
(10) A resin sheet comprising a resin composition for a resin sheet for embedding treatment of a groove according to (8), which has a thickness of 1 μm or more.

In the present specification, “(meth) acrylic acid” is a concept including both “acrylic acid” and “methacrylic acid”.

According to the first embodiment of the present invention, a chipped laminate or a plurality of chipped laminates is obtained by cutting a laminated sheet in which a large number of ceramic green sheets and internal electrodes are alternately stacked. For a body aligned laminate, a resin sheet is provided that can easily cover the exposed cutting surface.

According to the second embodiment of the present invention, a resin composition which can be laminated on a ceramic green sheet and is excellent in the conformity to irregularities and the smoothness of the surface, and a resin sheet are provided.

It is a sectional view showing typically the example of the lamination resin sheet concerning a first embodiment of the present invention. It is sectional drawing which shows typically the other specific example of the laminated resin sheet which concerns on 1st embodiment of this invention. It is sectional drawing for demonstrating typically an example of the usage method of the laminated resin sheet shown in FIG.

First Embodiment
<Laminated resin sheet>
In the laminated resin sheet of the first embodiment, 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, and the temperature is 80 ° C., and the shear rate is 7.6 s. Assuming that the viscosity of the first resin sheet is V1 kPa · s and the viscosity of the second resin sheet is V2 kPa · s under the condition of ⁻¹ , Log (V2) / Log (V1) is 0.7 to 1. It is four.

The laminated resin sheet of the first embodiment can easily cover, for example, the surface of a target member or product with an inorganic material layer such as a dielectric layer derived from the first resin sheet.
When the first resin sheet contains an inorganic substance, when the first resin sheet is heat-treated at a high temperature on the surface of a target member or product, resin components such as the first resin component disappear and the inorganic substance remains. The inorganic substance is sintered to form an inorganic substance layer, whereby the surface of the target member or product is coated with the inorganic substance layer.
Here, as a target member or product, for example, a chipped laminated body obtained by cutting a laminated sheet in which a large number of ceramic green sheets and internal electrodes are alternately stacked, or chip formation The layered product in the state where a plurality of previous chipping planned sites were connected in a row may be mentioned (in the present specification, unless otherwise noted, these are collectively referred to as “laminated body”). And as a surface which an inorganic layer coats, the cut section which became exfoliation of the above-mentioned layered product which arose newly by cutting of the above-mentioned lamination sheet, for example is mentioned.

Immediately after the laminated sheet is cut, a large number of the laminates generated by the cutting are aligned, and the cut sections of the laminates face each other between the laminates. Therefore, for example, in the case of using a resin composition containing an inorganic substance to form the inorganic layer, it is necessary to change the direction of the cutting plane in order to apply the resin composition, and the number of steps increases. It is inefficient. For example, when the cut surface just after cutting is horizontal, it is necessary to change the orientation of the laminate so that the cut surface is directed upward.

On the other hand, in the case where the laminated resin sheet of the present invention is used, the laminated resin sheet is brought into contact such that the first resin sheet is in contact with the upper surface of these laminated bodies, Layer Next, the laminated resin sheet is pressurized, preferably while being heated, to press the laminated body. Thereby, the first resin sheet in the laminated resin sheet intrudes between the laminates and covers the cut surface. Next, the laminated resin sheet is subjected to heat treatment at a high temperature to eliminate resin components such as the first resin component and the second resin component, and coat the cut surface with the inorganic layer. Thus, the cut surface of the said laminated body can be easily coat | covered with an inorganic layer by using the laminated resin sheet of 1st embodiment.
When the laminate is in a state in which a plurality of planned chipping sites are connected in a line, the resin component is eliminated by the step of invading the laminated resin sheet between the laminates or by heat treatment. It may be made into chips by cutting at a certain stage or the like.

The laminated resin sheet of the first embodiment exerts such an excellent effect because the first resin sheet easily indents between the laminates when the laminated resin sheet is pressed. 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 in} the laminated resin sheet is that the first resin sheet easily indents between the laminates. When the viscosity of the second resin sheet is V2 kPa · s under the conditions of a temperature of 80 ° C. and a shear rate of 7.6 s ⁻¹ with V1 kPa · s, Log (V2) / Log (V1) (this specification) In the book, it may be simply abbreviated as “logarithmic ratio of viscosity”) because it is within the specific range as described above.

The inorganic layer formed by using the laminated resin sheet of the first embodiment can function as a protective layer on the surface of the member or product.
Hereinafter, the resin sheet and the laminated resin sheet of the first embodiment will be described in more detail with reference to the drawings. In the drawings to be referred to, there may be a case where a main part is enlarged for convenience, in order to make the features of the first embodiment intelligible, and the dimensional ratio of each component is the same as the actual It does not have to be.

(First example)
FIG. 1 is a cross-sectional view schematically showing a first specific example of the laminated resin sheet of the first embodiment.
The laminated resin sheet 1 shown here is configured by laminating the first resin sheet 11 and the second resin sheet 12.

The first resin sheet 11 contains a first resin component and an inorganic substance.

The melting point or glass transition temperature of the first resin component is preferably less than 100 ° C., and such a first resin component is not particularly limited.

The melting point or glass transition temperature of the first resin component is more preferably 99 ° C. or less, and still more preferably 95 ° C. or less.
When the melting point or glass transition temperature of the first resin component is less than 100 ° C., the effect that the cut surface of the laminate can be easily covered with the inorganic layer is more significantly obtained.
The lower limit value of the melting point or glass transition temperature of the first resin component is not particularly limited, but the melting point or glass transition temperature is preferably 40 ° C. or more, and more preferably 50 ° C. or more.
When the melting point or glass transition temperature of the first resin component is 40 ° C. or higher, the effect of suppressing the deformation of the first resin sheet 11 at the time of manufacturing the laminated resin sheet 1 is further enhanced.

The first resin component preferably contains an ethylene-based copolymer (ethylene-based elastomer). It may contain an ethylene-based copolymer and other resins (which may be referred to as "optional first resin" in the present specification). It may be ethylene copolymer only.
In the present specification, the "ethylene-based copolymer" means a copolymer having a structural unit derived from ethylene.

The ethylene-based copolymer is a copolymer having a constituent unit derived from ethylene and a constituent unit derived from ethylene having at least a polar group as a substituent that substitutes a hydrogen atom (hereinafter referred to as “polar group It may be referred to as "ethylene-based copolymer having the
The ethylene-based copolymer having the polar group has high affinity to metals. By using such an ethylene-based copolymer, as the first resin composition described later, one having a higher degree of dispersion of the inorganic substance can be prepared. Similarly, in the first resin sheet 11 containing such a first resin composition, the degree of dispersion of the inorganic substance becomes higher, and the strength also becomes higher.

Examples of the polar group in ethylene having at least a polar group as described above include an alkylcarbonyloxy group such as an acetyloxy group; a carboxy group; and an alkoxycarbonyl group such as a methoxycarbonyl group and an ethoxycarbonyl group.
As a substituent other than a polar group in ethylene which has the above-mentioned at least polar group, alkyl groups, such as a methyl group, etc. are mentioned, for example.

Examples of the above-mentioned 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, 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.

  The ethylene-based copolymer having the polar group is not limited to the structural unit derived from ethylene and the above-described structural unit derived from ethylene having at least the polar group, as long as the effects of the present invention are not impaired. You may have the other structural unit which does not correspond to any of.

Examples of the monomer from which the other structural unit is derived include α-olefins other than ethylene such as propylene, n-butene and isobutylene; acrylamide; N-methyl acrylamide, N-ethyl acrylamide, N, N-dimethyl acrylamide, di- Acetone acrylamide, acrylamidopropane sulfonic acid and salts thereof, dimethylaminopropyl acrylamide, acid salt of dimethylaminopropyl acrylamide, quaternary salt of dimethylaminopropyl acrylamide, acrylamide derivatives such as N-methylol acrylamide and derivatives thereof; methacrylamide; N- Methyl methacrylamide, N-ethyl methacrylamide, methacrylamide propane sulfonic acid and its salts, N- (3-dimethylaminopropyl) methacrylamide, N- ( Acid salts of -dimethylaminopropyl) methacrylamide, quaternary salts of N- (3-dimethylaminopropyl) methacrylamide, methacrylamide derivatives such as N-methylol methacrylamide and derivatives thereof; methyl vinyl ether, ethyl vinyl ether, n-propyl Vinyl ethers such as vinyl ether, 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; And vinylidene halides such as vinylidene fluoride; allyl acetate (2-propenyl acetate), allyl chloride (3-chloro-1-propene) and the like Ryl compounds (compounds having an allyl group (2-propenyl group)); vinylsilyl compounds such as vinyltrimethoxysilane (a silyl compound having a vinyl group (ethenyl group)); and the like.

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

In the ethylene-based copolymer having a polar group, the ratio of the structural units derived from ethylene having at least the polar group described above is preferably 5 to 50% by mass in all the structural units, and 10 to 45. More preferably, it is mass%. When the ratio is 5% by mass or more, the first resin sheet 11 can contain a sufficient amount of an inorganic material that can more remarkably obtain the effect of using the inorganic material. Moreover, the effect which suppresses blocking of the 1st resin sheet 11 becomes higher because the said ratio is 50 mass% or less.

In the ethylene-based copolymer having a polar group, the proportion of the other constituent unit is preferably 10% by mass or less in all constituent units, and may be 0% by mass. When the ratio is 10% by mass or less, the effect of the first embodiment can be more remarkably obtained that the cut surface of the laminate can be easily covered with the inorganic layer.

Preferred examples of the ethylene-based copolymer having a polar group include ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid methyl copolymer, and Ethylene-ethyl acrylate copolymer etc. are mentioned.
Among these, the ethylene-based copolymer having the polar group is ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer (EMA), ethylene-methyl methacrylate copolymer (EMMA) Or 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 at the molecular chain or at the molecular chain end, as long as the effects of the present invention are not impaired. You may have.

The molecular weight of the ethylene copolymer is not particularly limited.
However, in order to further improve the moldability of the first resin sheet 11, the weight average molecular weight of the ethylene copolymer is preferably 1 × 10 ⁴ to 2 × 10 ⁶ .
In addition, in this specification, a "weight average molecular weight" is a polystyrene conversion value measured by the gel permeation chromatography (GPC) method unless there is particular notice.

The molecular weight dispersity (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of the ethylene-based copolymer is not particularly limited, but the stickiness of the first resin sheet 11 is reduced and the appearance becomes good, It is preferably 1.0 to 3.5, and more preferably 1.1 to 3.0.

The first resin component contained in the first resin sheet 11 may be only one type or two or more types. When the first resin component is two or more, the combination and ratio thereof can be optionally selected according to the purpose.

The first resin component is selected from the group consisting of an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic acid copolymer, an ethylene- (meth) acrylic acid methyl copolymer, and an ethylene-ethyl acrylate copolymer. It is preferable to include one or more selected ethylene-based copolymers.
The first resin component is selected from the group consisting of an ethylene-vinyl acetate copolymer, an ethylene- (meth) acrylic acid copolymer, an ethylene- (meth) acrylic acid methyl copolymer, and an ethylene-ethyl acrylate copolymer. It may be only one or more selected ethylene copolymers.
By using such a first resin component, the effects of the first embodiment can be more remarkably obtained.

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 100% by mass. When the content of the ethylene-based copolymer is 20% by mass or more, the mechanical degree of the first resin sheet 11 is further improved.
In addition, content (mass%) of the said ethylene-based copolymer which is a 1st resin component in the 1st resin sheet 11 is said ethylene-based copolymer weight which is a 1st resin component in the 1st resin composition mentioned later It is the same as the content (mass%) of uniting.

Examples of the optional first resin include modified polyolefin polymers and the like.
The modified polyolefin polymer is, for example, 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. Or the modified | denatured polyolefin polymer etc. which have 2 or more types of functional groups in 1 molecule are mentioned.
Further, as the modified polyolefin polymer, for example, a copolymer of an olefin monomer and a vinyl monomer other than the olefin monomer and a vinyl monomer having the functional group, and a hydrogenated copolymer thereof And copolymers in which one or more hydrogen atoms of these copolymers are substituted with the above functional group.

When the arbitrary first resin is a copolymer, its molecular structure is not particularly limited, and may be, for example, any of a random copolymer, a block copolymer, a graft copolymer, etc. It is preferably a block copolymer or a graft copolymer.

The arbitrary first resin contained in the first resin sheet 11 may be only one kind or two or more kinds. When two or more of the arbitrary first resins contained in the first resin sheet 11 are used, their combination and ratio can be arbitrarily selected according to the purpose.

The content of the optional first resin of the first resin component is preferably 50% by mass or less, more preferably 30% by mass or less, and 0% by mass. When the content of the optional first resin is 50% by mass or less, the effect of the first embodiment can be more remarkably obtained that the cut surface of the laminate can be easily covered with the inorganic layer.
In addition, content (mass%) of the said arbitrary 1st resin in the 1st resin sheet 11 is the same as content (mass%) of the said arbitrary 1st resin in the 1st resin composition mentioned later .

The content of the first resin component of the first resin sheet 11 is preferably 6 to 20% by mass, and more preferably 9 to 14% by mass. When the content of the first resin component of the first resin sheet 11 is in such a range, the first resin sheet 11 has strength and dielectric constant in a well-balanced manner.

The inorganic substance may be a known one and is not particularly limited. Preferred inorganic substances include, for example, insulators such as glass, mica and ceramics. By using these inorganic substances, a short circuit between electrodes can be prevented.

The ceramic is not particularly limited, but preferable examples include dielectric ceramics.
Preferred examples of the dielectric ceramic include barium titanate, strontium titanate, and lead zirconate titanate. By using the dielectric ceramic, the dielectric constant of the first resin sheet 11 can be improved.

The glass or mica is not particularly limited, and preferred examples thereof include glass fibers, glass flakes, glass beads, silica, synthetic mica, nano fillers of synthetic mica, and the like. By using glass or mica, the mechanical strength of the first resin sheet 11 can be improved.

The shape of the inorganic substance is not particularly limited, and can be arbitrarily selected according to the purpose.
For example, it is preferable that the shape of the inorganic substance is in the form of particles, such as a sphere, in that the degree of dispersion of the inorganic substance in the first resin sheet 11 and the first resin composition described later becomes higher. Moreover, in the point which the intensity | strength of the 1st resin sheet 11 improves more, it is preferable that the shape of an inorganic substance is plate shape or scale shape.

The particle size of the inorganic substance is not particularly limited, but the weighted average particle size of the inorganic substance is preferably 0.05 to 1.2 μm, and more preferably 0.1 to 1.0 μm. When the weighted average particle diameter is 0.05 μm or more, the specific surface area of the inorganic substance decreases, and the degree of dispersion of the inorganic substance in the first resin sheet 11 and the first resin composition described later becomes higher. In addition, when the weighted average particle diameter is 1.2 μm or less, the gaps between the inorganic particles become smaller, and the moisture resistance of the first resin sheet 11 and the first resin composition described later is further improved.

In the present specification, “weighted average particle size of inorganic substance” means one calculated by measuring the particle sizes of 100 inorganic substances by observation with a microscope.
In the case of non-particulate inorganic substances such as plate-like and scaly-like, the minor axis and the major axis of these non-particulate inorganic substances are measured to calculate the cross-sectional area of the inorganic substances and have the same cross-sectional area The diameter of the circle is calculated, and this diameter is used as the particle diameter to calculate the weighted average particle diameter as in the case of the particulate inorganic material. Thus, in the present invention, the "weighted average particle size of the inorganic substance" includes not only the weighted average particle size of the particulate inorganic substance but also the weighted average particle size of the nonparticulate inorganic substance.

The inorganic substance contained in the first resin sheet 11 may be only one or two or more. When the inorganic substance which the 1st resin sheet 11 contains is 2 or more types, those combinations and a ratio can be arbitrarily selected according to the objective.

For example, the first resin sheet 11 may use two or more groups of inorganic materials having different weighted average particle sizes in combination. Thus, it becomes possible to increase more content of the inorganic substance of the 1st resin sheet 11 by using together 2 or more groups of inorganic substances from which a weighted average particle diameter differs. For example, in the case where two groups of inorganic substances are used in combination, the weighted average particle diameter of one group of inorganic substances is 0.05 to 0.3 μm, and the other of the inorganic substances from the viewpoint that the above-mentioned effects are more remarkably obtained. It is preferable that the weighted average particle diameter of these is 0.3-1.0 micrometer.

The content of the inorganic substance in the first resin sheet 11 is preferably 40% by volume or more, more preferably 40 to 70% by volume, and particularly preferably 45 to 65% by volume.
When the content of the inorganic substance is in such a range, the first resin sheet 11 has sufficiently high flexibility and fluidity at the time of heating, and as will be described later, a space in which the coating target surface of the laminate is narrow. Even in the case of facing the target surface, the first resin sheet 11 can easily cover the target surface.
When the inorganic substance is a dielectric ceramic, a dielectric layer having a high dielectric constant can be formed from the first resin sheet 11 covering the target surface.
Furthermore, when the content of the inorganic substance is 40% by volume or more, the volume of the first resin sheet 11 before sintering, which will be described later, and the volume of a layer (for example, a dielectric layer) obtained by sintering Difference is smaller, and such a layer can be formed more stably. Moreover, the mechanical degree of the 1st resin sheet 11 improves more because content of the said inorganic substance is 70 volume% or less.
In addition, in this specification, content (volume%) of the inorganic substance of a 1st resin sheet is preferably content at normal temperature. Here, "normal temperature" means a temperature which is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C and the like.

The inorganic substance preferably comprises one or more dielectric ceramics selected from the group consisting of barium titanate, strontium titanate and lead zirconate titanate.
The inorganic substance may be only one or two or more dielectric ceramics selected from the group consisting of barium titanate, strontium titanate and lead zirconate titanate.
By using such a dielectric ceramic, the effect of the first embodiment can be more remarkably obtained that the cut surface of the laminate can be easily covered with a dielectric layer having a sufficiently high dielectric constant.

The first resin sheet 11 may contain other components in addition to the first resin component and the inorganic substance as long as the effects of the present invention are not impaired.
Examples of the other components include resin components other than the first resin component (sometimes referred to as “third resin component” in the present specification), various additives, and the like.

The other components contained in the first resin sheet 11 may be only one or two or more. When the said other component which the 1st resin sheet 11 contains is 2 or more types, those combinations and a ratio can be arbitrarily selected according to the objective.

The content of the other component of the first resin sheet 11 may be appropriately adjusted according to the type of the other component, for example, the content of the inorganic substance may be 40% by volume or more.

The third resin component (a resin component other than the first resin component) is 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, cerium stearate and the like; hindered amines, hindered phenols, sulfur-containing compounds Antioxidants such as acrylates and phosphorus organic compounds or heat resistant stabilizers; UV absorbers such as benzophenones, salicylates, benzotriazoles and the like; weathering agents; light stabilizers; release agents; lubricants; crystal nucleating agents; 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; anti-coloring agents; red phosphorus; metal hydroxide flame retardants; Flame retardants such as flame retardants, silicone flame retardants, halogen flame retardants, and mixtures of the above mentioned halogen flame retardants and antimony trioxide; wood powder; fir powder; walnut powder; waste paper; phosphorescent pigment; Antibacterial agents such as antibacterial agents or antifungal agents; Mold corrosion inhibitors such as hydrotalcites such as magnesium-aluminum hydroxyhydrate; Antistatic agents; Antiblocking agents; Surfactants; Deodorants; Plasticizers; Dispersion Agents and the like.
The additive is preferably a plasticizer in that the flexibility of the first resin composition described later is improved.

Among the additives, the plasticizer is not particularly limited.
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. A plasticizer, a castor oil plasticizer, etc. are mentioned.
As the plasticizer, more specifically, for example, neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di (2-ethyl butyrate), polyoxyethylene diacetate, polyoxyethylene di (2-ethyl hexa) Polyol esters such as polyoxypropylene monolaurate, polyoxypropylene monostearate, polyoxyethylene dibenzoate, and polyoxypropylene dibenzoate; aliphatic carboxylic acid esters such as butyl oleate; acetyl triethyl citrate, Oxyates such as tributyl acetyl citrate, ethoxycarbonyl methyl dibutyl citrate, di (2-ethylhexyl) citrate, methyl acetyl ricinoleate, 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 compounds such as coconut oil fatty acid; pentaerythritol; sorbitol; polyacrylic acid ester; silicone oil; paraffins and the like.

In the first resin sheet 11, the ratio of the content of the plasticizer to the total content of the components other than the inorganic substance is preferably 70% by mass or less, more preferably 60% by mass or less, and 0% by mass It may be%. When the ratio of the content is 70% by mass or less, the flexibility of the first resin sheet 11 is improved without losing the strength.

When the inorganic substance is a dielectric ceramic, the relative dielectric constant of the first resin sheet 11 is preferably 15 or more, and more preferably 20 or more. When the dielectric constant of the first resin sheet 11 is 15 or more, for example, a member obtained by forming a dielectric layer using the laminated resin sheet 1 or in the chipped laminated body described above The electrical capacity of the product (e.g., a multilayer ceramic capacitor etc.) is further increased.
The upper limit of the relative dielectric constant of the first resin sheet 11 is not particularly limited, but considering the ease of preparation of the first resin sheet 11, the relative dielectric constant of the first resin sheet 11 is 100 or less. Is preferred.
The relative dielectric constant can be measured under the condition of a frequency of 10 MHz using a commercially available dielectric constant measurement device (for example, one manufactured by Keysight Technologies).

The first resin sheet 11 may be formed of one layer (single layer), or may be formed of two or more layers. When the first resin sheet 11 includes 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 first embodiment are not impaired.

In the present specification, not only in the case of the first resin sheet 11, but “a plurality of layers may be the same as or different from each other” means “all the layers may be the same or all the layers”. It means that the layers may be different, and only some of the layers may be identical.
Furthermore, "a plurality of layers are different from each other" means that "at least one of a constituent material and a thickness of each layer is different from each other".

The thickness of the first resin sheet 11 is preferably 10 to 200 μm, and more preferably 50 to 150 μm.
When the thickness of the first resin sheet 11 is 10 μm or more, the strength of the first resin sheet 11 is further improved.
In addition, when the thickness of the first resin sheet 11 is 200 μm or less, the thickness of the first resin sheet 11 does not become excessive. For example, even when the surface to be covered faces a narrow space, such as a surface to be covered is present between a large number of the laminates in an aligned state, the surface to be covered can be easily made with the first resin sheet 11 It can be coated.
When the first resin sheet 11 is composed of a plurality of layers, the total thickness of the plurality of layers may be set to be the thickness of the preferable first resin sheet 11 described above.

The second resin sheet 12 contains a second resin component.
The second resin component is not particularly limited as long as it satisfies the above-mentioned logarithmic ratio of viscosity.

The second resin component is a general-purpose resin such as polyethylene (PE) resin, polypropylene (PP) resin, polyvinyl chloride (PVC) resin, or thermoplastic elastomer (TPE) (hereinafter, these polymers are comprehensively included) It is preferable to include "a second polymer". The second resin component may contain a second polymer and another resin other than that (which may be referred to herein as “optional second resin”), or the second polymer. It may be only.

More specifically, as the second resin component, polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid Ethyl 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.
More specifically, as the thermoplastic elastomer among the second resin component, for example, an olefin-based elastomer (TPO), a polyvinyl chloride-based elastomer (TPVC), a styrene-based elastomer (SBC), a urethane-based elastomer (TPU) And polyester-based elastomers (TPEE) and polyamide-based elastomers (TPAE).

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 to 2 × 10 ⁶ in that the moldability of the second resin sheet 12 is further improved.

The molecular weight dispersity (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of the second polymer is not particularly limited, but the stickiness of the second resin sheet 12 is reduced and the appearance becomes good as well. It is preferably 1.0 to 3.5, and more preferably 1.1 to 3.0.

The second resin component contained in the second resin sheet 12 may be only one type or two or more types. When the 2nd resin component which the 2nd resin sheet 12 contains is 2 or more types, those combinations and a ratio can be arbitrarily selected according to the objective.

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) acrylate / styrene (MS) resin, Ren / butadiene / styrene (SBS) resin, styrene / isoprene / butadiene / styrene (SIBS) resin, olefin elastomer (TPO), polyvinyl chloride elastomer (TPVC), styrene elastomer (SBC), urethane elastomer (TPU) It is preferable to include a second polymer selected from the group consisting of polyester elastomer (TPEE) and polyamide elastomer (TPAE). The second polymer may be one or two or more. By using such a second resin component, the effect of the first embodiment can be more remarkably obtained that the cut surface of the laminate can be easily covered with the inorganic layer.

The content of the second polymer of the second resin component is preferably 20% by mass or more, more preferably 50% by mass or more, and 100% by mass. When the content of the second polymer is 20 mass or more, the mechanical degree of the second resin sheet 12 is further improved.
The content (% by mass) of the second polymer as the second resin component in the second resin sheet 12 is the content of the second polymer as the second resin component in the second resin composition described later. The same as (mass%).

Examples of the optional second resin include the same as the optional first resin.

When the optional second resin is a copolymer, its molecular structure is not particularly limited, and may be, for example, any of a random copolymer, a block copolymer, a graft copolymer, etc. It is preferably a block copolymer or a graft copolymer.

The optional second resin contained in the second resin sheet 12 may be only one type or two or more types. When two or more of the optional second resins contained in the second resin sheet 12 are used, the combination and ratio thereof can be arbitrarily selected according to the purpose.

The content of the optional second resin of 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 effects of the first embodiment can be more remarkably obtained.
The content (% by mass) of the optional second resin as the second resin component in the second resin sheet 12 is the optional second resin component as the second resin component in the second resin composition described later. It is the same as the content (mass%) of resin.

The content of the second resin component of the second resin sheet 12 is preferably 40 to 100% by mass, and more preferably 60 to 100% by mass. When the content of the second resin component of the second resin sheet 12 is in such a range, the strength of the second resin sheet 12 is further improved.

The second resin sheet 12 may contain other components in addition to the second resin component as long as the effects of the present invention are not impaired.
As said other component, various additives etc. are mentioned, for example.

The other components contained in the second resin sheet 12 may be only one or two or more. When the said other component which the 2nd resin sheet 12 contains is 2 or more types, those combinations and a ratio can be arbitrarily selected according to the objective.

The content of the other component of the second resin sheet 12 may be appropriately adjusted according to the type of the other component.

Examples of the additive in the second resin sheet 12 include the same as the additives in the first resin sheet 11.
The additive in the second resin sheet 12 is preferably a plasticizer in that adjustment of the viscosity V2 of the second resin sheet is facilitated.

When using the said plasticizer, it is preferable that it is 1-60 mass%, and, as for content of the plasticizer of the 2nd resin sheet 12, it is more preferable that it is 5-40 mass%. The effect by using a plasticizer is more notably acquired because content of a plasticizer is 1 mass% or more. Moreover, the intensity | strength of the 2nd resin sheet 12 improves more because content of a plasticizer is 60 mass% or less.

The second resin sheet 12 may be formed of one layer (single layer) or may be formed of two or more layers. When the second resin sheet 12 includes 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 first embodiment are not impaired.

The thickness of the second resin sheet 12 is preferably 20 to 1000 μm, and more preferably 150 to 800 μm. By the thickness of the 2nd resin sheet 12 being 20 micrometers or more, the intensity of the 2nd resin sheet 12 improves more. In addition, when the thickness of the second resin sheet 12 is 1000 μm or less, the thickness of the second resin sheet 12 is not excessive, and the handleability is improved.
When the second resin sheet 12 is composed of a plurality of layers, the total thickness of the plurality of layers may be set to be the thickness of the above-mentioned preferable second resin sheet 12.

In the laminated resin sheet 1, the viscosity of the first resin sheet 11 under the conditions of a temperature of 80 ° C. and a shear rate of 7.6 s ⁻¹ is V ¹ kPa · s, and the viscosity of the second resin sheet 12 under the same conditions Log (V2) / Log (V1) (logarithmic ratio of viscosity) is 0.7-1.4, when V2kPa.s.
When the logarithmic ratio of the viscosity is in such a range, even when the surface to be covered with the first resin sheet 11 faces a narrow space, the surface can be easily covered with the first resin sheet 11. As a result, the target surface can be easily coated with the inorganic layer.
For example, a chipped laminate obtained by cutting a laminate sheet in which a large number of ceramic green sheets and internal electrodes are alternately stacked, or a plurality of chipped planned portions before chipping are arranged in a row The exposed cut surface of the connected laminate can be easily coated with the first resin sheet 11 and finally with the inorganic layer. The method of forming such an inorganic layer will be described in detail later.

Thus, in the laminated resin sheet 1, the logarithmic ratio of the viscosity is preferably 0.72 to 1.37 from the viewpoint of easier covering of the target surface with the first resin sheet 11.

The viscosity (V1) of the first resin sheet 11 is not particularly limited as long as the condition of the logarithmic ratio of the viscosity is satisfied.
However, in the present invention, V1 is preferably 1500 kPa · s or less, more preferably 1200 kPa · s or less, and particularly preferably 1000 kPa · s or less. By the said V1 being 1500 kPa * s or less, the coating | cover by the 1st resin sheet 11 (inorganic material layer) of an object surface becomes easier.

On the other hand, V1 is preferably 1 kPa · s or more, more preferably 5 kPa · s or more, and particularly preferably 10 kPa · s or more. When the V1 is 1 kPa · s or more, the strength of the first resin sheet 11 is further improved, and the deformation is further suppressed.

The V1 can be adjusted, for example, by adjusting the type or content of the component contained in the first resin sheet 11, the thickness of the first resin sheet 11, or the like.

The viscosity (V2) of the second resin sheet 12 is not particularly limited as long as the condition of the logarithmic ratio of the viscosity is satisfied.
However, in the present invention, the V2 may be the same as or different from the V1, but is preferably equal to or less than the V1.

That is, V2 is preferably 1500 kPa · s or less, more preferably 1200 kPa · s or less, and particularly preferably 900 kPa · s or less. By the said V2 being 1500 kPa * s or less, the coating | cover by the 1st resin sheet 11 (inorganic material layer) of an object surface becomes easier.

On the other hand, V2 is preferably 0.5 kPa · s or more, more preferably 1 kPa · s or more, and particularly preferably 5 kPa · s or more. When the V2 is 0.5 kPa · s or more, the strength of the second resin sheet 12 is further improved, and the deformation is further suppressed.

The V2 can be adjusted, for example, by adjusting the type or content of the component contained in the second resin sheet 12, the thickness of the second resin sheet 12, or the like.

The V1 and V2 can be measured, for example, using a viscosity measuring apparatus (for example, “Capillograph” manufactured by Toyo Seiki Co., Ltd.) by the following method.
(Measurement method of viscosity)
A heated cylinder is filled with a first resin sheet or a second resin sheet (hereinafter abbreviated as "resin pellet") processed into a pellet shape, which is sufficiently preheated, and then is plungerd with a constant speed plunger The resin pellet heated to 80 ° C. is extruded from the orifice (2 mmφ × 10 mm L) provided in the lower part of the cylinder, and the melt viscosity is calculated from the stress measured at that time. At this time, measurement is carried out by changing the lowering speed of the plunger, and the melt viscosity at a shear rate of 7.6 s ⁻¹ is determined from the change curve of the melt viscosity with respect to the shear rate of the resin pellet. Or adopted as V2.

Although the first resin sheet 11 and the second resin sheet 12 satisfy the above-described conditions of viscosity, the operating temperature of the first resin sheet 11 and the second resin sheet 12, in other words, the laminated resin sheet 1, is The temperature is not limited to 80 ° C., and the operating temperature can be set arbitrarily according to the purpose.

The laminated resin sheet of the present invention is not limited to the above-described embodiment, and some of the configurations may be changed, deleted or added without departing from the scope of the present invention.
For example, although the laminated resin sheet 1 shown in FIG. 1 includes the first resin sheet 11 and the second resin sheet 12, the laminated resin sheet of the present invention may have other layers (sheets). .

(Second example)
FIG. 2 is a cross-sectional view schematically showing another specific example (second specific example) of the laminated resin sheet of the first embodiment.
In FIGS. 2 and 3, the same components as those shown in FIG. 1 are designated by the same reference numerals and their detailed description will be omitted.

In the laminated resin sheet 2 shown here, the third resin sheet 13 is further laminated on the side opposite to the side of the second resin sheet 12 on which the first resin sheet 11 is laminated.
That is, in the laminated resin sheet 2, the first resin sheet 11, the second resin sheet 12, and the third resin sheet 13 are laminated in this thickness direction in this order.

Thus, the laminated resin sheet of the second specific example is one in which one or more resin sheets are further laminated on the side opposite to the side on which the first resin sheet is laminated of the second resin sheet, It is also good.

The third resin sheet 13 is not particularly limited as long as it contains a resin that can maintain the sheet shape, and can be set arbitrarily according to the purpose.
For example, the third resin sheet 13 may contain only a resin component (sometimes referred to herein as a "third resin component"), or the resin component (third resin component) and the like. The other components may be contained together. The components of the third resin sheet 13 may be appropriately selected according to the purpose.

The third resin component is not particularly limited, and may be, for example, the same as or different from the resin components listed as the first resin component or the second resin component.

The third resin component and the other components contained in the third resin sheet 13 may be either alone or in combination of two or more. When the third resin component and the other components contained in the third resin sheet 13 are two or more, the combination and ratio thereof can be optionally selected according to the purpose.

The third resin sheet 13 may be surface-treated. As such a third resin sheet 13, for example, a release sheet in which one surface or both surfaces of the resin sheet is subjected to release processing can be mentioned.
Preferred examples of the third resin component contained in the release sheet include 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.
In the laminated resin sheet 2, when the third resin sheet 13 is the release sheet, it is preferable that the third resin sheet 13 be disposed such that at least the release treated surface is in contact with the second resin sheet 12. .

The third resin sheet 13 may be formed of one layer (single layer), or may be formed of two or more layers. When the third resin sheet 13 is composed of a plurality of layers, the plurality of layers may be identical to or different from each other. The combination of these multiple layers is not particularly limited as long as the effects of the present invention are not impaired.

The thickness of the third resin sheet 13 may be appropriately selected according to the type of the third resin sheet 13, but in general, the thickness is preferably 12 to 100 μm.

The laminated resin sheet of the present invention is not limited to the above-described embodiment, and some of the configurations may be changed, deleted or added without departing from the scope of the present invention.

<Method of manufacturing laminated resin sheet>
The laminated resin sheet of the first embodiment can be manufactured, 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 in which the said other component is mix | blended as needed in a sheet form.
In addition, the second resin sheet is formed into a sheet by molding the second resin composition in which the second resin component or the second resin component and, if necessary, another component other than the second resin component are blended. It can be manufactured by doing.

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

The first resin composition, for example, heats the resin component such as the first resin component to a temperature above the melting point or glass transition temperature to make it in a molten state (liquid state) or rubbery state, and the inorganic substance is necessary. According to the above, it can be produced by adding and kneading non-resin components such as the above-mentioned other components.
Similarly, for the second resin composition, for example, the resin component such as the second resin component is heated to a temperature equal to or higher than the melting point or the glass transition temperature to bring it into a molten state (liquid state) or a rubbery state. It can be produced by adding non-resin components such as the above-mentioned other components to this and kneading.

As described above, the method for heating the resin component to a temperature equal to or higher than the melting point or glass transition temperature is not particularly limited, and known methods can be applied. However, it is preferable to be a method of heating using a closed-type kneader, so-called internal mixer.
As described above, the method of adding and kneading the non-resin component to the molten or rubber resin component is not particularly limited, and known methods can be applied. However, the method of kneading using a kneader such as an open roll, a single screw extruder, a twin screw kneader, a kneader or a Banbury mixer is preferable.

As described above, the first resin composition or the second resin composition obtained as a kneaded material after kneading can be formed into a pellet or a tablet, for example, by further performing granulation, cooling treatment and the like. .

Although the method to shape | mold a 1st resin composition in a sheet shape at the time of manufacture of a 1st resin sheet is not specifically limited, As a specific example, the method etc. which are shape | molded using the extrusion apparatus provided with T die are mentioned. .
Similarly, the method for forming the second resin component or the second resin composition into a sheet at the time of production of the second resin sheet is not particularly limited, but as a specific example, an extrusion apparatus equipped with a T-die is used And the like.

Lamination of the first resin sheet and the second resin sheet may be performed by a known method. For example, the laminated resin sheet of the first embodiment is obtained by laminating these sheets by thermal lamination or the like.

As the laminated resin sheet, one or more resins on the side opposite to the side on which the first resin sheet is laminated, such as the one on which the third resin sheet is laminated, as described above, etc. The laminated sheet can be produced, for example, by the following method.
That is, first, the one or more resin sheets (for example, the third resin sheet) are manufactured by the same method as in the case of the first resin sheet or the second resin sheet. At this time, the resin composition (for example, the third resin composition) is the same as the case of the first resin composition except that the one or more resin sheets (for example, the third resin sheet) are different in blending components. Can be produced by using this resin composition.
Next, the step of laminating the one or more resin sheets on the second resin sheet on the side opposite to the side on which the first resin sheet is laminated or on the side to which the first resin sheet is to be laminated In the method, it performs additionally at appropriate timing. Thereby, the target laminated resin sheet can be manufactured. Alternatively, when laminating the first resin sheet and the second resin sheet as described above, the intended laminated resin sheet can be produced by simultaneously laminating the one or more resin sheets.

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

<How to use laminated resin sheet>
By using the laminated resin sheet of the first embodiment, for example, the surface of a target member or product can be easily covered with an inorganic layer such as a dielectric layer derived from the first resin sheet.
Hereinafter, the usage method of such a laminated resin sheet is demonstrated, referring drawings.
FIG. 3: is sectional drawing for demonstrating typically an example of the usage method of the laminated resin sheet 1 shown in FIG. Here, the case where the chipped laminated body described above is the use target of the laminated resin sheet will be described.

At the time of use of the laminated resin sheet, first, as shown in FIG. 3A, the plurality of laminated bodies 9 are put together, and the first resin sheet 11 is formed on the exposed first surface 9a. The laminated resin sheet 1 is superposed on the laminated body 9 so as to be in contact. Thereby, a first laminated structure 71 which is a laminate of the plurality of laminates 9 and the laminated resin sheet 1 is formed. The first laminated structure 71 is supported by the support member 6 on the laminate 9 side, and the first surface 9 a of the laminate 9 is a surface opposite to the side supported by the support member 6. (Exposed surface).

The plurality of laminates 9 are, for example, chip-formed laminates obtained by cutting a laminate sheet in which a large number of ceramic green sheets and internal electrodes (both not shown) are alternately stacked. Yes, it has been aligned by cutting. Further, the side faces 9c of the laminate 9 are all exposed bare surfaces newly produced by cutting the laminate sheet, and the end of the laminate 9 including the facet 9c is fragile. . The plurality of laminates 9 are arranged adjacent to each other with the gap portion 8 generated by the cutting, and the facets 9 c of the laminates 9 face each other between the laminates 9.
The laminate 9 may be a laminate obtained by cutting the laminate sheet, in which a plurality of planned chipping sites before chipping are connected in a row, and such a laminate Also, it will be in the state aligned by cutting.

Next, when using the laminated resin sheet, the first laminated structure 71 is added in the laminating direction of the laminated body 9 and the laminated resin sheet 1 (in other words, in the thickness direction of the first laminated structure 71). Press down.

At this time, for example, as shown in FIG. 3B, pressure is applied from both sides of the laminated resin sheet 1 side of the first laminated structure 71 and the laminated body 9 side (arrow P1 direction and The pressure may be applied by applying pressure in the P2 direction, or the pressure may be applied from the laminated resin sheet 1 side without applying pressure from the laminate 9 side of the first laminate structure 71 (only in the arrow P1 direction). The pressure may be applied by applying pressure, or pressure may be applied from the laminate 9 side without applying pressure from the laminate resin sheet 1 side of the first laminate structure 71 (pressure is applied only in the direction of arrow P2) You may go by.

As described above, by pressing the first laminated structure 71, the laminated resin sheet 1 is pressed, and as shown in FIG. 3C, the first resin sheet 11 in the laminated resin sheet 1 is the laminated body 9 Invaginate the gap 8 between each other and cover the facet 9c. As described above, the first resin sheet 11 easily indents the void portion 8 by simply pressing the first laminated structure 71 and covers the cut surface 9 c of the laminated body 9. In addition to the fact that 11 has appropriate properties, the second resin sheet 12 is present adjacent to the first resin sheet 11. The logarithmic ratio (Log (V2) / Log (V1)) of the viscosity specified by the viscosity (V1) of the first resin sheet and the viscosity (V2) of the second resin sheet is 0.7 to 1. By being within the specific range of 4, such excellent effects are achieved.

Thus, when the first resin sheet 11 intrudes into the void portion 8, as shown in FIG. 3C, the second resin sheet 12 also does not contact the edge 9c of the laminate 9 at all. Invading, typically, the second resin sheet 12 invades to a depth of half or more of the cavity 8.

The pressurization of the first stacked structure 71 can be performed by a known method. For example, both surfaces of the first laminated structure 71, that is, a surface on the side opposite to the side on which the first resin sheet 11 of the laminate 9 is provided (herein, referred to as "second surface" And 9b, and the surface 12a of the second resin sheet 12 on the side opposite to the side on which the first resin sheet 11 is provided (sometimes referred to herein as the "first surface"). A pressure plate for applying pressure is disposed (laminated) on one or both of the buffer sheets, and the first laminated structure 71 can be pressurized by applying pressure to the pressure plate. The buffer sheet and the pressure plate may be disposed on the side to which the pressure of the first laminated structure 71 is not applied (that is, the side only supporting the first laminated structure 71). The buffer sheet is for suppressing damage to the laminated resin sheet 1 when pressurized.

As described above, when the buffer sheet and the pressure plate are used, a release sheet may be further disposed (laminated) between the first laminated structure 71 and the buffer sheet. The release sheet in this case is for preventing sticking between the first laminated structure 71 and the buffer sheet, and for example, one surface of the resin film or both surfaces are subjected to release processing Can be mentioned.
As said resin film, a polyethylene terephthalate (PET) film etc. are mentioned, for example. Moreover, as said mold release process, what is performed using well-known mold release process agents, such as a silicone treatment agent, etc. are mentioned, for example. Thus, as the release sheet, the same one as described above as the third resin sheet 13 can be mentioned.
That is, the pressurization of the laminated resin sheet 1 performed using the said release sheet means the same thing as the pressurization of the laminated resin sheet 2 in case the 3rd resin sheet 13 is a release sheet.
In the present specification, as described above, a structure in which at least a buffer sheet and a pressure plate are laminated on a first laminated structure is referred to as a "second laminated structure".

The pressurization of the first laminated structure 71 is preferably performed while heating at least the laminated resin sheet 1, and may be performed while heating the entire laminated resin sheet 1 or the entire first laminated structure 71. By doing this, the cut surface 9c of the laminate 9 can be more easily covered with the first resin sheet 11 in the laminated resin sheet 1 as described later.
The heating temperature at the time of pressurization may be appropriately adjusted in consideration of the melting point or the glass transition temperature of the first resin component and the second resin component, but in general, the temperature is preferably 70 to 100 ° C.

The pressure at the time of pressurization of the first laminated structure 71 may be appropriately adjusted in consideration of the heating temperature at the time of pressurization, the type of the laminated resin sheet 1 and the like, but it is usually 50 to 1000 kg / cm ² . Is preferred.
Moreover, although the pressurization time of the 1st laminated structure 71 may be suitably adjusted in consideration of the heating temperature at the time of pressurization, pressure, etc., it is usually preferable that it is 1 to 30 minutes.

Next, when the laminated resin sheet is used, the laminated resin sheet 1 in the state of being thus invaginated in the void portion 8 is subjected to heat treatment at a high temperature to obtain a resin such as the first resin component and the second resin component. The ingredients are allowed to dissipate and the inorganics remain. This mineral is sinterable and forms a mineral layer. As a result, the inorganic layer 10 is formed from the first resin sheet 11 and the second resin sheet 12 disappears, so the facet 9c of the laminate 9 is covered with the inorganic layer 10 as shown in FIG. Be done. Since the inorganic material layer 10 is formed only by heat-treating the laminated resin sheet 1 at a high temperature, as a result, the facet 9 c of the laminate 9 can be easily covered with the inorganic material layer 10.
At this time, the inorganic layer 10 is also formed on the first surface 9 a of the laminate 9 and the support member 6 at the same time. However, in the places where the coating with the inorganic layer 10 is unnecessary, the extra inorganic layer 10 is formed. As appropriate.

As described above, by using the laminated resin sheet 1, the laminated body 9 in the aligned state immediately after the cutting of the laminated sheet is not subjected to a complicated operation such as changing its direction, for example. 9c can be easily coated with the inorganic layer 10.

Although the method of using the laminated resin sheet 1 shown in FIG. 1 has been described here, other laminated resin sheets of the first embodiment such as the laminated resin sheet 2 shown in FIG. Play an effect.

<Resin sheet>
A resin sheet for embedding a groove, wherein the groove has a depth / width ratio of 0.5 or more, and covers the groove on the surface of the object to be treated having the groove. When a resin sheet is placed and pressed while heating the resin sheet against the object to be treated under the conditions of a temperature of 190 ° C. and a pressure of 92 kg / cm ² , the resin sheet is indented in the groove to embed the groove The resin sheet that is possible (sometimes referred to herein as the "fourth resin sheet") is novel.
Among the fourth resin sheets, one containing an inorganic substance similar to the inorganic substance in the first resin sheet may be included in the first resin sheet.

A resin sheet for embedding the groove in the same manner, wherein the viscosity V5 under the conditions of temperature 80 ° C. and shear rate 7.6 s ⁻¹ is 1500 kPa · s or less, and the groove has a depth / depth The resin sheet is disposed on the surface of the object to be treated having a width ratio of 0.5 or more so as to cover the grooves, and the temperature is 80 ° C., and the pressure is 92 kg / cm ^2. When pressed while heating a resin sheet against the object to be treated, a resin sheet which can be recessed in the groove and can be embedded in the groove (referred to as a "fifth resin sheet" in the present specification) May also be new.
Among the fifth resin sheets, one containing an inorganic substance similar to the inorganic substance in the first resin sheet may be included in the first resin sheet.

The first resin sheet in the above-mentioned laminated resin sheet is also novel.

In the present specification, when the first resin sheet, the fourth resin sheet, and the fifth resin sheet described above are individually handled, these resin sheets may be collectively referred to simply as “resin sheet”. The mere description of "resin sheet" does not mean the above-mentioned laminated resin sheet, unless otherwise noted.

Any of the resin sheets (first resin sheet, fourth resin sheet, fifth resin sheet) can be used in the same manner as in the case of the laminated resin sheet, and in this case, the grooves between the laminated bodies are easily embedded. It plays an effect.

That is, immediately after the cutting of the laminated sheet, the resin sheets are overlapped on the upper surface of the laminated body with a large number of the laminated bodies in an aligned state as one, and the grooves between the laminated bodies are covered. The resin sheet is disposed, and the resin sheet is pressurized while preferably heated, and pressed against the laminate, whereby the resin sheet indents in the grooves between the laminates and embeds the grooves. If these resin sheets contain an inorganic substance, then the resin sheet in such a state is subjected to heat treatment at a high temperature to lose the resin component (for example, the first resin component in the case of the first resin sheet) Then, the groove can be embedded with the inorganic layer. Thus, the groove of the laminate can be easily embedded with the resin sheet or the inorganic layer by using the resin sheet. A laminated ceramic capacitor or the like can be manufactured from the laminate in which the groove is embedded with the inorganic layer (the cut surface is covered with the inorganic layer). On the other hand, in the laminated body in which the grooves are embedded with the resin sheet, the resin sheet can be, for example, a protective layer of the cut surface, that is, the resin sheet can be used as a protective sheet. By covering the cut surface of the laminate with a protective layer, breakage of the laminate (particularly, the cut surface thereof) can be prevented during handling of the laminate, for example, when transporting or processing the laminate. it can.

In the case where the laminate, which is the target of the embedding process, is obtained by cutting the laminate sheet and a plurality of planned chipping sites are connected in a line, the groove is formed by the resin sheet. Cutting may be performed at the embedding stage, the stage at which the resin component is eliminated by heat treatment, or the like.
In addition, the resin sheet embedded in the groove may be cut, for example, at the time of cutting of such a laminate, or may be heat-treated at a high temperature at any timing before and after cutting. When the resin sheet does not contain an inorganic substance, the heat treatment at a high temperature can completely eliminate the resin sheet.

As a state in which the resin sheet (the first resin sheet, the fourth resin sheet, the fifth resin sheet) embeds the groove, for example, in FIG. 3C, the laminated resin sheet 1 (the first resin sheet 11 and the The state which replaced 2 resin sheet 12) with the single resin sheet is mentioned. However, this is only an example, and even when the resin sheet reaches the bottom of the groove and does not completely embed the groove without gaps, the resin sheet is significantly superior to the conventional resin sheet in groove embedding. ing.

In the groove to be embedded with the resin sheet, the ratio of depth / width ([depth of groove] / [width of groove]) is preferably 0.5 or more, and is 0.5 to 20. Is more preferable, and 1 to 15 is particularly preferable. By the ratio being 0.5 or more, the groove filling effect is further improved. On the other hand, when the ratio is 20 or less, there is no need to increase the fluidity (for example, V1 or V5 or V4 described later) of the resin sheet when heated, and the resin sheet strength at normal temperature Improve.

The fourth resin sheet can have the same configuration as the first resin sheet except that the inorganic substance is not an essential component, and the components of the fourth resin sheet include the components of the first resin sheet and The same thing is mentioned. Moreover, as a resin component which a 4th resin sheet contains, polyolefin, such as a polypropylene, a polystyrene, 4-methyl- 1-pentene, for example; The derivative of the said polyolefin etc. are mentioned, for example.
The fourth resin sheet containing an inorganic substance may be the same as or different from the first resin sheet.

The viscosity V4 of the fourth resin sheet under the conditions of a temperature of 190 ° C. and a shear rate of 7.6 s ⁻¹ is preferably 1 to 1500 kPa · s, more preferably 1 to 1200 kPa · s, and 1 to 1 It is particularly preferable that it is 1000 kPa · s, and for example, it may be any of 1 to 500 kPa · s, 1 to 250 kPa · s, 1 to 120 kPa · s, and 1 to 60 kPa · s. The filling property of a groove | channel improves more because the said V4 is 1500 kPa * s or less. In addition, when the V4 is 1 kPa · s or more, the strength of the fourth resin sheet is further improved, and the deformation is further suppressed.
However, the operating temperature of the fourth resin sheet is not limited to 190 ° C., and the operating temperature can be set arbitrarily according to the purpose.

The V4 can be adjusted, for example, by adjusting the type or content of the component contained in the fourth resin sheet, the thickness of the fourth resin sheet, or the like.

The fifth resin sheet can have the same configuration as the first resin sheet except that the inorganic substance is not an essential component, and the components of the fifth resin sheet include the components of the first resin sheet and The same thing is mentioned. The fifth resin sheet containing an inorganic substance may be the same as or different from the first resin sheet.

The V5 is 1500 kPa · s or less, and preferably in the same range as the V1.
That is, the V5 is preferably 1200 kPa · s or less, and more preferably 1000 kPa · s or less. The filling property of a groove | channel improves more because the said V5 is 1500 kPa * s or less.
On the other hand, V5 is preferably 1 kPa · s or more, more preferably 5 kPa · s or more, and particularly preferably 10 kPa · s or more. When the V5 is 1 kPa · s or more, the strength of the fifth resin sheet is further improved, and the deformation is further suppressed. However, the operating temperature of the fifth resin sheet is not limited to 80 ° C., and the operating temperature can be set arbitrarily according to the purpose.

The V5 can be adjusted, for example, by adjusting the type or content of the component contained in the fifth resin sheet, the thickness of the fifth resin sheet, or the like.

The V4 can be measured, for example, in the same manner as in the cases of V1 and V2 except that the heating temperature when extruding the resin pellet is changed to 80 ° C. to 190 ° C.
The V5 can be measured, for example, in the same manner as the V1 and V2.

The fourth resin sheet and the fifth resin sheet can be manufactured by the same method as in the case of the first resin sheet when the contained component is the same as the first resin sheet. On the other hand, the fourth resin sheet and the fifth resin sheet can be manufactured by the same method as in the case of the first resin sheet except that the components to be used are different when the contained component is different from the first resin sheet.

Second Embodiment
Hereinafter, the resin composition of 2nd embodiment to which this invention is applied, and the resin sheet using this resin composition are demonstrated in detail.

<Resin composition>
First, an example of the configuration of the resin composition according to the second embodiment of the present invention will be described. The resin composition of the second embodiment contains a resin component having a melting point or a glass transition temperature of less than 100 ° C., and an inorganic substance.

(Resin component)
The resin component applicable to the resin composition of the second embodiment is not particularly limited as long as the melting point or the glass transition temperature is less than 100 ° C. When the resin component has a melting point or a glass transition temperature of less than 100 ° C., it can be used in the step of pressing a ceramic green sheet using PVA. The lower limit of the melting point or glass transition temperature of the resin component is not particularly limited, but is preferably 40 ° C. or more, more preferably 50 ° C. or more. When the melting point or the glass transition temperature is 40 ° C. or more, deformation during lamination can be prevented.

The resin component is ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, vinyl chloride-vinyl acetate copolymer, ethylene- (meth) At least one or more ethylene-based copolymer in the group consisting of acrylic acid copolymer, ethylene- (meth) acrylic acid methyl copolymer, ethylene-methyl acrylic acid copolymer, and ethylene-ethyl acrylic acid copolymer It is preferred to include coalescing. Among these, ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer (EMA), ethylene-methyl methacrylate copolymer (EMMA), and ethylene-ethyl acrylate copolymer (EEA) Preferably, ethylene-methyl acrylate copolymer (EMA) and ethylene-methyl methacrylate copolymer (EMMA) are more preferable. When the resin component contains an ethylene-based copolymer (ethylene-based elastomer) having high metal affinity, the inorganic substance in the resin composition can be highly dispersed, and the film strength can be improved.

The ethylene copolymer has ethylene as a monomer unit and a vinyl group having a polar group as a monomer unit. The proportion of the vinyl group having a polar group in the ethylene-based copolymer is preferably 5 to 50% by mass, and more preferably 10 to 45% by mass, in the total mass of the ethylene-based copolymer. . When the proportion of the vinyl group having a polar group is 5% by mass or more, an inorganic material can be contained in a sufficient amount. On the other hand, generation | occurrence | production of blocking can be suppressed as it is 50 mass% or less.

The ethylene-based copolymer may contain other monomer units as long as the effects of the present invention are not impaired. Other monomer units include, for example, α-olefins such as ethylene, propylene, n-butene and isobutylene; acrylic acid and salts thereof; methyl acrylate, ethyl acrylate, n-propyl acrylate, i-acrylate Acrylates such as propyl, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc .; methacrylic acid and salts thereof; methyl methacrylate, Ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, methacrylates such as dodecyl methacrylate, octadecyl methacrylate Acid esthetic Acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N, N-dimethyl acrylamide, diacetone acrylamide, acrylamidopropane sulfonic acid and its salts, acrylamidopropyldimethylamine or its acid salt or its quaternary salt, N-methylol Acrylamide derivatives such as acrylamide and derivatives thereof; methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, methacrylamidopropane sulfonic acid and salts thereof, methacrylamidopropyldimethylamine or an acid salt thereof or a quaternary salt thereof, N- Methacrylamide derivatives such as methylol methacrylamide or derivatives thereof; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl ether Vinyl ethers such as vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether; nitriles such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride and vinyl fluoride; mentioned isopropenyl acetate and the like; vinylidene chloride, vinylidene halide such as vinylidene fluoride; allyl acetate, allyl compounds such as allyl chloride; maleic acid and salts or esters or anhydrides thereof; vinyl silyl compounds such as vinyl trimethoxysilane Be 10 mass% or less is preferable, and 0 mass% may be sufficient as content of another monomer unit.

The ethylene-based copolymer has a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride group, an amino group or a trimethoxysilyl group in the molecular chain or at the molecular chain end, as long as the effects of the present invention are not impaired. It may be

The molecular weight of the ethylene-based copolymer is not particularly limited, but from the viewpoint of film formability, it is 1 × 10 ⁴ to 2 × 10 as a weight average molecular weight in terms of polystyrene determined by gel permeation chromatography (GPC) measurement. ⁶ is preferable, and 1 × 10 ⁴ to 2 × 10 ⁶ is more preferable.

The molecular weight distribution (weight-average molecular weight / number-average molecular weight (Mw / Mn)) of the ethylene-based copolymer is not particularly limited, but is preferably 1.0 to 3.5, from the viewpoint of film stickiness and appearance. 1 to 3.0 is more preferable.

The content of the ethylene-based copolymer in the total mass of the resin component is preferably 20% by mass or more, and more preferably 40% by mass or more. When the content of the ethylene-based copolymer is 20% by mass or more, the strength required at the time of handling the film can be maintained.

The resin composition of the second embodiment may contain another resin component other than the ethylene-based copolymer in the resin component as a binder, as long as the effects of the present invention are not impaired. The other resin component includes, for example, a modified polyolefin polymer, which comprises an epoxy group, a carboxyl 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. There may be mentioned modified polyolefin polymers comprising at least one functional group selected from the group. In addition, copolymers of olefin monomers, olefin monomers and other vinyl monomers (hereinafter referred to as "other vinyl monomers") other than vinyl monomers having the above functional group, and hydrogenated copolymers thereof And those obtained by adding the functional group to these copolymers can also be used as the modified polyolefin polymer. There is no restriction | limiting in particular as a structure of these copolymers, For example, a random copolymer, a block copolymer, a graft copolymer etc. are mentioned, A block copolymer and a graft copolymer are more preferable. The said modified polyolefin polymer may be used individually by 1 type, or may use 2 or more types together. 50 mass% or less is preferable, as for content of another resin component in the total mass of a resin component, 30 mass% or less is more preferable, and 0 mass% may be sufficient.

(Inorganic substance)
Although the inorganic substance applicable to the resin composition of this embodiment is not specifically limited, For example, the inorganic substance which the 1st resin sheet of 1st embodiment contains may be sufficient.

The content of the inorganic substance is 40% by volume or more and 70% by volume or less, and more preferably 45% by volume or more and 65% by volume or less in the total amount of the resin composition. The volume change after a sintering process can be suppressed moderately as content of an inorganic substance is 40 volume% or more. If it is 70 volume% or less, appropriate strength of the resin composition obtained can be maintained.

(Other ingredients)
The resin composition of the present embodiment may contain other components in addition to the resin component as the binder component and the inorganic substance as long as the effects of the present invention are not impaired. Other components include, for example, metal salt stabilizers such as copper chloride, copper iodide, copper acetate, cerium stearate, hindered amines, hindered phenols, sulfur-containing compounds, acrylates, phosphorus organic compounds Antioxidants and heat stabilizers, benzophenone series, salicylate series, benzotriazole series UV absorbers and weathering agents, light stabilizers, mold release agents, lubricants, crystal nucleating agents, viscosity modifiers, colorants, silanes Surface treatment agents such as coupling agents, pigments, fluorescent pigments, dyes, fluorescent dyes, coloring inhibitors, flame retardants (red phosphorus, metal hydroxide flame retardants, phosphorus flame retardants, silicone flame retardants, halogen flame retardants Flame retardants and combinations of these halogen flame retardants and antimony trioxide, etc.), wood flour, rice husk flour, walnut powder, waste paper, phosphorescent pigments, boric acid glass and silver based antimicrobial agents Antibacterial agents and antifungal agents, mold corrosion inhibitors such as hydrotalcite represented by magnesium-aluminum hydroxyhydrate, crystal nucleating agents, antistatic agents, antiblocking agents, surfactants, dyes, deodorants And additives such as plasticizers, release agents, and dispersants. Among these, from the viewpoint of improving the flexibility of the resin composition, it is preferable to add a plasticizer.

The plasticizer and the release agent are not particularly limited, and for example, the plasticizer used in the first embodiment can be used.
70 mass% or less is preferable in the total mass of this resin composition, as for content of a plasticizer, 60 mass% or less is more preferable, and 0 mass% may be sufficient. When the content of the plasticizer is 70% by mass or less, it is possible to improve the flexibility of the resin composition without impairing the strength of the resin composition.

In addition, when it contains another component, it is preferable to adjust the usage-amount so that each content of the resin component in a resin composition and an inorganic substance may become in the range which already mentioned above.

The resin composition of the present embodiment preferably has a vibration frequency of 1 Hz and a storage elastic modulus (E ′) at 80 ° C. of 1.0 × 10 ¹⁰ Pa or less in dynamic viscoelasticity (DMA) measurement. And 1.0 × 10 ⁹ Pa or less is more preferable. When the storage elastic modulus of the resin composition is not more than 1.0 × 10 10 ^Pa, it is possible to smooth the irregularities during the pressing process. The lower limit value of the storage elastic modulus of the resin composition is not particularly limited, but is preferably 1.0 × 10 ⁵ Pa or more, and more preferably 1.0 × 10 ⁶ Pa or more. Since it is possible to maintain appropriate strength at 1.0 × 10 ⁵ Pa or more, dimensional change during film transport can be prevented.
In addition, the dynamic viscoelasticity (DMA) measurement of a resin composition may be measured using the following measurement conditions using a commercially available dynamic viscoelasticity measuring apparatus (for example, SII company make, "DMS6100" etc.) it can.
(Elastic modulus measurement)
・ Frequency: 1 Hz
Temperature range: 20 to 200 ° C.
· Heating rate: 5 ° C / min
Test specimen: about 10 mm width Test mode: tension

(Method for producing resin composition)
Next, an example of the manufacturing method of the resin composition of this embodiment is demonstrated.
In the method for producing a resin composition according to this embodiment, the above-mentioned resin component is heated to a melting point or a glass transition temperature or more to form a molten state (liquid state) or a rubber state, and an inorganic substance is added thereto and kneaded. A composition is obtained.

The method for heating the resin component to the melting point or the glass transition temperature or higher is not particularly limited, but it is preferable to use a closed-type kneader, so-called internal mixer. Further, the method of adding the inorganic substance to the resin component in the molten or rubber state and kneading is not particularly limited, but using a kneader such as an open roll, single screw extruder, twin screw kneader, kneader, or Banbury mixer. preferable.

After kneading, granulation, cooling, and the like are performed to obtain a resin composition such as pellets and tablets.

<Resin sheet>
Next, an example of the resin sheet according to the second embodiment will be described.
The resin sheet of the present embodiment is formed by molding the above-described resin composition into a sheet, and therefore the components are substantially the same as the resin composition as long as an additional component is not added at the time of molding into a sheet. Is identical to

The thickness of the resin sheet of the present embodiment is preferably 1 μm or more and 10000 μm or less, and more preferably 30 μm or more and 3000 μm or less. If the thickness of the resin sheet is 30 μm or more, film breakage during handling can be prevented.

(Production method of resin sheet)
Next, an example of the manufacturing method of the resin sheet of this embodiment is demonstrated. In the method for producing a resin sheet according to the present embodiment, in the method for producing a resin composition described above, an inorganic substance is added to a resin component in a molten state or a rubber state and kneaded, and then molded into a sheet or film. Get the sheet.

Although the method in particular of shape | molding a resin composition in a sheet form or a film form is not restrict | limited, It is preferable to use the extrusion apparatus using a T-die.

(How to use resin sheet)
Next, an example of usage of the resin sheet of the present embodiment will be described.
The resin sheet of the present embodiment is laminated on one or both surfaces of the laminated sheet in the production of the above-described general laminated ceramic capacitor. Thereby, the resin sheet of this embodiment can smooth a surface of the laminated sheet while embedding a level difference following the unevenness of the surface of the laminated sheet generated due to the density difference at the time of lamination.

The method of laminating the resin sheet on the laminated sheet in which the irregularities are generated is not particularly limited, but a conventional general laminating method can be applied. Specifically, a vacuum heating press method, a plane press method, a roll press method, a method combining them, etc. using a heat press or a laminator can be mentioned.

Although the press conditions in particular at the time of laminating a resin sheet are not restricted, it is preferred that temperature shall be 60-150 ° C. The pressure is preferably 0.1 to 10 t / cm ^2, and the time is preferably 6 seconds to 60 minutes. Also, a plurality of resin sheets may be stacked.

(Resin sheet embedding performance)
The resin sheet of the present embodiment has a width of 20 to 2000 μm, a depth of 10 to 1000 μm, and an interval of 70 to 70, when the appropriate sheet thickness is 0.05 to 1.0 mm and appropriate pressing conditions are selected. A level difference of about 12000 μm can be embedded. These steps may be provided in the same direction, or may be intersections in two or more directions.
Moreover, the unevenness | corrugation of the surface (surface on the opposite side to a level | step difference) of the said resin sheet at the time of embedding the said level | step difference can make a resin sheet of this embodiment a smooth surface about +/- 5 micrometers. In addition, the unevenness | corrugation of the surface of a resin sheet can be measured by the method similar to the Example mentioned later.

By using the resin sheet of the present embodiment as the embedding sheet, the surface of the laminated sheet becomes smooth, and thus cutting of the laminated sheet becomes easy when forming the chip. Moreover, since the resin sheet becomes only an inorganic substance by heating the laminated body chipped by cutting and decomposing and removing a binder, it can sinter as it is. Furthermore, since it is excellent also in the shape after sintering, formation of a terminal electrode also becomes easy.

As described above, according to the resin composition of the present embodiment, the resin composition having a melting point or glass transition temperature of less than 100 ° C. and a predetermined inorganic substance, and the content of the inorganic substance is 40 vol% or more And 70% by volume or less, and has flexibility and flowability, so that it is excellent in conformity to irregularities and surface smoothness.

According to the resin sheet of the present embodiment, since the above-described resin composition is molded into a sheet, it can be laminated on a ceramic green sheet, and has excellent followability to irregularities and surface smoothness.

The technical scope of the present invention is not limited to the above embodiment, and various modifications can be made without departing from the scope of the present invention.
For example, in the embodiment described above, the resin component is heated to a melting point or higher than the glass transition temperature to be in a molten state (liquid state) or rubber state, and an inorganic substance is added thereto to knead the resin composition and the resin sheet. Although the method of obtaining is described as an example, it is not limited thereto. For example, a resin component may be dissolved in a solvent to form a resin solution, and an inorganic substance may be added to the resin solution and stirred to obtain a coating solution. Moreover, it is good also as a resin sheet by apply | coating the obtained coating solution to base materials, such as a PET film.

Moreover, although embodiment mentioned above demonstrated the method to laminate | stack a resin sheet with respect to the base-material surface which has unevenness as an example, it is not restrict | limited to this. For example, the resin composition in a molten or rubber state may be laminated on the surface of a substrate having irregularities by a coating method.

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. However, the present invention is not limited at all to the examples shown below.

In Examples and Comparative Examples shown below, V1 of the first resin sheet, V2 of the second resin sheet, and V4 of the fourth resin sheet are respectively measured using a viscosity measuring apparatus ("Capillograph" manufactured by Toyo Seiki Co., Ltd.) , It measured by the following methods.
That is, the first resin sheet, the second resin sheet or the fourth resin sheet (resin pellets) processed into pellets are filled in a heated cylinder, which is sufficiently preheated and then plungers of a constant speed are used. Resin pellets heated to 80 ° C. in the case of the first resin sheet or the second resin sheet, and to 190 ° C. in the case of the fourth resin sheet from the orifice (2 mmφ × 10 mm L) provided at the lower part of the cylinder The melt viscosity was calculated from the stress measured at the time of extrusion. At this time, measurement is carried out by changing the lowering speed of the plunger, and the melt viscosity at a shear rate of 7.6 s ⁻¹ is determined from the change curve of the melt viscosity with respect to the shear rate of the resin pellet. , V2 or V4.

<Production of resin sheet (fourth resin sheet)>
Example 1
A resin sheet (fourth resin sheet) (thickness: 200 μm) was produced by heat-pressing polypropylene (“FS2011 DG2” manufactured by Sumitomo Chemical Co., Ltd., melting point: 158 ° C.).
The viscosity (V4) of the obtained resin sheet was 5 kPa · s. The results are shown in Table 1.

Example 2
A resin sheet (fourth resin sheet) (thickness: 200 μm) was produced by heat-pressing syndiotactic polystyrene (“S104” manufactured by Idemitsu Kosan Co., Ltd., melting point 270 ° C.). The viscosity (V4) of the obtained resin sheet was 10 kPa · s. The results are shown in Table 1.

[Example 3]
A resin sheet (fourth resin sheet) (thickness: 200 μm) by heat-pressing a 4-methyl-1-pentene resin (“MX004” manufactured by Mitsui Chemicals, melting point 228 ° C., melt flow rate 2.5 g / 10 min) Was produced.
The viscosity (V4) of the obtained resin sheet was 4 kPa · s. The results are shown in Table 1.

<Production of resin sheet (first resin sheet)>
Example 4
Ethylene-methyl acrylate copolymer (Japan polyethylene Co., Ltd. "EB440H", melting point 77 ° C, melt flow rate 18 g / 10 min), barium titanate ("BTC-4 FA" manufactured by Nippon Chemical Industrial Co., Ltd.), paraffin oil ( Idemitsu Kosan Co., Ltd. “PW90”), and 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 resin composition (1st resin composition) which is 30 mass% was prepared. Subsequently, the resin composition (first resin sheet) (200 μm in thickness) was produced by heating and pressing this resin composition.
The viscosity (V1) of the obtained resin sheet was 300 kPa · s. The results are shown in Table 1.

[Example 5]
A resin composition (first resin) was prepared in the same manner as Example 4, except that the proportion of the content of paraffin oil to the total content of components other than barium titanate was changed to 30% by mass to 40% by mass. A resin sheet (first resin sheet) (thickness: 200 μm) was produced in the same manner as in Example 4 except that the composition was prepared and this resin composition was used.
The viscosity (V1) of the obtained resin sheet was 130 kPa · s. The results are shown in Table 1.

[Example 6]
A resin composition (first resin) was prepared in the same manner as Example 4, except that the proportion of the content of paraffin oil to the total content of components other than barium titanate was changed to 30% by mass to 60% by mass. A resin sheet (first resin sheet) (thickness: 200 μm) was produced in the same manner as in Example 4 except that the composition was prepared and this resin composition was used.
The viscosity (V1) of the obtained resin sheet was 20 kPa · s. The results are shown in Table 1.

Comparative Example 1
A resin composition (first resin composition) is prepared in the same manner as in Example 4 except that the content of barium titanate is changed to 55% by volume to 70% by volume, and this resin composition is used. A resin sheet (first resin sheet) (200 μm in thickness) was produced in the same manner as in Example 4 except for the above point.
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 7]
(Manufacturing of first resin sheet and second resin sheet)
A resin composition (first resin composition) was prepared by the same method as in Example 4, and the resin composition was heat-pressed to prepare a first resin sheet (80 μm in thickness).
Separately, as a second resin component, a polyolefin-based elastomer ("8032NS" manufactured by Mitsui Chemicals, Inc., softening point 120 ° C.) is prepared and heat-pressed to produce a second resin sheet (200 μm thick) did.

The viscosity (V1) of the first resin sheet is 300 kPa · s, the viscosity (V2) of the second resin sheet is 60 kPa · s, and the logarithmic ratio of viscosity (Log (V2) / Log (V1)) is 0. It was 72. The results are shown in Table 1.

(Manufacture of laminated resin sheet)
Subsequently, the first resin sheet obtained above and the second resin sheet were heat-pressed to produce a laminated resin sheet in which the first resin sheet and the second resin sheet are laminated.

[Example 8]
A resin composition (first resin composition) was prepared by the same method as in Example 5, and a first resin sheet (thickness 80 μm) and a resin sheet by the same method as in Example 7 except that this resin composition was used. A laminated resin sheet in which the second resin sheet (200 μm in thickness) was laminated was produced.
The viscosity (V1) of the first resin sheet is 130 kPa · s, the viscosity (V2) of the second resin sheet is 60 kPa · s, and the logarithmic ratio (Log (V2) / Log (V1)) of the viscosity is 0. It was 84. The results are shown in Table 1.

[Example 9]
A resin composition (first resin composition) was prepared by the same method as in Example 6, and a first resin sheet (thickness 80 μm) and a resin sheet by the same method as in Example 7 except that this resin composition was used A laminated resin sheet in which the second resin sheet (200 μm in thickness) was laminated was produced.
The viscosity (V1) of the first resin sheet is 20 kPa · s, the viscosity (V2) of the second resin sheet is 60 kPa · s, and the logarithmic ratio of viscosity (Log (V2) / Log (V1)) is 1. It was 37. The results are shown in Table 1.

Comparative Example 2
A resin composition (first resin composition) was prepared by the same method as Comparative Example 1, and a first resin sheet (80 μm in thickness) and a resin sheet were prepared by the same method as Example 7, except that this resin composition was used. A laminated resin sheet in which the second resin sheet (200 μm in thickness) was laminated was produced.
The viscosity (V1) of the first resin sheet is 2600 kPa · s, the viscosity (V2) of the second resin sheet is 60 kPa · s, and the logarithmic ratio of the viscosity (Log (V2) / Log (V1)) is 0. It was 52. The results are shown in Table 1.

Comparative Example 3
A first resin sheet (thickness 80 μm) and a second resin component were prepared in the same manner as in Example 8 except that polyethylene (“F522NH” manufactured by Ubemaruzen Polyethylene Co., Ltd.) was used as the second resin component instead of the polyolefin elastomer. 2 A laminated resin sheet in which resin sheets (200 μm in thickness) are laminated was produced.
The viscosity (V1) of the first resin sheet is 130 kPa · s, the viscosity (V2) of the second resin sheet is 3000 kPa · s, and the logarithmic ratio of viscosity (Log (V2) / Log (V1)) is 1. It was 64. The results are shown in Table 1.

<Evaluation of first resin sheet>
About the resin sheet (1st resin sheet) of the Example and comparative example which were obtained above, the embedding property of the groove | channel in the said laminated body was evaluated by the following method.
That is, instead of the laminated body formed into chips, a model body in which a plurality of grooves 50 μm wide and 500 μm deep were arranged at intervals of 500 μm on the surface was used. Then, a resin sheet was superimposed on the surface of the model body on which the grooves are provided, to form a third laminated structure which is a laminate of the model body and the resin sheet. Furthermore, of the both surfaces of this third laminated structure, polyethylene terephthalate (PET) of which one surface is subjected to release treatment on the exposed surface on the side opposite to the side on which the resin sheet of the model body is mounted. The release sheet was superposed. At this time, the release-treated surface of the release sheet was brought into contact with the exposed surface of the model body. Furthermore, a rubber sheet (3 mm in thickness) and a pressure plate (5 mm in thickness) made of stainless steel (SUS 304) were laminated in this order on the superposed release sheets. Similarly, the release sheet is overlapped on the exposed surface of the third laminated structure opposite to the side where the resin sheet is in contact with the model body, and the rubber is further added to the rubber. The sheet and the pressure plate were laminated in this order. At this time, the release treatment surface of the release sheet was brought into contact with the exposed surface of the resin sheet. By the above-described operation, the fourth laminated structure in which the pressure plate, the rubber sheet, the release sheet, the model body, the resin sheet, the release sheet, the rubber sheet and the pressure plate are laminated in this thickness direction is Made.

While heating the fourth laminate structure obtained above so that the temperature of the resin sheet is 80 ° C., the pressure plate of the fourth laminate structure closer to the model body is supported, and the resin sheet The laminated resin sheet was pressed against the model body by applying a pressure of 92 kg / cm ² for 2 minutes to the pressure plate closer to the above.
Then, the pressurization was released, and the third laminated structure after pressurization was taken out from the fourth laminated structure. Then, the third laminated structure was cut in the thickness direction, and the state of the grooves of the model body was observed with a microscope. And [[the depth (μm) of the groove embedded by the resin sheet] / [500 (μm)] × as an index indicating the degree to which the groove is embedded by the resin sheet invaginated therein The value “100” was calculated, and this was taken as the filling rate, and the filling property of the groove (the filling property at 80 ° C.) in the laminate was evaluated according to the following evaluation criteria. Here, "the depth of the groove embedded by the resin sheet" is synonymous with "the distance from the opening of the groove embedded by the resin sheet". The results are shown in Table 1.
(Evaluation criteria)
◎: All the grooves are completely embedded by the resin sheet to a depth of 500 μm, and the embedding ratio is 100%.
Good: The depth embedded by the resin sheet in all the grooves is 50 μm or more and less than 500 μm, and the embedding rate is 10% or more and less than 100%.
X: In at least some of the grooves, the depth embedded by the resin sheet is less than 50 μm, and the embedding rate is less than 10%.

<Evaluation of the 4th resin sheet>
When the fourth laminated sheet is heated using the fourth resin sheet of the example obtained above instead of the first resin sheet as the resin sheet, the temperature of the resin sheet is changed to 80 ° C. and the temperature is 190 ° C. The embedding property (embedding property at 190 ° C.) of the groove in the laminate of the fourth resin sheet was evaluated in the same manner as in the case of the first resin sheet described above except that the above was applied. The results are shown in Table 1.
Furthermore, about these 4th resin sheets, the embedding (the embedding at 80 degreeC) of the groove | channel in the said laminated body was evaluated also by the same method as the case of the above-mentioned 1st resin sheet. The results are shown in Table 1.

<Evaluation of laminated resin sheet>
With respect to the laminated resin sheets of the examples and the comparative examples obtained above, the dielectric layer forming characteristics in the laminate cut surface were evaluated by the following method.
That is, instead of the laminated body formed into chips, a model body in which a plurality of grooves 50 μm wide and 500 μm deep were arranged at intervals of 500 μm on the surface was used. Then, the first resin sheet is brought into contact with the surface of the model body on which the grooves are provided, and the laminated resin sheet obtained above is overlapped to form a laminate of the model body and the laminated resin sheet. A first laminated structure was formed. Furthermore, polyethylene terephthalate (PET) of which one surface is subjected to mold release treatment on the exposed surface of the first laminated structure on the opposite side to the side on which the laminated resin sheet of the model body is mounted. A release sheet made of paper was superposed. At this time, the release-treated surface of the release sheet was brought into contact with the exposed surface of the model body. Furthermore, a rubber sheet (3 mm in thickness) and a pressure plate (5 mm in thickness) made of stainless steel (SUS 304) were laminated in this order on the superposed release sheets. Of the both sides of the first laminated structure, the release sheet is also similarly exposed to the exposed surface of the laminated resin sheet on the side opposite to the side in contact with the model laminated body (in other words, the exposed surface of the second resin sheet). And the rubber sheet and the pressure plate were further laminated in this order on the release sheet. At this time, the release treatment surface of the release sheet was brought into contact with the exposed surface of the second resin sheet. By the above operations, the pressure plate, rubber sheet, release sheet, model body, laminated resin sheet (first resin sheet, second resin sheet), release sheet, rubber sheet, and pressure plate are in this order of thickness. The 2nd laminated structure laminated in the direction was produced.

While heating the second laminated structure obtained above so that the temperature of the laminated resin sheet is 80 ° C., the pressure plate of the second laminated structure closer to the model body is supported and laminated. A pressure of 92 kg / cm ² was applied to the pressure plate closer to the resin sheet for 2 minutes to press the laminated resin sheet against the model body.
Then, the pressurization was released, and the pressurized first laminated structure was taken out from the second laminated structure. Then, the first laminated structure was cut in the thickness direction, and the state of the groove of the model body was observed with a microscope. And, when the second resin sheet is indented inside the groove, the distance from the opening of the groove to the tip of the second resin sheet indented inside the groove (indentation distance) Were measured, and dielectric layer coating characteristics in the laminate cut surface were evaluated according to the following evaluation criteria. The results are shown in Table 1.
(Evaluation criteria)
Good: The surface is covered with the first resin sheet in all the grooves, and the average value of the indented distances of the second resin sheet is 300 μm or more.
X: In at least a part of the grooves, the surface is not covered at all by the first resin sheet, or in all the grooves, the surface is covered by the first resin sheet, but the invagination of the second resin sheet The average value of the distances is less than 300 μm.

In addition, in Table 1, the description of "-" means that the physical property of the item is unmeasured, or the evaluation of the item is not performed.

As is clear from the above results, in Examples 1 to 3, the viscosity (V4) was 4 to 10 kPa · s, and the embeddability of the groove at 80 ° C. of the fourth resin sheet was insufficient. The filling ratio of the groove at 10 ° C. was 10% or more and less than 100%, and the groove embedding at 190 ° C. was good.

In Examples 4 to 6, the viscosity (V1) is 20 to 300 kPa · s, and the embedding ratio of the groove by the first resin sheet is 10% or more and less than 100%, and the embedding property of the groove at 80 ° C. Was good.
On the other hand, in Comparative Example 1, the viscosity (V1) was large, and the embedding property of the groove at 80 ° C. was inferior.

On the other hand, in Examples 7 to 9, the logarithmic ratio (Log (V2) / Log (V1)) of the viscosity is 0.72 to 1.37, and the average value of the invaginated distances of the second resin sheet is 300 μm. As described above, the surface of the groove was covered with the first resin sheet to at least this distance. Thus, the laminated resin sheet using the resin sheet (1st resin sheet) of Examples 4-6 was excellent in the dielectric material layer coating characteristic. In any of Examples 7 to 9, the second resin sheet was invaginated without being in contact with the surface of the groove at all in the region inside the groove whose surface is covered with the first resin sheet.

On the other hand, in Comparative Example 2, the logarithmic ratio of the viscosity was small, and in Comparative Example 3, the logarithmic ratio of the viscosity was large, and in each case, the laminated resin sheet was inferior in the dielectric layer covering characteristics. Thus, the laminated resin sheet using the resin sheet (1st resin sheet) of Comparative Examples 1-2 was inferior to the dielectric material layer coating characteristic.

[Example 10]
Ethylene-methyl acrylate copolymer resin (manufactured by Japan Polyethylene Corporation, EB440H, melting point: 77 ° C, MFR: 18 g / 10 min) 22.6 g and barium titanate (manufactured by Nippon Chemical Industry Co., Ltd., BTC-4 FA) and 144.6 g The mixture was kneaded for 15 minutes at 100.degree. C. using a mixer (Laboplast Mill, manufactured by Toyo Seiki Seisaku-sho, Ltd.) to obtain a resin composition.
By pressing the obtained resin composition, a resin sheet having a thickness of 0.1 to 1.0 mm was produced.

[Example 11]
20.4 g of ethylene-methyl acrylate copolymer resin (manufactured by Japan Polyethylene Corporation, EB440H, melting point: 77 ° C., MFR: 18 g / 10 min), and 158.8 g of barium titanate (manufactured by Nippon Chemical Industrial Co., Ltd., BTC-4FA) The mixture was kneaded for 15 minutes at 100.degree. C. using a mixer (Laboplast Mill, manufactured by Toyo Seiki Seisaku-sho, Ltd.) to obtain a resin composition.
By pressing the obtained resin composition, a resin sheet having a thickness of 0.1 to 1.0 mm was produced.

[Example 12]
18.1 g of ethylene-methyl acrylate copolymer resin (manufactured by Japan Polyethylene Corporation, EB440H, melting point: 77 ° C., MFR: 18 g / 10 min), and 173.5 g of barium titanate (BTC-4FA manufactured by Nippon Chemical Industrial Co., Ltd.) The mixture was kneaded for 15 minutes at 100.degree. C. using a mixer (Laboplast Mill, manufactured by Toyo Seiki Seisaku-sho, Ltd.) to obtain a resin composition.
By pressing the obtained resin composition, a resin sheet having a thickness of 0.1 to 1.0 mm was produced.

[Example 13]
22.6 g of ethylene-methyl methacrylate copolymer resin (Sumitomo Chemical, WK402, melting point: 79 ° C., MFR: 20 g / 10 min) and 144.6 g of barium titanate (BTC-4FA, manufactured by Nippon Chemical Industrial Co., Ltd.) It knead | mixed for 15 minutes at 100 degreeC using (Toyoseiki Co., Ltd. make, Labo Plasto mill), and the resin composition was obtained.
By pressing the obtained resin composition, a resin sheet having a thickness of 0.1 to 1.0 mm was produced.

Example 14
22.6 g of ethylene-ethyl acrylate copolymer resin (NUC, NUC-6570, melting point: 91 ° C., MFR: 20 g / 10 min) and 144.6 g of barium titanate (BTC-4FA, manufactured by Nippon Chemical Industrial Co., Ltd.) It knead | mixed for 15 minutes at 100 degreeC using the mixer (the Toyo Seiki Seisaku-sho make Labo Plasto mill), and the resin composition was obtained.
By pressing the obtained resin composition, a resin sheet having a thickness of 0.1 to 1.0 mm was produced.

[Example 15]
22.9 g of ethylene-vinyl acetate copolymer resin (manufactured by NUC, DQDJ-3269, melting point: 69 ° C., MFR: 20 g / 10 min) and 145.2 g of barium titanate (BTC-4 FA, manufactured by Nippon Chemical Industrial Co., Ltd.) It knead | mixed for 15 minutes at 100 degreeC using the mixer (the Toyo Seiki Seisaku-sho make Labo Plasto mill), and the resin composition was obtained.
By pressing the obtained resin composition, a resin sheet having a thickness of 0.1 to 1.0 mm was produced.

[Example 16]
22.8 g of ethylene-methyl methacrylate copolymer resin (Sumitomo Chemical, CM5022, melting point: 63 ° C., MFR: 450 g / 10 min) and 144.5 g of barium titanate (BTC-4FA, manufactured by Nippon Chemical Industrial Co., Ltd.) It knead | mixed for 15 minutes at 100 degreeC using (Toyoseiki Co., Ltd. make, Labo Plasto mill), and the resin composition was obtained.
By pressing the obtained resin composition, a resin sheet having a thickness of 0.1 to 1.0 mm was produced.

Comparative Example 4
22.0 g of ethylene-methyl methacrylate copolymer resin (Sumitomo Chemical, WD106, melting point: 101 ° C., MFR: 0.32 g / 10 min) and 144.5 g of barium titanate (BTC-4 FA, manufactured by Nippon Chemical Industrial Co., Ltd.) A resin composition was obtained by kneading at 100 ° C. for 15 minutes using a mixer (Laboplast Mill, manufactured by Toyo Seiki Seisakusho Co., Ltd.).
By pressing the obtained resin composition, a resin sheet having a thickness of 0.1 to 1.0 mm was produced.

Comparative Example 5
22.0 g of polyethylene resin (Tosoh, 203, melting point: 105 ° C., MFR: 8.0 g / 10 min) and 144.5 g of barium titanate (BTC-4FA, manufactured by Nippon Chemical Industrial Co., Ltd.) The resin composition was obtained by kneading at 100 ° C. for 15 minutes using Laboplast Mill).
By pressing the obtained resin composition, a resin sheet having a thickness of 0.1 to 1.0 mm was produced.

Comparative Example 6
27.1 g of ethylene-methyl acrylate copolymer resin (manufactured by Japan Polyethylene Corporation, EB440H, melting point: 77 ° C., MFR: 18 g / 10 min), 115.6 g of barium titanate (BTC-4 FA, manufactured by Nippon Chemical Industrial Co., Ltd.) The mixture was kneaded for 15 minutes at 100.degree. C. using a mixer (Laboplast Mill, manufactured by Toyo Seiki Seisaku-sho, Ltd.) to obtain a resin composition.
By pressing the obtained resin composition, a resin sheet having a thickness of 0.1 to 1.0 mm was produced.

<Measurement method of dynamic viscoelasticity (DMA)>
A sheet piece of 7 cm × 1 cm was cut out from the sheets obtained in Examples and Comparative Examples, and placed in a sample holder as a sample of measurement length: 2 cm × film width: 1 cm. Next, using a dynamic viscoelasticity measuring apparatus (DMS6100 manufactured by Seiko Instruments Inc.), a temperature range of room temperature 20 ° C. to 130 ° C. in tension mode, displacement: 5 μm, vibration frequency: 1 Hz, heating rate: 5 ° C./min The storage modulus E ′ and the loss factor tan δ were measured using the following conditions. The tan δ was determined by the ratio of the loss modulus E ′ ′ to the storage modulus E ′. Moreover, the storage elastic modulus E 'at 80 ° C. was read from the obtained graph. Also, the measurement results are shown in Table 2 below.

<Method of evaluating smoothness>
First, two types of molded articles were prepared: grooves with a width of 300 μm width × 80 μm depth × 500 μm intervals and grooves with a width direction of 300 μm width × 40 μm depth × 1000 μm intervals. Next, the 100 ± 20 μm sheet obtained in the example and the comparative example is placed on the surface layer of the above-mentioned molded product, and the both sides of the structure of the biaxially stretched PET which has been subjected to the release treatment of 38 μm thickness from above A 3 mm-thick rubber and a 5 mm-thick SUS plate were sandwiched, and pressed at a temperature of 80 ° C., a pressure of 1.0 t / cm ² , and a pressure of 2 minutes. Next, the surface asperity of the molded product after pressure bonding was measured using a surface roughness meter (Handy Surf E-35B) with a measurement length of 4 mm. Evaluation was performed according to the following criteria. The evaluation results are shown in Table 2 below.

(Smoothness)
○ Judgment: Surface unevenness is ± 5 μm in both vertical and horizontal directions Δ judgment: Either vertical or horizontal direction, surface unevenness exceeds ± 5 μm × Judgment: surface unevenness in both vertical and horizontal directions Exceeds ± 5 μm

<Method for checking cracks after heat treatment>
The sheets obtained in Examples and Comparative Examples were cut into φ5 mm and treated at 600 ° C. for 1 hour to completely decompose the resin portion.
The samples before and after the heat treatment were visually checked for cracks and deformation of the surface shape. Evaluation was performed according to the following criteria. The evaluation results are shown in Table 2 below.

(In the case of a crack)
○ Judgment: Cracks of 3 μm or less are newly formed after heat treatment Δ Judgment: Cracks of more than 3 μm and 5 μm or less newly formed after heat treatment × Judgment: Cracks of 5 μm or more after heat treatment are new Formed in

(In the case of deformation)
○ Judgment: After heat treatment, surface unevenness is within ± 10 μm × judgment: After heat treatment, surface unevenness exceeds ± 10 μm

As shown in Table 2, according to Examples 10 to 7, in the dynamic viscoelasticity (DMA) measurement, the vibration frequency is 1 Hz, and the storage elastic modulus (E ′) at 80 ° C. is 1.0 × in all cases. It was 10 ⁸ Pa or less.
Moreover, it confirmed that all can smooth | blunt an unevenness | corrugation at the time of a press process.
Furthermore, after the heat treatment, it was confirmed that cracking and deformation were small.

On the other hand, in Comparative Example 4 and Comparative Example 5, it was confirmed that the melting point of the resin component was 100 ° C. or higher, and the smoothness was not sufficient.
Moreover, in the comparative example 6, content of the inorganic substance was less than 40 volume%, and it confirmed that a big deformation | transformation arises after heat processing.

The resin sheet and the laminated resin sheet according to the first embodiment of the present invention can be used as a surface protection material such as a chipped laminate having a structure in which a large number of ceramic green sheets and internal electrodes are alternately stacked. is there.
Furthermore, the resin composition and the resin sheet according to the second embodiment of the present invention can be used as a surface protective material of a ceramic green sheet when producing a multilayer ceramic capacitor.

1, 2 · · · laminated resin sheet 11 · · · first resin sheet 12 · · · second resin sheet 13 · · · third resin sheet

Claims (10)

A laminated resin sheet having a viscosity V5 of 1500 kPa · s or less under the conditions of a temperature of 80 ° C. and a shear rate of 7.6 s ⁻¹ , and for embedding treatment of grooves,
The groove has a depth / width ratio of 0.5 or more,
The resin sheet is disposed on the surface of the object to be treated so as to cover the groove, and the resin sheet is heated relative to the object under the conditions of a temperature of 80 ° C. and a pressure of 92 kg / cm ^2. When pressed, it is possible to indent the groove and embed the groove,
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;
Assuming that the viscosity of the first resin sheet is V1 kPa · s and the viscosity of the second resin sheet is V2 kPa · s under the conditions of a temperature of 80 ° C. and a shear rate of 7.6 s ⁻¹ , Log (V2) / Log ( V1) is 0.7 to 1.4,
The melting point or glass transition temperature of the first resin component is less than 100 ° C.,
The content of the inorganic substance in the first resin sheet is 40% by volume or more,
Said V2 is 1500 kPa * s or less,
Said V1 is 1500 kPa * s or less,
A laminated resin sheet, wherein the inorganic substance is a dielectric ceramic.   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 as the first resin component The laminated resin sheet according to claim 1, comprising one or more selected ethylene-based copolymers.   The laminated resin sheet according to claim 1 or 2, wherein the dielectric ceramic is one or more dielectric ceramic selected from the group consisting of barium titanate, strontium titanate and lead zirconate titanate. .   The laminated resin sheet according to any one of claims 1 to 3, wherein a relative dielectric constant of the first resin sheet is 15 or more.   The laminated resin sheet according to any one of claims 1 to 4, wherein a thickness of the first resin sheet is 10 to 200 μm.   The laminated resin sheet according to any one of claims 1 to 5, wherein a thickness of the second resin sheet is 20 to 1000 μm.   The laminated resin according to any one of claims 1 to 6, wherein one or more resin sheets are further laminated on the side opposite to the side of the second resin sheet on which the first resin sheet is laminated. Sheet. A resin composition for a resin sheet for embedding a groove , which contains a resin component having a melting point or a glass transition temperature of less than 100 ° C. and an inorganic substance, and the content of the inorganic substance is 40 vol% or more.
The inorganic substance is a dielectric ceramic,
A resin composition for a resin sheet for embedding treatment of grooves having a vibration frequency of 10 Hz and a storage elastic modulus at 80 ° C. of 1.0 × 10 ⁸ Pa or less in dynamic viscoelasticity (DMA) measurement. The resin composition for resin sheets for embedding processing of the groove | channel of Claim 8 in which the said resin component contains an ethylene-type copolymer. The resin sheet formed by containing the resin composition for resin sheets for embedding processing of the groove | channel of Claim 8 whose thickness is 1 micrometer or more.

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