JP2000101379A - High-frequency multilayer laminated parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high-frequency multilayer laminated parts, which will not generate deviation between layers at the time of laminating, can reduce the number of printing times, will not generates shrinkage at baking, etc., prevents the generation of the distortion of shape, thickness and interval of a pattern inside of a substrate and the position, etc., of the internal pattern of an individual product after dividing, will not generates burrs, etc., is satisfactory in dividing efficiency at manufacturing, is superior in yield and cost of products, and is equivalent with ceramics in performance. SOLUTION: In the high-frequency multilayer laminated parts of a multilayered structure, obtained by making a chip from a laminate layer of a large area and provided with a dielectric layer and a conductor layer, the dielectric layer is a resin composition constituted of one kind or at least two kinds of resin of a weight-average absolute molecular weight of 1,000 or larger, the sum of the number of the carbon atoms and the hydrogen atoms of the composition is not smaller than 99%, and a part or all between resin molecules are formed of a composite dielectric material composition, including heat- resistant low dielectric high-molecule material chemically connected with each other and a ceramic dielectric material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-frequency multilayer component, which is one of electronic components used in a microwave or millimeter-wave band, such as a mobile communication device, in addition to a portable telephone.

[0002]

2. Description of the Related Art Conventionally, as an electronic component such as a filter and a coupler used in a high frequency part of a radio communication device in a microwave or millimeter wave band, an SMD type high frequency multilayer having a multilayer structure as shown in FIG. Laminated components are known. These components are manufactured in a multi-cavity process in which a plurality (several to hundreds) of conductive patterns are formed in a ceramic, fired to form one substrate, and then divided into individual products.

Conventional electronic components using such ceramics have the following problems. In the method of printing and laminating a conductive paste on a ceramic green sheet, interlayer misalignment tends to occur during lamination. Further, in a so-called printing multi-layer system in which ceramic is printed in paste form, the number of times of printing becomes large. Further, in any of the methods, shrinkage of 10% or more is usually observed during firing, and the shape, thickness, interval, and position of the internal pattern of the individual product after division are likely to be distorted. Maintaining uniformity is very difficult and has a significant adverse effect on product yield, cost, and performance. Also, in the step of dividing the substrate to form an individual product, if the division is performed before firing the substrate, the shape of the individual product may be distorted. In a method in which a snap is formed before firing and then divided after firing, burrs may be generated. Furthermore, in the method of dividing by firing after dicing, the rigid ceramic after firing is cut, so that the dividing efficiency is low.

As an alternative to the above ceramic substrate,
A resin substrate such as a glass epoxy resin and a resin substrate such as BT resin and PPO for high frequency use have recently become widespread.
δ) is from 0.03 to 0.05 or more, and the value of.
001 or less.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to reduce the number of times of printing without causing interlayer displacement during lamination, to reduce the number of printings, and to reduce the shape and thickness of the pattern inside the substrate without causing shrinkage during firing or the like. , Spacing, the position of the internal pattern of the individual product after division, etc. can be prevented from occurring, without burr, etc., the division efficiency at the time of manufacture is good, the product yield, cost is excellent, and the performance is ceramic. It is to realize a normal high-frequency multilayer component.

[0006]

That is, the above object is achieved by the following constitution of the present invention. (1) A high-frequency multilayer laminated component having a multilayer structure, which is obtained by forming a chip from a large-area laminate and has a dielectric layer and a conductive layer, wherein the dielectric layer has a weight average absolute molecular weight of 1,000 or more. Wherein the sum of the number of carbon atoms and hydrogen atoms in the composition is 99% or more, and some or all of the resin molecules Is a high-frequency multilayer component formed of a composite dielectric material composition containing a heat-resistant low-dielectric polymer material having a chemical bond with each other and a ceramic dielectric material. (2) The high-frequency multilayer component according to (1), wherein the heat-resistant low-dielectric polymer material has at least one chemical bond selected from cross-linking, block polymerization and graft polymerization. (3) The heat-resistant low-dielectric polymer material is a non-polar α-
An olefin polymer segment and / or a non-polar conjugated diene polymer segment and a vinyl aromatic polymer segment are chemically bonded copolymers, and the dispersed phase formed by one segment is the other. The high frequency multilayer component according to the above (1) or (2), which is a thermoplastic resin exhibiting a multiphase structure finely dispersed in a continuous phase formed from segments. (4) The heat-resistant low dielectric polymer material is a non-polar α-
The high-frequency multilayer component according to the above (3), wherein the olefin-based polymer segment and the vinyl aromatic-based polymer segment are copolymers chemically bonded to each other. (5) In the heat-resistant low-dielectric polymer material, the vinyl aromatic polymer segment is a vinyl aromatic copolymer segment containing a divinylbenzene monomer (3).
Or the high frequency multilayer component of (4). (6) The heat-resistant low dielectric polymer material is a non-polar α-
The copolymer in which the olefin polymer segment and / or the non-polar conjugated diene polymer segment and the vinyl aromatic polymer segment are chemically bonded to each other is a copolymer chemically bonded by graft polymerization. (4) or the high frequency multilayer laminated component according to (5). (7) The heat-resistant low dielectric polymer material further comprises 4-
The high-frequency multilayer component according to any one of the above (1) to (6), comprising a nonpolar α-olefin polymer containing a methylpentene-1 monomer. (8) A high-frequency multilayer laminate component having a multilayer structure, which is obtained by being chipped from a large-area laminate and has a dielectric layer and a conductor layer, wherein the dielectric layer is formed of at least fumar as a monomer. A high-frequency multilayer component formed of a composite dielectric material composition containing a dielectric polymer material obtained by polymerizing a monomer composition containing an acid diester and a ceramic dielectric material. (9) The high frequency multilayer laminated component according to any one of the above (1) to (8), wherein the fumaric acid diester is represented by the following formula (I).

[0007]

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[In the formula (I), R ¹ represents an alkyl group or a cycloalkyl group, R ² represents an alkyl group, a cycloalkyl group or an aryl group, and R ¹ and R ²
May be the same or different. (10) The high-frequency multilayer component according to any one of the above (1) to (9), wherein the monomer composition further contains a vinyl monomer represented by the following formula (II).

[0009]

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[In the formula (II), X represents a hydrogen atom or a methyl group, and Y represents a fluorine atom, a chlorine atom, an alkyl group, an alkenyl group, an aryl group, an ether group, an acyl group or an ester group. ]

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION
A high-frequency multilayer laminated component having a multilayer structure obtained by forming a chip from a large-area laminate and having a dielectric layer and a conductive layer, wherein the dielectric layer has a weight average absolute molecular weight of 100
A resin composition comprising one or more resins of 0 or more resins, wherein the sum of the number of carbon atoms and hydrogen atoms of the composition is 99% or more, and a part between resin molecules. Alternatively, they are all formed of a composite dielectric material composition containing a heat-resistant low-dielectric polymer material having a chemical bond with each other and a ceramic dielectric material.

By forming a high-frequency multilayer laminated component obtained by forming a chip from a large-area laminate by using a composite dielectric material composition, cutting at the time of forming a chip becomes easy, and the displacement between layers during lamination is facilitated. Does not occur, and the number of printings can be reduced. In addition, it is possible to prevent distortion in the shape, thickness, interval, the position of the internal pattern of the individual product after division, and the like without causing shrinkage during firing or the like. Further, it is possible to obtain a high-frequency multilayer component having good dividing efficiency at the time of manufacturing without producing burrs and the like, and having excellent product yield and cost.

Here, the large-area laminate (laminate precursor) refers to a precursor before cutting and forming the chip body. The size is usually 4 to 25 cm in length and 4 to 2 in width.
5cm, thickness: 0.02-0.5cm, especially vertical: 4-12c
m, the width: 4 to 12 cm, and the thickness: 0.05 to 0.2 cm are preferable.

[0014] To form the laminated precursor, a dielectric layer,
A conductor layer may be laminated on the dielectric layer or at a necessary place between the dielectric layers, and pressure may be applied in the vertical direction. Moreover, you may heat at the time of pressurization. The pressure of the pressurization, preferably 3~10kg / cm ^2, in particular in the range of 5~7kg / cm ² is preferred. The heating temperature is usually 100 to 2
The temperature is about 60 ° C, especially about 180 to 220 ° C.

The number of chips obtained by cutting the laminated precursor depends on the shape of the chips, but is usually 10 to
5000, especially 20-500.

As a method of obtaining a chip body from the laminated precursor, it is usually sufficient to cut or punch out with a shear, a circular saw, a band saw, a grindstone, an ultrasonic machine or the like.

The yield of the high-frequency multilayer component of the present invention thus obtained is preferably at least 90%, particularly about 97 to 100%.

The dielectric layer has a weight average absolute molecular weight of 100
A resin composition comprising one or more resins of 0 or more, wherein the sum of the number of carbon atoms and the number of hydrogen atoms is 99 or more.
%, And contains a heat-resistant low-dielectric polymer material in which some or all of the resin molecules are chemically bonded to each other, and a high-frequency ceramic dielectric material. With such a configuration, in a high frequency band, good characteristics of a high dielectric constant and a low dielectric loss tangent can be obtained. On the other hand, when only the heat-resistant low-dielectric polymer material is contained without containing the high-frequency ceramic dielectric material, the relative dielectric constant becomes low, which is not practical. Further, the use of the heat-resistant low-dielectric polymer material of the resin composition having the weight average absolute molecular weight as described above is to obtain sufficient strength, adhesion to metal, and heat resistance,
On the other hand, the reason why the sum of the number of atoms of carbon and hydrogen is 99% or more is that
This is for making the existing chemical bond a non-polar bond, which makes it easy to obtain a low dielectric loss tangent. Therefore, if the weight average absolute molecular weight is less than 1000, mechanical properties,
Heat resistance is insufficient and is not suitable. In addition, when the sum of the numbers of carbon and hydrogen atoms is less than 99%, particularly when the number of atoms forming polar molecules such as oxygen atoms and nitrogen atoms is more than 1%, the dielectric loss tangent becomes particularly high. Not suitable.

A particularly preferred weight average absolute molecular weight is 300
0 or more, most preferably 5000 or more. The upper limit of the weight average absolute molecular weight at this time is not particularly limited, but is usually about 10 million (however, in the case of a thermoplastic resin, it may be much larger than this).

Further, a heat-resistant low-dielectric polymer material will be described.

Specific examples of the resin constituting the polymer material include low-density polyethylene, ultra-low-density polyethylene,
Ultra low density polyethylene, high density polyethylene, low molecular weight polyethylene, ultra high molecular weight polyethylene, ethylene
Non-polar α-olefin homo- or copolymers (hereinafter also referred to as (co) polymers) such as propylene copolymer, polypropylene, polybutene, and poly-4-methylpentene, butadiene, isoprene, pentadiene, hexadiene, heptadiene, octadiene Phenylbutadiene, (co) polymers of each monomer of conjugated diene such as diphenylbutadiene, styrene, nucleus-substituted styrene, for example, methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorostyrene, α-substituted styrene, for example (co) polymers of each monomer of carbon ring-containing vinyl such as α-methylstyrene, α-ethylstyrene, divinylbenzene, vinylcyclohexane and the like.

In the above description, polymers of non-polar α-olefin monomers, conjugated diene monomers, and carbon ring-containing vinyl monomers are mainly exemplified.
Olefin monomer and conjugated diene monomer, non-polar α-
Copolymers obtained from monomers of different compound types, such as an olefin monomer and a carbon ring-containing vinyl monomer, may be used.

As described above, a resin composition is composed of one or more of these polymers, that is, resins, and some or all of these resin molecules are chemically bonded to each other. There must be. Therefore, some may be in a mixed state. By having a chemical bond at least in part as described above, the strength, adhesion to metal, and heat resistance when used as a heat-resistant low-dielectric polymer material are sufficient. On the other hand, when it is a mere mixture and has no chemical bond, it is insufficient from the viewpoint of heat resistance and mechanical properties.

The form of the chemical bond in the present invention is not particularly limited, and examples thereof include a crosslinked structure, a block structure, and a graft structure. A known method may be used to generate such a chemical bond. Preferred embodiments of the graft structure and the block structure will be described later. As a specific method for generating a crosslinked structure, thermal crosslinking is preferable,
The temperature at this time is preferably about 50 to 300 ° C. Other examples include cross-linking by electron beam irradiation.

The presence or absence of a chemical bond according to the present invention depends on the degree of crosslinking,
In the case of the graft structure, it can be confirmed by obtaining the graft efficiency and the like. It can also be confirmed by a transmission electron microscope (TEM) photograph or a scanning electron microscope (SEM) photograph. Usually, one polymer segment has the other polymer segment dispersed as fine particles of about 10 μm or less, more specifically 0.01 to 10 μm. On the other hand, in a mere mixture (blend polymer), compatibility between the two polymers such as a graft copolymer is not observed, and the particle size of the dispersed particles becomes large.

The resin composition of the present invention is a copolymer in which a non-polar α-olefin polymer segment and a vinyl aromatic copolymer segment are chemically bonded. A preferred example is a thermoplastic resin having a multiphase structure in which the formed dispersed phase is finely dispersed in the continuous phase formed from the other segment.

The non-polar α-olefin-based polymer which is one of the segments in the thermoplastic resin having the specific multiphase structure as described above is a non-polar α-olefin polymer obtained by high-pressure radical polymerization, medium-low pressure ionic polymerization or the like. It must be a homopolymer of an α-olefin monomer or a copolymer of two or more non-polar α-olefin monomers. Copolymers with polar vinyl monomers are unsuitable because of their high dielectric loss tangent. As the non-polar α-olefin monomer of the polymer, ethylene, propylene, butene-1, hexene-1, octene-1, 4-
Methylpentene-1s, among which ethylene,
Propylene, butene-1, 4-methylpentene-1
The non-polar α-olefin polymer obtained is preferable because of its low dielectric constant.

Specific examples of the nonpolar α-olefin (co) polymer include low-density polyethylene, ultra-low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, low-molecular-weight polyethylene, ultra-high-molecular-weight polyethylene,
Ethylene-propylene copolymer, polypropylene, polybutene, poly-4-methylpentene and the like can be mentioned. These non-polar α-olefin (co) polymers can be used alone or in combination of two or more.

The preferred molecular weight of such a nonpolar α-olefin (co) polymer is 1000 in terms of weight average absolute molecular weight.
That is all. There is no particular upper limit, but 1000
It is about ten thousand.

On the other hand, the vinyl aromatic polymer which is one of the segments in the thermoplastic resin having a specific multiphase structure is a non-polar polymer, and specifically, styrene,
Nuclear-substituted styrene such as methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorostyrene, α-substituted styrene such as α-methylstyrene, α-ethylstyrene, o-, m-, p-divinylbenzene (preferably m-styrene) -, P-divinylbenzene, particularly preferably p-divinylbenzene). Such non-polarity is achieved by introducing a monomer having a polar functional group by copolymerization.
This is because the dielectric loss tangent becomes high and is not suitable. The vinyl aromatic polymers can be used alone or in combination of two or more.

Among the vinyl aromatic copolymers, a vinyl aromatic copolymer containing a divinylbenzene monomer is preferred in terms of improving heat resistance. The vinyl aromatic copolymer containing divinylbenzene is, specifically, styrene,
Copolymers of each monomer such as a nuclear-substituted styrene such as methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorostyrene and α-substituted styrene such as α-methylstyrene and α-ethylstyrene, and a monomer of divinylbenzene It is a polymer.

The ratio between the divinylbenzene monomer and the other vinyl aromatic monomer as described above is not particularly limited. However, in order to satisfy the solder heat resistance, the divinylbenzene monomer is used. Is preferably 1% by weight or more. The divinylbenzene monomer may be 100% by weight, but the upper limit is preferably 90% by weight in view of synthesis.

The molecular weight of the vinyl aromatic polymer as one of the segments is 10% by weight average absolute molecular weight.
It is preferably at least 00. The upper limit is not particularly limited, but is about 10 million.

The thermoplastic resin having a specific multiphase structure according to the present invention contains 5-95% by weight, preferably 40-90% by weight, and most preferably 50% by weight of the olefin-based polymer segment.
~ 80% by weight. Accordingly, the content of the vinyl polymer segment is 95 to 5% by weight, preferably 60 to 50% by weight.
10 to 10% by weight, most preferably 50 to 20% by weight.

If the number of the olefin polymer segments is small, the molded product becomes brittle, which is not preferable. Further, when the number of the olefin-based polymer segments increases, the adhesion to the metal is low, which is not preferable.

The weight average absolute molecular weight of such a thermoplastic resin is 1,000 or more. The upper limit is not particularly limited, but is about 10,000,000 from the viewpoint of moldability.

Specific examples of the copolymer having a structure in which an olefin polymer segment and a vinyl polymer segment are chemically bonded include a block copolymer and a graft copolymer. Above all, a graft copolymer is particularly preferred because of ease of production. These copolymers may include an olefin-based polymer or a vinyl-based polymer without departing from the characteristics of the block copolymer, the graft copolymer, and the like.

The method for producing the thermoplastic resin having a specific multiphase structure of the present invention may be any of the generally known grafting methods such as chain transfer method and ionizing radiation irradiation method. Most preferred is the method described below. This is because the grafting efficiency is high and secondary aggregation due to heat does not occur, so that the expression of performance is more effective and the production method is simple.

Hereinafter, the method for producing a graft copolymer which is a thermoplastic resin having a specific multiphase structure of the present invention will be described in detail. That is, 100 parts by weight of an olefin-based polymer are suspended in water, and the vinyl aromatic-based monomer 5 to 40 is separately added.
One part or a mixture of two or more kinds of radically polymerizable organic peroxides represented by the following general formula (1) or (2) is added to 0.1 part by weight with respect to 100 parts by weight of the vinyl monomer. ~
10 parts by weight and a radical polymerization initiator having a decomposition temperature of 40 to 90 ° C. for obtaining a half-life of 10 hours are added in an amount of 0 to a total of 100 parts by weight of the vinyl monomer and the radically polymerizable organic peroxide. And a solution prepared by dissolving the vinyl monomer, the radically polymerizable organic peroxide and the radical polymerization initiator under conditions that do not substantially decompose the radical polymerization initiator. The olefin polymer is impregnated, the temperature of the aqueous suspension is increased, and the vinyl monomer and the radical polymerizable organic peroxide are copolymerized in the olefin copolymer to form the graft precursor. obtain.

Next, the grafting precursor was added in an amount of 100 to 30.
The graft copolymer of the present invention can be obtained by kneading while melting at 0 ° C. At this time, the graft copolymer can be obtained by separately mixing an olefin polymer or a vinyl polymer with the grafting precursor and kneading the mixture under melting. Most preferred is a graft copolymer obtained by kneading a grafting precursor.

[0041]

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In the general formula (1), R ₁ represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₂ represents a hydrogen atom or a methyl group, and R ₃ and R ₄ each represent 1 to 4 carbon atoms.
R ₅ represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms. m ₁ is 1 or 2
It is.

[0043]

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In the general formula (2), R ₆ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₇ represents a hydrogen atom or a methyl group, and R ₈ and R ₉ each represent 1 to 4 carbon atoms.
R ₁₀ represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms. m ₂ is 0, 1 or 2.

Examples of the radical polymerizable organic peroxide represented by the general formula (1) include t-butylperoxyacryloyloxyethyl carbonate; t-amylperoxyacryloyloxyethyl carbonate T-hexylperoxyacryloyloxyethyl carbonate;
1,1,3,3-tetramethylbutyl peroxyacryloyloxyethyl carbonate; cumyl peroxyacryloyloxyethyl carbonate; p-isopropylcumylperoxyacryloyloxyethyl carbonate ;
t-butylperoxymethacryloyloxyethyl carbonate; t-amylperoxymethacryloyloxyethyl carbonate; t-hexylperoxymethacryloyloxyethyl carbonate; 1,1,3,3-carbonate Tetramethylbutyl peroxymethacryloyloxyethyl carbonate; cumyl peroxymethacryloyloxyethyl carbonate; p-isopropylcumylperoxymethacryloyloxyethyl carbonate; t-butylperoxymethacryloyloxyethyl carbonate Ethyl carbonate-bonate; t-
Amyl peroxyacryloyloxyethoxyethyl car
Carbonate; t-hexylperoxyacryloyloxyethoxyethyl carbonate; 1,1,3,3-tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate; cumylperoxyacryloyloxyethoxyethyl Carbonate; p-isopropylcumylperoxyacryloyloxyethoxyethyl carbonate;
t-butyl peroxymethacryloyloxyethoxyethyl carbonate; t-amylperoxymethacryloyloxyethoxyethyl carbonate; t-hexylperoxymethacryloyloxyethoxyethyl carbonate;
1,1,3,3-tetramethylbutyl peroxymethacryloyloxyethoxyethyl carbonate; cumyl peroxymethacryloyloxyethoxyethyl carbonate
P-isopropylcumylperoxymethacryloyloxyethoxyethyl carbonate; t-butylperoxyacryloyloxyisopropylcarbonate; t-amylperoxyacryloyloxyisopropylcarbonate; t-hexyl Peroxyacryloyloxyisopropyl carbonate; 1,1,3,3-tetramethylbutylperoxyacryloyloxyisopropyl carbonate; cumylperoxyacryloyloxyisopropyl carbonate; p-isopropyl alcohol Milperoxyacryloyloxyisopropyl carbonate; t-butylperoxymethacryloyloxyisopropyl carbonate
T; t-amyl peroxymethacryloyloxyisopropyl carbonate; t-hexylperoxymethacryloyloxyisopropyl carbonate; 1,1,3,3-
Examples thereof include tetramethylbutyl peroxymethacryloyloxyisopropyl carbonate; cumyl peroxymethacryloyloxyisopropyl carbonate; p-isopropylcumylperoxymethacryloyloxyisopropyl carbonate.

Further, as the compound represented by the general formula (2), t-butylperoxyallylcarbonate;
Amyl peroxy allyl carbonate; t-hexyl peroxy allyl carbonate; 1,1,3,3-tetramethylbutyl peroxy allyl carbonate; p-menthane peroxy allyl carbonate Cumyl peroxy allyl carbonate; t-butyl peroxy methallyl carbonate; t-amyl peroxy methallyl carbonate; t-hexyl peroxy methallyl carbonate;
1,1,3,3-tetramethylbutyl peroxymethallyl carbonate; p-menthaneperoxymethallyl carbonate
Carbonate; cumyl peroxymethallyl carbonate; t
-Butyl peroxyallyloxyethyl carbonate; t
-Amyl peroxy allyloxyethyl carbonate; t
Hexyl peroxyallyloxyethyl carbonate;
t-butylperoxymetalaryloxyethylcarbonate
G; t-amyl peroxymetalaryloxyethyl carbonate
T-hexyl peroxymetalloxyethyl carbonate; t-butylperoxyallyloxyisopropyl carbonate; t-amylperoxyallyloxyisopropyl carbonate; t-hexylperoxyaryloxyisopropyl carbonate Bonnet; t-butyl peroxy metalaryloxy isopropyl carbonate; t-amyl peroxy metalaryloxy isopropyl carbonate; t-hexyl peroxy metalaryloxy isopropyl carbonate
And the like.

Among them, t-butylperoxyacryloyloxyethyl carbonate; t-butylperoxymethacryloyloxyethyl carbonate; t-butylperoxyallylcarbonate; t-butylperoxy Methallyl carbonate.

The graft efficiency of the thus obtained graft copolymer is 20 to 100% by weight. Grafting efficiency is performed by solvent extraction of ungrafted polymer,
It can be obtained from the ratio.

The thermoplastic resin having a specific multiphase structure of the present invention is preferably a graft copolymer of the above nonpolar α-olefin polymer segment and a vinyl aromatic polymer segment. In such a graft copolymer, a non-polar conjugated diene-based polymer segment may be used instead of or in addition to the non-polar α-olefin-based polymer segment. As the nonpolar conjugated diene-based polymer, those described above can be used, and they may be used alone or in combination of two or more.

The non-polar α-olefin-based polymer in the above graft copolymer may contain a conjugated diene monomer, and the non-polar conjugated diene-based polymer may include α-olefin.
An olefin monomer may be contained.

In the present invention, the obtained graft copolymer can be further crosslinked using divinylbenzene or the like. Particularly, a graft copolymer containing no divinylbenzene monomer is preferable from the viewpoint of improving heat resistance.

On the other hand, the thermoplastic resin having a specific multiphase structure of the present invention may be a block copolymer,
Examples of the block copolymer include a block copolymer containing at least one polymer of a vinyl aromatic monomer and at least one polymer of a conjugated diene.
It may be a linear type or a radial type, that is, a type in which a hard segment and a soft segment are radially bonded. Further, the polymer containing a conjugated diene may be a random copolymer with a small amount of a vinyl aromatic monomer, and a so-called tapered block copolymer, that is, 1
The vinyl aromatic monomer may be gradually increased in one block.

The structure of the block copolymer is not particularly limited, and may be any of (AB) _n type, (AB) _n -A type or (A, B) _n -C type. . Where A
Represents a polymer of a vinyl aromatic monomer, B represents a polymer of a conjugated diene, C represents a residue of a coupling agent, and n represents an integer of 1 or more. In addition, in this block copolymer, it is also possible to use a block copolymer in which a conjugated diene portion is hydrogenated.

In such a block copolymer, the above-mentioned non-polar α-olefin-based polymer may be used in place of or in addition to the above-mentioned non-polar conjugated diene-based copolymer. The diene-based polymer may contain an α-olefin monomer, and may be a non-polar α-olefin monomer.
The olefin-based polymer may contain a conjugated diene monomer. The ratio of each segment in the block copolymer and the preferred embodiment are the same as those of the graft copolymer.

The resin composition of the present invention, preferably a thermoplastic resin having a specific multiphase structure (particularly preferably a graft copolymer), is added with 4-methylpentene-1 to improve heat resistance. It is preferable to add a nonpolar α-olefin-based polymer containing a monomer. In the present invention, 4-
The non-polar α-olefin-based polymer containing the monomer of methylpentene-1 may be contained in the resin composition without forming a chemical bond, but in such a case, the addition is not necessarily required. Not required. However, it may be further added to obtain predetermined characteristics.

In such a nonpolar α-olefin-based copolymer containing a monomer of 4-methylpentene-1, 4-
The proportion of the monomer of methylpentene-1 is preferably at least 50% by weight. In addition, such a nonpolar α-olefin-based copolymer may include a conjugated diene monomer.

In particular, as the non-polar α-olefin copolymer containing a 4-methylpentene-1 monomer, poly-4- (4-methylpentene-1) monomer homopolymer is used.
Methylpentene-1 is preferred.

Poly 4-methyl pentene-1 is crystalline poly 4-methyl pentene-1,
Isotactic poly-4-methylpentene-1 obtained by polymerizing 4-methylpentene-1 as a monomer using a Ziegler-Natta catalyst or the like is preferred.

The ratio of poly-4-methylpentene-1 to a thermoplastic resin having a specific multiphase structure is not particularly limited.
In order to satisfy heat resistance and adhesion to metal, poly 4
The proportion of -methylpentene-1 is preferably from 10 to 90% by weight. When the proportion of poly-4-methylpentene-1 is small, the solder heat resistance tends to be insufficient. Also poly 4
When the ratio of -methylpentene-1 increases, the adhesion to metal tends to be insufficient. Poly 4-methylpentene-1
Instead, the amount of addition when the copolymer is used may be in accordance with this.

The softening point of the resin composition of the present invention (including those to which a non-polar α-olefin polymer containing a monomer of 4-methylpentene-1 is added) is 200 to 260 ° C.
Sufficient solder heat resistance can be obtained by appropriately selecting and using.

The electric performance of the heat-resistant low-dielectric polymer material of the present invention is preferably in a frequency band of 500 MHz to 3 GHz.
z, especially in the microwave and millimeter wave bands of 800 MHz to 2 GHz, the relative dielectric constant (εr) is 5 or more, especially 10 to 2
0, and the dielectric loss tangent (tan δ) is 0.01
Hereinafter, it is usually 0.005 to 0.001.

Incidentally, the insulation resistivity of the polymer material of the present invention is 2 to 5 × 10 ¹⁴ Ωcm or more in normal volume resistivity. Further, it has a high dielectric breakdown strength and exhibits excellent characteristics of 15 KV / mm or more, particularly 18 to 30 KV / mm. Furthermore, it has excellent heat resistance.

One of these polymer materials may be used alone, or two or more thereof may be used in combination. These polymer materials are used as granules.

The ceramic dielectric material used in the present invention is not particularly limited, but preferably has a relative dielectric constant (εr) of 1
0 or more, more preferably 30 or more, still more preferably 8
5 to 100, preferably a dielectric loss tangent (tan δ) of 0.00
2 or less, Q is preferably 2500 to 20000/1 GHz
Is desirable.

The ceramic dielectric material preferably used in the present invention includes, for example, titanium-barium-neodymium composite oxide, lead-calcium composite oxide, titanium dioxide ceramic, barium titanate ceramic, lead titanate. Ceramics, strontium titanate ceramics, calcium titanate ceramics, bismuth titanate ceramics, magnesium titanate ceramics, lead zirconate ceramics, and the like. Furthermore, CaWO ₄ ceramics, Ba (Mg, Nb) O ₃ ceramics, Ba
(Mg, Ta) O ₃ ceramics, Ba (Co, M)
g, Nb) O ₃ ceramics, Ba (Co, Mg, T)
a) O ₃ -based ceramics; They are,
They may be used alone or as a mixture of two or more.

The above-mentioned titanium dioxide-based ceramics refers to a system containing only titanium dioxide or a system containing a small amount of other additives in titanium dioxide. Is held. The same applies to other ceramics. Titanium dioxide is a substance represented by TiO ₂ and can have various crystal structures. Among them, the one used as a dielectric ceramic has a rutile structure.

The particle diameter of the ceramic dielectric material is 1 μm.
It is preferable in terms of characteristics that the particles are distributed in the range from m diameter to 200 μm diameter, and the average particle diameter is preferably 90 to 150 μm. If the particle diameter of the ceramic dielectric material is too large, it is difficult to uniformly disperse and mix it in the polymer dielectric material. On the other hand, if the particle size is too small, handling becomes difficult, for example, mixing of the ceramic dielectric material and the polymer material becomes impossible, or particles of the ceramic dielectric material aggregate to form a non-uniform mixture.

As the ceramic dielectric material, in order to obtain a high dielectric constant and a low dielectric loss tangent in a high frequency band, a titanium-barium-neodymium-based material or a lead-calcium-based material is particularly preferable. The content of these preferably used ceramic dielectric materials in the composite dielectric material composition is 5%.
The content is preferably 0 to 95 wt%, more preferably 50 to 90 wt%.
%, And particularly preferably 60 to 90% by weight. With such a content, a high dielectric constant and a low dielectric loss tangent can be easily obtained. On the other hand, when the content of the ceramic dielectric material decreases, the relative dielectric constant decreases,
The dielectric loss tangent tends to increase. On the other hand, when the content of the ceramic dielectric material is too large, the mechanical properties are reduced, and the moldability is deteriorated.

Such a ceramic dielectric material is obtained by firing by a known method, and the firing conditions are not particularly limited.
Preferably it is 400 ° C.

The composite dielectric material composition of the present invention can be obtained by melt-kneading a predetermined amount of a heat-resistant low-dielectric polymer material and a ceramic dielectric material. Specifically, melt kneading can be performed using a commonly used kneader such as a Banbury mixer, a pressure kneader, a kneading extruder, a twin-screw extruder, or a roll.

The composite dielectric material in the form of use can be obtained from the composite dielectric material composition of the present invention by a method such as molding into a desired shape such as a thin film (film) by hot pressing or the like. With a shearing force, for example,
It can also be obtained by a method of melt-mixing with another thermoplastic resin and molding into a desired shape with a lumixer, Banbury mixer, kneader, single-screw or twin-screw extruder or the like.

Alternatively, the dielectric layer of the high-frequency laminated electronic component of the present invention may use the following dielectric polymer material, but is preferably the above graft polymer.

The dielectric polymer material is preferably obtained by polymerizing a monomer composition containing a fumaric acid diester as a monomer, and is a fumarate-based material having a repeating unit derived from the fumaric acid diester. It is a polymer.

The polymer of the fumaric acid diester in the present invention is not particularly limited as long as it imparts low dielectric property and heat resistance to the polymer material. ) A compound represented by the above formula 3 is preferred.

As for the formula (I), in the formula (I), R
¹ represents an alkyl group or a cycloalkyl group, R ² represents an alkyl group, a cycloalkyl group or an aryl group, and R ¹ and R ² may be the same or different.

The alkyl group represented by R ¹ and R ² preferably has 2 to 12 carbon atoms, may be linear or branched, and further has a substituent. You may have. When the compound has a substituent, examples of the substituent include a halogen atom (F, Cl), an alkoxy group (such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group);
And an aryl group (eg, a phenyl group).

Specific examples of the alkyl group represented by R ¹ and R ² include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group. (N-amyl group), sec-amyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 4-methyl-2-pentyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl Group, dodecyl group, trifluoroethyl group, hexafluoroisopropyl group, perfluoroisopropyl group, perfluorobutylethyl group, perfluorooctylethyl group, 2-chloroethyl group, 1-butoxy-2-
Examples include a propyl group, a methoxyethyl group, and a benzyl group.

The cycloalkyl group represented by R ¹ and R ² is preferably a cycloalkyl group having a total of 3 to 14 carbon atoms, and may be a monocyclic or bridged ring. It may have a group. In this case, the substituent may be the same as those exemplified above for the alkyl group, and examples thereof include an alkyl group (a linear or branched one having 1 to 14 carbon atoms such as a methyl group). be able to.

Specific examples of the cycloalkyl group represented by R ¹ and R ² include a cyclopentyl group, a cyclohexyl group, an adamantyl group and a dimethyladamantyl group.

The aryl group represented by R ² is preferably an aryl group having a total of 6 to 18 carbon atoms, and is preferably a monocyclic ring, but may be a polycyclic ring (condensed ring or ring assembly). May be. In this case, the substituents are the same as those exemplified for the alkyl group and the cycloalkyl group.

Specific examples of the aryl group represented by R ² include a phenyl group.

As R ¹ and R ² , an alkyl group and a cycloalkyl group are preferable. As the alkyl group, an alkyl group having a branch is preferable, and an isopropyl group, sec-
A butyl group and a tert-butyl group are preferred. Also,
As the cycloalkyl group, a cyclohexyl group or the like is preferable.

Preferable examples of the fumaric acid diester monomer represented by the formula (I) include diethyl fumarate,
Di-n-propyl fumarate, di-n-hexyl fumarate, isopropyl-n-hexyl fumarate, diisopropyl fumarate, di-n-butyl fumarate, di-
sec-butyl fumarate, di-tert-butyl fumarate, di-sec-amyl fumarate, n-butyl-
Isopropyl fumarate, isopropyl-sec-butyl fumarate, tert-butyl-4-methyl-2-pentyl fumarate, isopropyl-tert-butyl fumarate, isopropyl-sec-amyl fumarate,
Dialkyl fumarate such as di-4-methyl-2-pentyl fumarate, di-isoamyl fumarate, di-4-methyl-2-hexyl fumarate, tert-butyl-isoamyl fumarate; dicyclopentyl fumarate;
Dicycloalkyl fumarate such as dicyclohexyl fumarate, dicycloheptyl fumarate, cyclopentyl-cyclohexyl fumarate, bis (dimethyladamantyl) fumarate, bis (adamantyl) fumarate; isopropyl-cyclohexyl fumarate, isopropyl-dimethyl adamantyl fumarate; Alkylcycloalkyl fumarate such as isopropyl-adamantyl fumarate and tert-butyl-cyclohexyl fumarate; alkylaryl fumarate such as isopropyl-phenyl fumarate; alkyl such as tert-butylbenzyl fumarate and isopropyl-benzyl fumarate Aralkyl fumarate; ditrifluoroethyl fumarate, dihexafluoroisopropyl fumarate, diperfluoroi Di-fluoroalkyl fumarate such as propyl fumarate and dibis (perfluorobutylethyl) fumarate; alkyl fluoroalkyl fumarate such as isopropyl-perfluorooctylethyl fumarate and isopropyl-hexafluoroisopropyl fumarate; 1-butoxy -2-propyl-
Other substituted alkylalkyl fumarate such as tert-butyl fumarate, methoxyethyl-isopropyl fumarate, 2-chloroethyl-isopropyl fumarate and the like can be mentioned.

Among them, diisopropyl fumarate, dicyclohexyl fumarate, di-sec-butyl fumarate, di-tert-butyl fumarate, isopropyl-tert-butyl fumarate, n-butyl-isopropyl fumarate, n-hexyl-fumarate Isopropyl fumarate and the like are particularly preferred.

These diesters can be synthesized by combining ordinary esterification techniques and isomerization techniques.

In obtaining a fumarate-based polymer which is a dielectric polymer material, the fumaric acid diester (fumarate-based compound) may be used alone or in combination of two or more. Therefore, the fumarate-based polymer of the present invention may be a homopolymer obtained by polymerizing only one type of the above fumaric acid diester, or a copolymer obtained by polymerizing two or more types. The copolymer may be any of a random copolymer, an alternating copolymer, a block copolymer and the like.

As described above, the fumarate-based polymer of the present invention may use only the fumaric acid diester as a monomer component. However, it is possible to use other monomers in addition to the fumaric acid diester. And a copolymer with another monomer component. As such another monomer component, a vinyl monomer (monomer) may be used, and the vinyl monomer which is a comonomer imparts moldability, film forming property, and mechanical strength. The compound is not particularly limited as long as it can be copolymerized with the fumarate-based compound, but preferably includes a compound represented by the formula (II) [Formula 4].

Referring to the formula (II), X represents a hydrogen atom or a methyl group, Y represents a fluorine atom, a chlorine atom,
Alkyl group, alkenyl group, aryl group, ether group,
Represents an acyl group or an ester group.

The alkyl group represented by Y is preferably one having a total carbon number of 1 to 14, and may be linear or branched.

The alkenyl group represented by Y is preferably one having a total of 2 to 14 carbon atoms, which may be linear or branched, and further having a substituent. Examples thereof include a vinyl group, an allyl group, a propenyl group, and a butenyl group.

The aryl group represented by Y is preferably one having a total of 6 to 18 carbon atoms, and may be a single ring or a polycyclic ring such as a condensed ring.
l) may have a substituent of an alkyl group (eg, a methyl group). Specifically, phenyl group, α-naphthyl group, β
-Naphthyl group, (o-, m-, p-) tolyl group, (o
-, M-, p-) chlorophenyl group and the like.

The ether group represented by Y is represented by —OR ³ , and R ³ in this case includes an alkyl group, an aryl group and the like. The alkyl group represented by R ³ preferably has 1 to 8 carbon atoms in total, and may be linear or branched, and further has a substituent (eg, a halogen atom). You may have. The aryl group represented by R ³ preferably has 6 to 18 carbon atoms in total, and is preferably a single ring, but may be a polycyclic ring such as a condensed ring.

Examples of the ether group represented by Y include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isobutoxy group and a phenoxy group.

The acyl group represented by Y is represented by —COR ^{4. In} this case, R ⁴ includes an alkyl group, an aryl group and the like. The alkyl group represented by R ⁴ preferably has 1 to 8 carbon atoms in total, and may be linear or branched, and further has a substituent (eg, a halogen atom). It may be. The aryl group represented by R ⁴ preferably has 6 to 18 carbon atoms, and is preferably a single ring, but may be a polycyclic ring such as a condensed ring.

The acyl group represented by Y includes an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a benzoyl group and the like.

The ester group represented by Y is —OCOR ⁵
Or represented by -COOR ^5, the alkyl group as R ⁵ in this case, and an aryl group. The alkyl group represented by R ⁵ preferably has 1 to 20 carbon atoms in total, and may be linear or branched, and further has a substituent (eg, a halogen atom). You may have. The aryl group represented by R ⁵ preferably has 6 to 18 carbon atoms in total, and is preferably a single ring, but may be a polycyclic ring such as a condensed ring.

Examples of the ester group represented by Y include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, an isovaleryloxy group, —OCOC ₄ H ₉ (−sec), and —OCOC.
_{4 H 9 (-tert), -} OCOC (CH 3) 2 CH 2
CH ₃ , —OCOC (CH ₃ ) ₂ CH ₂ CH ₂ CH ₃ ,
Stearoyloxy group, benzoyloxy group, tert
-Butylbenzoyloxy group, methoxycarbonyl group,
Examples include an ethoxycarbonyl group, a butoxycarbonyl group, a 2-ethylhexyloxycarbonyl group, and a phenoxycarbonyl group.

The copolymer component used for the dielectric polymer material is a vinyl comonomer mainly composed of an olefinic hydrocarbon. Examples of the vinyl monomer represented by the formula (II) include vinyl acetate and vinyl pivalate. Carboxylic acids such as vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, vinyl propionate, vinyl stearate, and vinyl 2-ethyl-2-methylbutanoate Vinyls; p-tert
Aromatic vinyl monomers such as -butyl vinyl benzoate, N, N-dimethylamino vinyl benzoate and vinyl benzoate; styrene, o-, m-, p-chloromethylstyrene, α-methylstyrene and the like. Α-
Substituted styrene derivatives; alkyl nucleus-substituted styrenes such as o-, m- and p-methylstyrene; α-olefins such as vinyl chloride and vinyl fluoride; o-, m- and p- such as p-chlorostyrene. Halogen nucleus substituted styrene such as halogenated styrene; vinyl ethers such as ethyl vinyl ether, vinyl butyl ether and isobutyl vinyl ether; naphthalene derivatives such as α- and β-vinyl naphthalene; alkyl vinyl ketones such as methyl vinyl ketone and isobutyl vinyl ketone; butadiene And diene such as isoprene; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-
Known radical polysynthetic monomers such as (meth) acrylates such as ethylhexyl (meth) acrylate and phenyl (meth) acrylate can be preferably exemplified.

In order to produce such a vinyl monomer, for example, a transesterification reaction between vinyl acetate and a corresponding organic acid is carried out in the presence of mercury acetate or sulfuric acid, or another catalyst such as platinum or rhodium. Can be easily synthesized by performing the reaction in the presence of a metal complex and a catalyst.

As such a vinyl monomer, only one kind may be used as a comonomer, or two or more kinds may be used in combination.

The fumarate-based polymer of the present invention having a repeating unit derived from such a vinyl-based monomer is a copolymer, such as a random copolymer, an alternating copolymer, or a block copolymer. Any of them may be used.

The polymer material having a repeating unit derived from the fumaric acid diester has a low dielectric property, and is excellent in film formability, film adhesion, mechanical properties and the like. As described above, such a polymer material includes a homopolymer using only the same fumaric acid diester, a copolymer of fumaric acid diesters, and another vinyl-based monomer copolymerizable with the fumaric acid diester. Any of a copolymer with a monomer may be used.

Although the molecular weight of the fumarate-based polymer is not particularly limited, for example, to form an electric insulating film and an electric insulating substrate obtained by laminating the same, considerable stress generated during the production of electronic parts is required. Since mechanical strength enough to withstand the electrically insulating substrate is required, a high molecular weight material is desirable in view of its use and the like, and the number average molecular weight is preferably 10,000 to 1500,000. When the molecular weight is small, mechanical strength and chemical stability are likely to be inferior, and heat resistance is also poor. In particular, it is desirable that the molecular weight be as high as possible in order to eliminate film defects, film adhesion to a substrate, and film defects. However, if the molecular weight is too large, workability is poor, such as difficulty in forming a uniform and smooth film, and workability is also poor.

The dielectric polymer material is prepared by polymerizing a monomer composition substantially containing only the above-mentioned fumaric acid diester as a monomer component, or further as a monomer component as described above. It is obtained by polymerizing a monomer composition containing a vinyl monomer.

In this case, the content of the fumaric acid diester is preferably at least 50% by weight, more preferably at least 60% by weight, particularly preferably at least 80% by weight, based on the total amount of the monomer (raw material monomer) as a raw material. When the amount of fumaric acid diester is small, electric characteristics (dielectric constant and low dielectric loss tangent), heat resistance and the like become insufficient, which is not preferable.

On the other hand, the ratio of the above-mentioned vinyl monomer to the total amount of the raw material monomers is as follows: low dielectric properties (low dielectric constant, low dielectric loss tangent), moldability, solution viscosity, film adhesion, mechanical properties, etc. In view of the above, it is preferably 0 to 50% by weight, more preferably 0 to 40% by weight, and particularly preferably 0 to 20% by weight.

The component derived from the fumaric acid diester in such a fumarate-based polymer is preferably at least 50% by weight, more preferably at least 60% by weight, particularly preferably at least 80% by weight.

The softening temperature of the fumarate-based polymer used in the present invention is 200 ° C. or higher, and is usually from 230 to 3
It is in the range of 50 ° C. Since the softening temperature is high as described above, the heat resistance in the soldering step essential for the device forming step is sufficient. The reason for having such a high softening temperature is that the main chain structure does not have a methylene group and the substituent is bonded on the carbon of the main chain, thereby suppressing the thermal kinetic of the main chain. Conceivable.

Thus, the fumarate-based polymer used in the present invention has a rod-like structure and is a rigid polymer. Therefore, they are not easily attacked by the side chain bond,
A polymer having excellent heat resistance, acid resistance and alkali resistance (etching resistance) can be obtained.

The fumarate-based polymers preferably used in the present invention are illustrated below. The polymer is represented by a raw material monomer.

I) Di-alkyl fumarate type I-1 di-isopropyl fumarate I-2 di-cyclohexyl fumarate I-3 di-sec-butyl fumarate I-4 di-tert-butyl fumarate I-5 tert-butyl-isopropyl fumarate I-6 di-isopropyl fumarate / di-sec-butyl fumarate I-7 tert-butyl-isopropyl fumarate /
Di-isopropyl fumarate I-8 Di-isopropyl fumarate / di-cyclohexyl fumarate I-9 Di-isopropyl fumarate / n-butyl-isopropyl fumarate I-10 Di-isopropyl fumarate / n-hexyl-
Isopropyl fumarate I-11 di-cyclohexyl fumarate / n-butyl-
Isopropyl fumarate I-12 di-cyclohexyl fumarate / di-sec-
Butyl fumarate

II) Di-alkyl fumarate / vinyl type II-1 di-isopropyl fumarate / styrene II-2 di-sec-butyl fumarate / vinyl tert-butyl benzoate II-3 di-cyclohexyl fumarate / 2 -Ethyl-
Vinyl 2-methylbutanoate II-4 Di-isopropyl fumarate / vinyl tert-butyl benzoate II-5 Di-isopropyl fumarate / vinyl p-N, N-dimethylaminobenzoate II-6 Di-cyclohexyl fumarate / tert -Butyl vinyl benzoate II-7 cyclohexyl-isopropyl fumarate / vinyl acetate II-8 di-tert-butyl fumarate / di-cyclohexyl fumarate-tert-vinyl vinyl benzoate II-9 di-isopropyl fumarate / di- Cyclohexyl fumarate / vinyl 2-ethyl-2-methylbutanoate II-10 di-isopropyl fumarate / di-sec-butyl fumarate / vinyl N, N-dimethylaminobenzoate II-11 di-sec-butyl fumarate / Di-cyclohexyl fumarate / tert-butyl Vinyl benzoate II-12 di - cyclohexyl fumarate / di - isopropyl fumarate / styrene

In the present invention, in order to produce the fumarate-based polymer, a usual radical polymerization method can be preferably used. The polymerization initiator used for the polymerization has a 10-hour half-life temperature of 80 to increase the molecular weight.
One or more of an organic peroxide and an azo compound having a temperature of not higher than
More than one species can be preferably used. Examples of such a polymerization initiator include benzoyl peroxide, diisopropyl peroxydicarbonate, tert-butyl peroxydi-2-ethylhexanoate, tert-butyl peroxydiisobutyrate, cumene peroxide,
Organic peroxides such as tert-butyl hydroperoxide, tert-butyl peroxypivalate, lauroyldiacyl peroxide, 2,2′-azobisbutyronitrile, 2,2′-azobis (2-methylbutyro Nitrile), azobis (2,4-dimethylvaleronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (isobutyric acid) dimethyl, 2,2′-azobis (2 Azo compounds such as 4-dimethylvaleronitrile) and tert-butylperoxyisopropyl carbonate. The amount of the polymerization initiator to be used is 10 to 100 parts by weight of the raw material monomer.
It is preferably at most 5 parts by weight, more preferably at most 5 parts by weight.

The conditions for polymerizing or copolymerizing each monomer in such a preparation method are as follows: the polymerization system is appropriately set to an inert gas such as nitrogen, carbon dioxide, helium, or the like.
It is preferable to carry out the polymerization under a substitution or atmosphere with argon or the like, or under degassing conditions. The temperature at the time of polymerization or copolymerization varies depending on the type of polymerization initiator used, but is preferably in the range of 30 ° C to 120 ° C. The total time required for the polymerization is desirably about 10 to 72 hours. It is also possible to polymerize the starting monomer by adding a coloring agent such as a dye or an additive such as an ultraviolet absorber.

The radical polymerization can be carried out by any of a number of polymerization methods used for radical polymerization of general-purpose vinyl monomers such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and radiation polymerization. In the present invention, in the application for a high frequency band, it is important to make the low dielectric loss tangent extremely low as an electrical characteristic of the low dielectric electric insulating substrate. The presence of low-molecular-weight polymers in the polymer material causes external plasticization, which increases the dielectric loss tangent, and deteriorates the dielectric properties in the high-frequency band, so that the molecular weight of the fumarate-based polymer and copolymer becomes extremely high. It is important to take such a polymerization method, it is possible to increase the concentration of the charged monomer, for example, fumaric acid diester which is a charged monomer at the time of copolymerization,
A bulk polymerization method or a suspension polymerization method that can sufficiently increase the concentration of both monomers with a vinyl monomer is most desirable. Further, as the polymerization temperature becomes higher, the molecular weight of the polymer or copolymer becomes smaller.
It is preferable to carry out radical polymerization or copolymerization at a low temperature of ° C.

The fumarate-based polymer of the present invention has a nuclear magnetic resonance spectrum (NMR) and an infrared absorption spectrum (IR).
And the like.

Various terminal groups can be introduced according to the purpose.

The dielectric polymer material is used together with the ceramic dielectric material, like the above-mentioned heat-resistant dielectric polymer material.

The ceramic dielectric material is the same as described above. The content of these preferably used ceramic dielectric materials in the composite dielectric material composition is 50 to 50%.
It is preferably 95% by weight, more preferably 50 to 90% by weight, and particularly preferably 60 to 85% by weight. With such a content, a high dielectric constant and a low dielectric loss tangent can be easily obtained. On the other hand, when the content of the ceramic dielectric material decreases, the relative dielectric constant decreases, and the dielectric loss tangent tends to increase. On the other hand, when the content of the ceramic dielectric material is too large, the mechanical properties are reduced, and the moldability is deteriorated.

The conductor layer formed on or between the dielectric layers or in the dielectric layer may be made of a single metal such as gold, silver, copper, nickel, chromium, titanium, or aluminum, or may be made of any of these. An alloy or the like can be used. These are usually formed by injection molding by casting a conductive layer (conductive plate) formed by etching, pressing, or the like, or by laying a conductive layer pattern on a dielectric layer formed by a printing method, and further thereon. The dielectric layers are formed one upon another.
In addition, it is also possible to bond and fuse a metal conductor film on the dielectric layer, and in addition, it can be formed by vapor deposition such as vapor deposition or sputtering, or wet plating. The element pattern can be obtained by etching (wet or dry) the formed conductor layer into a desired pattern. In this case, by using the above-mentioned dielectric layer, a material having good adhesion to the metal conductor film can be obtained. In this case, the thickness of the dielectric layer is preferably 50 to 1000 μm, particularly 100 to 800 μm, and more preferably 200 to 500 μm by molding or the like. The thickness of the metal conductor film is preferably 10 to 70 μm, particularly 18 to 35 μm. Further, if necessary, a through hole may be formed, and a through hole may be formed by plating or the like.

When the conductor layer is formed in a pattern, the metal conductor film may be patterned into a predetermined shape and then adhered. However, when the metal conductor film and the dielectric layer are brought into close contact with each other by lamination, the outermost metal conductor layer may be patterned and then adhered, or may be removed by etching and then patterned.

The frequency band used by the high-frequency multilayer component of the present invention is preferably 500 MHz to 3 GHz, particularly 8 MHz.
00 MHz to 2 GHz.

Hereinafter, the high-frequency multilayer component of the present invention will be described in detail with reference to specific examples.

FIG. 1 is an exploded perspective view of a filter showing a specific example of the high-frequency multilayer component of the present invention, and FIG. 2 is a partially transparent appearance perspective view of an assembled state of the filter. The illustrated filter has the dielectric layers 101 to 118. The dielectric layers 101 to 118 are formed with conductor layers that constitute circuit elements such as capacitors and inductors as necessary. The parameters of these circuit elements are
It is determined by the dielectric constant and thickness of the dielectric layer, the shape of the conductive layer, and the like. That is, in this example, the conductor layer 201 is formed on the dielectric layer 101, and the conductor layers 202a and 202b are formed on the dielectric layer 102. The conductor layer 201 and the conductor layer 202a constitute a capacitor CE11, and the conductor layer 201 and the conductor layer 202b constitute a capacitor CE21. Similarly, conductor layers 203a, 203c and 203d are formed on the dielectric layer 103, and the conductor layers 202a and
3a and the capacitor CE12, and the conductor layer 202b
And the conductor layer 203a constitute a capacitor CE22. The conductor layers 203c and 203d constitute so-called through holes, and are formed in the same positions of the conductor layers 202a and 202b and the conductor layers formed on the lower dielectric layer 104. 204a, 20
4b is electrically connected. Further, the conductor layer 204
a and the conductor layer 203a constitute a capacitor CE13,
The conductor layer 204b and the conductor layer 203a are
Constructs E23.

On the dielectric layer 105, a conductor layer 205a,
205b, 205c, and 205d are formed, and the conductor layer 205a and the conductor layer 204a constitute a capacitor Ci1, and the conductor layer 205b and the conductor layer 204b constitute a capacitor Ci2. In addition, the conductor layer 205c,
The portion of the chip end face side of 205d is the input end I
N, and functions as an output terminal OUT. The conductor layers 205c and 205d form through holes,
It is connected to a through hole formed at the same position on the conductor layers 204a and 204b. Conductive layers 206a, 206c and 206d are formed on dielectric layer 106. The conductor layer 206a and the conductor layer 205a constitute a capacitor Cp1, and the conductor layer 205a and the capacitor Cp1.
Makes up p2. Further, the conductor layers 206c and 206d
Constitutes a through hole, the through hole 205c,
205d.

Further, the dielectric layers 107 to 111 have through holes 207c, 207d, 20 as conductor layers.
8c, 208d, 209c, 209d, 210c, 21
0d, 211c and 211d are formed and connected to each other, and the through holes 206c and 206d are formed.
d, and the following conductive layers 212a, 212
2b is also connected. Conductive layers 212a and 212b are formed on the dielectric layer 112, and constitute the inductors L1 and L2, respectively. Further, a plurality of dielectric layers 113 to 117 are arranged below the lower layer. A conductor layer 218 is formed on the dielectric layer 118 below the layer, and functions as a ground pattern (E).

Then, these are laminated to form a filter as shown in FIG. FIG. 2 is a diagram in which a stacked multi-element structure is cut into one component chip.
In the figure, a filter 1 has a conductive layer 20
A terminal 11 connected to the input terminal IN of 5a is formed, and a terminal connected to the output terminal OUT of the conductor 205b is formed on the opposite side (not shown). In addition, the ground terminals 12 connected to the conductors 201 and 203a and the conductor 218 are formed on the long sides, and are connected to external circuits, respectively. The conductors 210, 203a, 212a, 212b, 2
A ground terminal (not shown) connected to the terminal 18 is formed.

FIG. 3 shows an equivalent circuit of the filter 1. In the figure, Cp = Cp1 + Cp2, and CE1 = CE11 + CE12.
+ CE13, and CE2 = CE21 + CE22 + CE23. Further, L1 and L2 are mutually coupled by a mutual inductance M.

In the filter of the present invention having such a structure, the conventional filter requires several to several hundreds (in some cases, thousands) per substrate by the ceramic green sheet method or the printed multilayer method. It is manufactured by a multi-cavity process in which a conductive pattern is formed, fired, and divided (or divided and fired), while injection molding is performed by casting a conductive plate formed by etching, pressing, etc., or printing. A conductive plate pattern can be placed on a resin substrate formed by the method, and the resin substrate can be further stacked thereon. In addition, a glass cloth is impregnated with a fumarate-based resin, a steel foil is applied to the substrate material, and a pattern is formed by etching or the like. The boards can be laminated and divided to produce.

The dielectric layer is formed of a fumarate-based or graft polymer-based resin mixed with a ceramic powder to adjust the relative dielectric constant to 10 to 20.
0.0001, which means that the same electrical characteristics as those of the ceramic can be obtained, and the weight is further reduced.

Since the high-frequency multilayer component of the present invention does not use ceramics as a laminate, it does not cause a layer shift due to viscosity before firing, shrinkage due to firing, and does not cause distortion in the internal structure. The division can be easily cut.

The multilayer laminated parts of the present invention are not limited to the above-mentioned filters, but are widely used in high-frequency circuits, for example, couplers, mixers, distributors, V
Applicable to CO and the like.

[0133]

EXAMPLES First, an example of synthesizing the polymer material used in the examples will be described.

(Synthesis Example) In a stainless steel autoclave having a volume of 5 liters, 2500 g of pure water was added, and 2.5 g of polyvinyl alcohol was dissolved as a suspending agent.
In this, polypropylene "J" was used as an olefin polymer.
Alloy 150G ”(trade name, Japan Polyolefin Co., Ltd.)
Was added and stirred and dispersed. Separately, 1.5 g of benzoyl peroxide as a radical polymerization initiator,
9 g of t-butylperoxymethacryloyloxyethyl carbonate as a radical polymerizable organic peroxide is dissolved in 300 g of styrene as a vinyl aromatic monomer,
This solution was charged and stirred into the autoclave.
Then, the autoclave was heated to 60 to 65 ° C. and stirred for 2 hours to impregnate the polypropylene with a vinyl monomer containing a radical polymerization initiator and a radically polymerizable organic peroxide. Next, the temperature was raised to 80 to 85 ° C., and maintained at that temperature for 7 hours to complete the polymerization. After filtration, washing and drying were performed to obtain a grafted precursor (a).

Next, the grafting precursor (a) was used as a Labo Plastomill single screw extruder (manufactured by Toyo Seiki Seisaku-sho, Ltd.).
At 200 ° C. to cause a grafting reaction to obtain a graft copolymer (A).

When the graft copolymer (A) was analyzed by pyrolysis gas chromatography, the weight ratio of polypropylene (PP): styrene (St) was 70:
30.

At this time, the graft efficiency of the styrene polymer segment was 50.1% by weight. The grafting efficiency was calculated by extracting an ungrafted styrene polymer with ethyl acetate using a Soxhlet extractor and determining the ratio.

For the molecular weight, the weight average absolute molecular weight was measured using high temperature GPC (manufactured by Waters Inc.). The contents of carbon and hydrogen in this resin were determined by elemental analysis.
As a result, the ratio of the sum of the numbers of carbon atoms and hydrogen atoms is 99%
% Or more. The molecular weight of PP was 300,000.

The resin particles were subjected to hot press molding at 220 ° C. using a hot press molding machine (manufactured by Kamishima Kikai Co., Ltd.) to form a 10 cm
× 10 cm × 0.1 cm specimens of an electrically insulating material were prepared.
In addition, 13 mm × 65 mm × 6 mm test pieces were prepared by an injection molding machine as Izod impact test pieces and solder heat resistance test pieces. Perform the following measurements using the obtained test piece,
The volume resistivity, dielectric strength, dielectric constant, dielectric loss tangent, Izod impact strength, and adhesion to metal were evaluated.
The water absorption was measured using the obtained resin pellets. Further, the resin molded and thermally cross-linked by a hot press was pulverized and heated in xylene, and the degree of cross-linking was confirmed from its solubility. The test method is shown below.

Insulation resistance test (volume resistivity); JIS K 6911
(Test voltage 500V) Dielectric breakdown test (dielectric strength); JIS C 2110 dielectric constant test; compliant with JIS L 1094 B method Dielectric loss tangent; compliant with ASTM D150

Izod impact strength (notched) (Izod in the table. The unit is kg · cm / cm.
² ); JIS K7110 Adhesion to metal; Aluminum was vacuum-deposited on a test piece, and the adhesiveness of the thin film when rubbed lightly with a cloth was examined.

Water absorption: according to ASTM D570 Degree of crosslinking: 1 g of the crushed resin was placed in 70 ml of xylene, heated to 120 ° C. while refluxing, and stirred for 10 minutes. Thereafter, the solubility of the resin was observed.

Moldability: The moldability when preparing an Izod impact test specimen with an injection molding machine, the moldability with a press machine,
And the moldability when the film was formed by extrusion molding was evaluated.

As a result of each test, volume resistivity: 3.1 × 10
¹⁶ (Ωcm), dielectric breakdown strength: 22 (kV / mm), dielectric constant: 2.27 at 2 GHz, 2.30 at 2 GHz, 2.30 at 5 GHz, 2.26 at 10 GHz, dielectric loss tangent: 1 GHz 0.84 × 10 ^-3 at 2 GHz, 0.52 × 10 ^-3 at 5 GHz
0.49 × 10 ⁻³ at 10 GHz, 0.48 × 10 ^{−3 at} 10 GHz, Izod impact value: 9 (Kg · cm / cm ² ), adhesion to metal:
Good, water absorption: 0.03% or less, moldability: good, degree of crosslinking (solubility): swelling.

The graft copolymer (A) and the ceramic dielectric material were quantitatively fed to a coaxial twin-screw extruder having a screw diameter of 30 mm and a screw diameter of 30 mm (PCM30, manufactured by Ikegai Iron & Steel Co., Ltd.) at a cylinder temperature of 230 ° C. (A twin screw extruder) and melt-kneaded to obtain a composite dielectric material composition. When this composite dielectric material composition was analyzed by the ashing method, the weight ratio of the resin and the ceramic was 15/85.
(The same as the preparation amount and the finished analysis amount).

As the ceramic dielectric material, titanium-
Barium-neodymium ceramics (average particle size 1
20 μm: firing temperature 1350 ° C.).

This composite dielectric material composition was heated at 220 ° C. and 300 kg / cm ² using a hot press molding machine (manufactured by Kamishima Kikai Co., Ltd.).
After hot press forming with 1mm x 1mm x 10
A 0 mm sample was obtained. The relative permittivity ε and the dielectric loss tangent (tan δ) at 1 GHz, 2 GHz, and 5 GHz of the sample were measured by a perturbation method, and the Q value was determined. Also,
Solder heat resistance was examined as follows.

Solder heat resistance: The test piece was immersed in solder heated to 200 ° C. and 230 ° C. for 2 minutes, and the degree of deformation was observed.

As a result, the dielectric constant was 10.4 and 2 at 1 GHz.
10.6 at GHz, 11.4 at 5 GHz, dielectric loss tangent: 1 GHz
2.10 × 10 ^-3 at 2.0 GHz and 2.07 × 10 ^-3 at 5 GHz
Hz: 2.03 × 10 ⁻³ , solder heat resistance: 200 ° C .: no deformation, 230 ° C .: no deformation.

<Example> The composite dielectric material composition was processed into a sheet-like film having a size of 150 mm in length, 100 mm in width and 100 mm in thickness. Using this composite dielectric material composition, a copper film having a thickness of 18 μm is attached as a conductor layer, patterned into a predetermined shape, laminated, and cut to form a filter as shown in FIG. did. Further, the outer shape of the obtained filter is 3.2 to 2.5 m in length.
m, width: 3.2 to 4.5 mm, height: 1.5 to 2 mm. An electrode as shown in FIG. 2 was formed on this filter body by an electroless Cu plating method, and an electrode was further formed by an electrolytic Cu plating method to obtain a filter element.

The pass characteristics and the reflection characteristics at 1 to 3 GHz of the obtained filter element were measured. FIG. 4 shows the results. In addition, the value of each measurement point in the passage characteristic is as follows. 1: frequency = 1.894 GHz, pass characteristic = −
0.7847 dB, 2: frequency = 1.92 GHz, pass characteristic = −0.81747 dB, 3: frequency = 1.68 GHz, pass characteristic = −9.2876 dB, 4: frequency = 1.415 G
Hz, pass characteristic = -43.354 dB, 5: frequency = 2.1
4 GHz, pass characteristic = -19.316 dB. As is clear from FIG. 4, the filter element of the present invention has almost the same performance as a filter element using a conventional ceramic.

In the above Examples, when the above-mentioned other resin was used in place of the resin of the above-mentioned Synthesis Example in place of the resin of the composite dielectric material composition used, almost the same results were obtained. In addition, better results were obtained by using a graft polymer-based resin than a fumarate-based resin. Further, the same was true even when the high frequency ceramic dielectric material was similarly replaced with the above-mentioned other example ceramics.

[0153]

As described above, according to the present invention, no misalignment occurs between layers at the time of lamination, the number of times of printing is reduced, and the shape and thickness of the pattern inside the substrate are prevented without shrinkage during firing or the like. , Spacing, the position of the internal pattern of the individual product after division, etc. can be prevented from occurring, without burr, etc., the division efficiency at the time of manufacture is good, the product yield, cost is excellent, and the performance is ceramic. A normal high-frequency multilayer laminated component can be realized.

[Brief description of the drawings]

FIG. 1 is an exploded perspective view of a filter showing a specific example of a high-frequency multilayer component of the present invention.

FIG. 2 is an assembly view of FIG.

FIG. 3 is an equivalent circuit diagram of the filters of FIGS. 1 and 2;

FIG. 4 is a graph showing pass characteristics and reflection characteristics at 1 to 3 GHz of filters having the structures shown in FIGS. 1 and 2 manufactured in the example.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Filter 11 Input terminal 12 Earth terminal 101-118 Dielectric layer 201-218 Conductive layer

Claims (10)

[Claims] 1. A high-frequency multilayer laminated component having a multilayer structure, which is obtained by forming a chip from a large-area laminate and has a dielectric layer and a conductive layer, wherein the dielectric layer has a weight average absolute molecular weight. A resin composition comprising one or more of 1,000 or more resins, wherein the total number of carbon atoms and hydrogen atoms in the composition is 9
A composite dielectric material composition comprising a heat-resistant low-dielectric polymer material having 9% or more and having some or all of the resin molecules chemically bonded to each other, and a ceramic dielectric material; Have high frequency multilayer parts. 2. The high-frequency multilayer component according to claim 1, wherein the heat-resistant low-dielectric polymer material has at least one chemical bond selected from cross-linking, block polymerization and graft polymerization. 3. The heat-resistant low-dielectric polymer material according to claim 1, wherein the non-polar α-olefin polymer segment and / or the non-polar conjugated diene polymer segment and the vinyl aromatic polymer segment form a chemical bond. 3. A thermoplastic resin having a multi-phase structure in which a dispersed phase formed by one segment is finely dispersed in a continuous phase formed by the other segment.
High frequency multilayer parts. 4. The high-frequency high frequency material according to claim 3, wherein the heat-resistant low-dielectric polymer material is a copolymer in which a nonpolar α-olefin polymer segment and a vinyl aromatic polymer segment are chemically bonded. Multi-layer laminated parts. 5. The high-frequency multilayer according to claim 3, wherein the heat-resistant low-dielectric polymer material has a vinyl aromatic polymer segment that is a vinyl aromatic copolymer segment containing a divinylbenzene monomer. Laminated parts. 6. The heat-resistant low-dielectric polymer material is characterized in that a non-polar α-olefin polymer segment and / or a non-polar conjugated diene polymer segment and a vinyl aromatic polymer segment form a chemical bond. The high-frequency multilayer laminate component according to claim 4 or 5, wherein the copolymer obtained is a copolymer chemically bonded by graft polymerization. 7. The high-frequency wave according to claim 1, wherein the heat-resistant low-dielectric polymer material further contains a non-polar α-olefin polymer containing a monomer of 4-methylpentene-1. Multi-layer laminated parts. 8. A high-frequency multilayer laminate component having a multilayer structure, which is obtained by forming a chip from a large-area laminate and has a dielectric layer and a conductor layer, wherein the dielectric layer is a monomer. A high-frequency multilayer component formed by a composite dielectric material composition containing a dielectric polymer material obtained by polymerizing a monomer composition containing at least a fumaric acid diester and a ceramic dielectric material. 9. The high-frequency multilayer component according to claim 1, wherein the fumaric acid diester is represented by the following formula (I). Embedded image [In the formula (I), R ¹ represents an alkyl group or a cycloalkyl group, R ² represents an alkyl group, a cycloalkyl group or an aryl group, and R ¹ and R ² may be the same or different. ] 10. The multilayer high-frequency component according to claim 1, wherein the monomer composition further contains a vinyl monomer represented by the following formula (II). Embedded image [In the formula (II), X represents a hydrogen atom or a methyl group, and Y represents a fluorine atom, a chlorine atom, an alkyl group, an alkenyl group, an aryl group, an ether group, an acyl group, or an ester group. ]