JPH0811781B2 - Shaped high dielectric polyphenylene oxide resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a shaped and highly dielectric polyphenylene oxide resin composition.

More specifically, the present invention relates to a shaped and highly dielectric polyphenylene oxide resin composition having excellent dielectric properties and shapeability.

(Prior Art) Various dielectric products such as band pass filters, low pass filters, bypass filters, etc. are used for wiring boards for electrical equipment such as precision equipment, electronic calculators, communication equipment, and electronic equipment. There is.

Further, as such a dielectric product, a ceramic capacitor or a ceramic capacitor block has been frequently used.

(Problems to be Solved by the Invention) However, in the conventional ceramic capacitors or ceramic capacitor blocks, etc., the multilayered printed wiring boards, the high precision and the fineness have been achieved in response to the recent demand for miniaturization and high density of electric devices and electronic devices. The reality is that we cannot fully meet the demands for commercialization.

For example, with the progress of higher density wiring, it is indispensable to reduce the thickness and size of dielectric products used for wiring boards. However, the conventional ceramic-based capacitor is easily broken, so that it is not possible to sufficiently reduce the film thickness and size of the product.

Further, since the ceramic type capacitor is formed by firing, and the dimension of the product is changed during firing, it is not possible to sufficiently meet the demand for high precision wiring.

Therefore, it has been strongly desired to develop a new dielectric material that has excellent dielectric properties and can realize thinning and miniaturization of the product with high accuracy, and to realize a product using the same. .

The present invention has been made in order to solve the conventional problems as described above, has excellent dielectric properties, and can be shaped into a resin composition such as high density miniaturization, small size and thin layer formation. The purpose is to provide things.

(Means for Solving the Problems) In order to achieve the above object, the present invention comprises a crosslinkable polymer and / or monomer together with polyphenylene oxide, and a ceramic dielectric powder, wherein the ceramic dielectric powder is titanium. Acid ceramics, zirconate metal ceramics and lead complex oxide ceramics, one or more selected from the group consisting of 1.0μ
The particle size distribution of m to 2.5 μm occupies 60% by weight or more, and
2000-100 for 100 parts by weight of polyphenylene oxide
Provided is a shaped high-dielectric polyphenylene oxide-based resin composition, which is blended in a proportion of 00 parts by weight.

The polyphenylene oxide used in the shaped high-dielectric polyphenylene oxide resin composition of the present invention is a thermosetting resin having a relatively high glass transition point, a low dielectric constant, and a low dielectric loss, and has recently attracted attention because it is inexpensive. It has been done. However, until now, it was not possible to improve its shapeability so that its dielectric characteristics were excellent and it could be easily and surely molded into a desired shape, so dielectrics used for high-density multilayer wiring, etc. It has not been put to practical use as a resin for body.

For example, the inventor of the present invention improves the dimensional stability and the solvent resistance by blending an inorganic filler such as alumina, silica, titania, and glass in order to use the polyphenylene oxide resin as a wiring board material. A composition capable of adjusting the dielectric constant has already been proposed (Japanese Patent Laid-Open No. 61-2217).
No. 58) has not found a composition which realizes more excellent dielectric properties and can be easily and surely shaped into a product shape such as a multilayer board.

However, in the present invention, by adding a specific ceramic dielectric powder to a polyphenylene oxide resin composition under limited conditions, it is possible to shape while controlling the dielectric constant to a desired value. By using a resin composition, a resin composition that has a good shapeability and enables a product having excellent dielectric properties is realized. of course,
This composition also makes the resin molded article excellent in heat resistance, chemical resistance, processability, and dimensional stability.

In the shaped high dielectric polyphenylene oxide resin composition of the present invention, polyphenylene oxide contains a crosslinkable polymer and / or a crosslinkable monomer and a ceramic dielectric powder, and the polyphenylene oxide used in the present invention is For example, the following general formula (1) (R represents hydrogen or a hydrocarbon group having 1 to 3 carbon atoms, and each R may be the same or different.). For example, as an example thereof, poly (2,6-dimethyl-1,4-phenylene oxide), poly (2,5-dimethyl-1,4-phenylene oxide), poly (2-methyl-1,4-phenylene oxide) ), Poly (2,6-diethyl-1,4-phenylene oxide), and the like.

The molecular weight is not particularly limited, but for example, the weight average molecular weight (Mw) is 50,000, the molecular weight distribution Mw / Mn
= 4.2 (Mn is number average molecular weight).

Examples of the crosslinkable polymer include 1,2-polybutadiene, 1,4-polybutadiene, styrene-butadiene copolymer, modified 1,2-polybutadiene (malein-modified,
Acrylic modification, epoxy modification), rubbers and the like can be used, and each can be used alone or in combination of two or more. The state of these polymers may be elastomer or rubber.

However, when a sheet molded product is produced by the casting method described below using the composition of the present invention, it is preferable to use polystyrene having a relatively high molecular weight from the viewpoint of improving the film-forming property of the sheet.

Examples of the crosslinkable monomer include acrylates such as ester acrylates, epoxy acrylates, urethane acrylates, ether acrylates, melamine acrylates, alkyd acrylates, and silicon acrylates, triallyl cyanurate, and triallyl isocyanate. Examples include polyfunctional monomers such as nurate, ethylene glycol dimethacrylate, divinylbenzene and diallyl phthalate, monofunctional monomers such as vinyltoluene, ethylvinylbenzene, styrene and paramethylstyrene, and polyfunctional epoxies, each of which may be used alone or Two or more can be used together. Of these, triallyl cyanurate and / or triallyl isocyanurate are preferable because they have good compatibility with polyphenylene oxide and improve film formability, crosslinkability, heat resistance and dielectric properties.

This triallyl cyanurate and triallyl isocyanurate have an isomer relationship in terms of chemical structure and have almost the same film-forming property, compatibility, solubility, reactivity, etc., so either one or Both can be used as well.

Either one of the above-mentioned crosslinkable polymer and crosslinkable monomer may be used, or both may be used in combination, but the combined use is more effective in improving the characteristics.

As the ceramic dielectric powder used in the present invention,
The relative dielectric constant is preferably 20 or more, and more preferably 100 to 100.
At least one selected from the group consisting of metal titanate-based ceramics, metal zirconate-based ceramics, and lead complex oxide-based ceramics having a frequency of about 00 (MHz) is appropriately used according to the dielectric properties given to the product. Examples of such ceramic dielectric powder include barium titanate-based ceramics, lead titanate-based ceramics, calcium titanate-based ceramics, magnesium titanate-based ceramics, bismuth titanate-based ceramics, strontium titanate-based ceramics, and zirconic acid. lead-based ceramics, barium zirconate-based _{ceramic, K 2 O-PbO-SiO} 2 based ceramic, Ba
Powders of _0.5 Pb _0.5 Nd ₂ Ti ₅ O ₁₄ series ceramics or the like, or mixed powders of two or more of these can be used.

When the above-mentioned crosslinkable polymer and / or monomer and ceramic dielectric powder are contained in polyphenylene oxide, an initiator can be further used.

As the initiator, an appropriate one can be selected depending on whether the polyphenylene oxide resin composition is an ultraviolet curing type or a thermosetting type.

Further, the initiator by ultraviolet rays and the initiator by heat may be used together.

In addition, in the shaped high dielectric polyphenylene oxide resin composition of the present invention, in addition to the above-mentioned initiator,
Needless to say, various additives can be contained as long as their properties are not impaired. For example, brominated polyphenylene oxide, brominated bisphenol type polycarbonate or the like can be contained as a flame retardant.

The ceramic dielectric powder contained in the shaped high-dielectric polyphenylene oxide resin composition imparts excellent dielectric properties to the product and, in order to improve the shapeability of the product, has the above-mentioned specificity. In addition to using the seed ceramic powder, its particle size and blending amount must be within a specific range.

First, regarding the particle size, the ceramic dielectric powder of the present invention has a particle size distribution of 1.0 μm to 2.5 μm as a whole amount.
It shall account for 60% by weight or more. In the case of less than this, it is difficult to obtain the desired shapeability, and by extension,
It also makes it difficult to obtain desired dielectric properties and solvent resistance.

Also, regarding the blending amount, polyphenylene oxide
It is blended in a ratio of 2000 to 10000 parts by weight to 100 parts by weight. When it is less than 2000, the dielectric properties are not sufficient, and when it exceeds 10,000, the shapeability is deteriorated.

Regarding the compounding ratio of the crosslinkable polymer and / or monomer, polyphenylene oxide 10 is usually used.
˜95 parts by weight, crosslinkable polymer / monomer 5 to 90 parts by weight are preferred.

The blending ratio of the initiator to be contained in addition to such blending is 0.1 to 5 parts by weight (more preferably 0.1 to 3 parts by weight).
Is preferred. This is because if the proportion of the initiator is less than the above range, the polyphenylene oxide resin composition may be insufficiently cured, and if it exceeds the above range, the physical properties after curing may be adversely affected.

The shaped high dielectric polyphenylene oxide resin composition of the present invention is usually dissolved in a solvent, dispersed, and mixed. As the solvent, halogenated hydrocarbons such as trichloroethylene, trichloroethane, chloroform, methylene chloride and chlorobenzene, aromatic hydrocarbons such as benzene, toluene and xylene, acetone and carbon tetrachloride can be used, and trichloroethylene is particularly preferable. These may be used alone or in combination of two or more.

Such shaped high-dielectric polyphenylene oxide resin composition can be shaped into various desired shapes such as a sheet by heat-molding. Further, it can also be molded into a laminate, in which case a sheet-like substrate is previously formed from the resin composition, or a resin composition is impregnated into a substrate such as glass mat or paper to form a prepreg, and If necessary, a core material or the like can be produced from these sheets and prepregs, and then laminated in a multilayer manner with other base materials, films, prepregs, metal foils and the like according to a conventional method.

For example, the above-mentioned casting method is a method in which a resin mixed with a solvent is cast or applied to form a thin layer and then the solvent is removed to obtain a cured sheet. According to this casting method, a cured product can be obtained at a low temperature without using a costly calendar method. This casting method will be described more specifically. On a mirror-finished iron plate or carrier film for casting of the shaped high dielectric polyphenylene oxide resin composition of the present invention mixed in a solvent, for example, 5 to A sheet substrate is obtained by casting (or coating) to a thickness of 700 (preferably 5 to 500) μm and sufficiently drying to remove the solvent.

The casting carrier film is not particularly limited, but a polyethylene terephthalate (hereinafter abbreviated as "PET") film, a polyethylene film, a polypropylene film, a polyester film, a polyimide film, or the like which is insoluble in the solvent is preferable, and Those subjected to release treatment are preferable.

Drying is performed by air drying or hot air drying. The temperature range in that case is lower than the boiling point of the upper limit of the solvent, or,
It is preferable that the temperature is lower than the heat resistant temperature of the casting carrier film (when drying is performed on the casting carrier film).

The lower limit should be determined by the drying time and processability. For example, trichlorethylene as a solvent and PET
When the film is used as a carrier film for casting, it is preferably in the range of room temperature to 80 ° C. If the temperature is raised within this range, the drying time can be shortened.

When a prepreg is manufactured by impregnating a base material with the shaped high dielectric polyphenylene oxide resin composition of the present invention, the following method can be generally adopted.

That is, the shaped high dielectric polyphenylene oxide resin composition is dispersed in a solvent, and a substrate such as a glass mat is dipped in the solvent dispersion (dipping),
The base material is impregnated with the shapeable polyphenylene oxide resin composition and attached. Then, the solvent is removed by drying or the like or semi-cured to obtain the B stage. The impregnated amount of the shaped high-dielectric polyphenylene oxide resin composition in this case is not particularly limited, but is preferably 30 to 80% by weight. The base material is, in addition to the above glass cloth,
It is possible to use resin-impregnated cloth-like materials such as aramid cloth, polyester cloth, nylon cloth, mat-like materials made of these materials and / or fibrous materials such as non-woven fabric, paper such as kraft paper and linter paper, Moreover, it is not limited to these. When the prepreg is manufactured in this manner, the resin does not have to be melted, and therefore it can be easily performed at a relatively low temperature.

When the metal-clad laminate is formed by using the above-mentioned sheet or substrate, as the metal foil for forming a circuit, those used for a normal wiring board can be widely used. For example,
A metal foil such as a copper foil or an aluminum foil can be used. In this case, a metal foil having a smooth adhesive surface and good conductivity is preferable for improving the dielectric property.

Such a metal foil can be formed by vapor deposition or the like, but may also be formed as a desired conductor (circuit, electrode, etc.) by a subtractive method, an additive method (full-additive method, semi-additive method) or the like. Good.

In the case of producing a laminated sheet using a core material, a sheet and a prepreg produced from the shaped high dielectric polyphenylene oxide resin composition of the present invention, the above-mentioned sheet and / or prepreg which has been appropriately dried is designed to have a predetermined design. Combine predetermined sheets so as to have a thickness, and also combine and combine metal foils if necessary, melt the resin by heating and pressing, etc., sheets, sheets and prepregs or core materials, prepregs, sheets and metal The foil, the prepreg and the metal foil are adhered to each other to form a laminate. By this fusion, strong adhesion can be obtained, but if heating at this time is caused to cause a crosslinking reaction by a radical initiator, even stronger adhesion can be obtained. Such a crosslinking reaction is carried out by photocrosslinking such as ultraviolet irradiation, thermal crosslinking, crosslinking by irradiation of radiation, or the like. Note that such adhesion may be performed by using an adhesive together. Here, there is a combination when a sheet, a prepreg, and a core material are used together, but there is no particular limitation, but a vertically symmetrical combination is preferable from the viewpoint of warpage prevention after molding and after secondary processing (etching etc.). . Further, it is preferable to combine them so that the sheet comes to the adhesive interface with the metal foil, because the adhesive force can be improved.

The temperature at the time of heat pressing depends on the combination of the metal foil and the sheet or the prepreg, but for example, the adhesion between the metal foil and the sheet can utilize the heat fusion property of the sheet, so the laminating pressing temperature is the glass of the sheet. Above the transition point, about 16
It is preferably in the range of 0 to 300 ° C.

Also, when crosslinking is carried out by placing it in a dryer and heating it, the crosslinking reaction depends on the reaction temperature of the initiator used, etc., so the heating temperature and heating time are selected according to the type of initiator. For example, the temperature is 150 to 300 ° C. and the time is 10 to 60 minutes.

Clamping is performed to bond sheet substrates to each other, sheet to prepreg, prepreg to each other, metal foil to sheet, metal foil to prepreg, etc., and to adjust the thickness of the laminate. To do.

For example, the pressure can be about 20 to 70 kg / cm ² .

The heating and pressing as described above is carried out by heating and laminating a predetermined number of the film and / or prepreg in advance, and laminating a metal foil on one side or both sides thereof,
The heating and pressing may be performed again.

(Operation) The resin composition of the present invention imparts excellent dielectric properties to molded products while maintaining the excellent heat resistance, dimensional stability and chemical resistance of the polyphenylene oxide resin composition, and is excellent. Demonstrates its shapeability. For example, according to the present invention, in a molded product such as a sheet or a prepreg, the relative dielectric constant is 30 or more, particularly 60 or more, and the dielectric loss is 0.010 (M
Hz, 23 ° C) or higher.

 Further, the shapeability is also extremely good.

Therefore, the substrate of the present invention can be manufactured in a high-precision small-sized thin layer form, and can realize high-density miniaturized wiring.

(Example) Next, an example is shown and this invention is further demonstrated.

Example 1 As shown in Table 1, 100 g of polyphenylene oxide, 30 g of styrene-butadiene copolymer (Asahi Kasei Kogyo Co., Ltd .: Sorprene T406), 70 g of triallyl isocyanurate (Nippon Kasei Co., Ltd .: TAIC) were placed in a reactor equipped with a decompressor 2 as shown in Table 1. , Dicumyl peroxide 3g, and further added trichlorethylene (Toagosei Kagaku Kogyo Co., Ltd .: trichlene) 2500g,
Stir well until a homogeneous solution is obtained. Then, as a ceramic dielectric powder, a BaTiO ₃ -based ceramic powder 220 of 68% by weight (average particle size 1.9 μm) having a particle size distribution of 1.0 to 2.5 μm
0 g was added, and the mixture was further stirred and uniformly dispersed. Then, this was defoamed to obtain a shaped high dielectric polyphenylene oxide resin composition solution.

Next, the obtained polyphenylene oxide-based resin composition solution was applied onto a PET film using a coating machine so as to have a thickness of 500 μm.

After drying this at 50 ° C for about 10 minutes, the resulting film is PET.
The film was released from the film, and further dried at 170 ° C. for 20 minutes to completely remove trichlorethylene, thereby obtaining a sheet made of the shapeable polyphenylene oxide resin composition. The thickness of this sheet was about 150 μm.

Four sheets were superposed on each other, and were pressed completely under the conditions of 220 ° C. and 50 kg / cm ² for 30 minutes to completely cure them to prepare a laminated plate in which the four sheets were laminated and integrated.

Examples 2 to 17 16 types of resin laminated plates were prepared in the same manner as in Example 1 by using the composition of the shapeable polyphenylene oxide resin composition as shown in Table 1 and using a ball mill for stirring if necessary.

Comparative Examples 1 to 8 Eight kinds of resin laminated plates were produced in the same manner as in Example 1 with the formulations shown in Table 1.

Comparative Examples 9 to 10 Resin laminates were produced in the same manner as in Example 1 except that the ceramic dielectric powder was not contained and the composition of Table 1 was used.

Therefore, the physical properties of the laminates obtained in the above Examples 1 to 17 and Comparative Examples 1 to 10, relative dielectric constant, dielectric loss, solvent resistance,
The shapeability and the like were investigated. The results are also shown in Table 1. The relative permittivity and the dielectric loss were measured by the methods shown in FIGS. 1 and 2. (A) shows a board | substrate, (b) has shown the conductor metal.

Table 2 shows the particle size and firing conditions of the various ceramic dielectric powders used in Examples 1 to 17 and Comparative Examples 1 to 8.

Example 18 A glass cloth was impregnated with the shapeable polyphenylene oxide resin composition obtained in Example 1, and the glass cloth was impregnated with the glass cloth at about 10 ° C. for about 10 minutes.
Min., Dried at 130 ° C. for about 20 minutes to remove trichlorethylene to prepare a prepreg.

4 pieces of the obtained prepregs are piled up, and then an electrolytic copper foil with a thickness of 18μm is piled up on both sides, and 200 ℃, 50kg / cm ² , 3
A metal-clad laminate was produced by pressing for 0 minutes to form an integrated laminate.

The obtained metal-clad laminate had good dielectric properties and excellent shapeability.

* 1: Styrene-butadiene copolymer * 2: Triallyl isocyanurate * 3: A ... Dicumyl peroxide B ... 2,5-Dimethyl-2,5-di- (tert-butylperoxy) hexyne-3 * 4: A … BaTiO ₃ system ceramic B… PbZrO ₃ system ceramic C… PbTiO ₃ system ceramic D… SrTiO ₃ system ceramic E… CaTiO ₃ system ceramic F… MgTiO ₃ system ceramic G… BaZrO ₃ system ceramic H… K ₂ O-PbO-SiO ₂ system glass I… Sintered body of PbTiO ₃ and PbZrO ₃ J… Bi ₄ Ti ₃ O ₁₂ system ceramic K… [TiO ₂ ] 1000g + [BaTiO ₃ ] 200g + [ZrO ₂ ] 10g are mixed and fired, then crushed Powder obtained by mixing L ... [TiO ₂ ] 700 g + [BaTiO ₃ ] 300 g + [SrTiO ₃ ] 300 g after mixing and firing, powder obtained by crushing N ... BaNd ₂ Ti ₅ O ₁₄ system ceramic O ... Ba _0.5 Pb _0.5 Nd ₂ Ti ₅ O ₁₄ series ceramics P ... Aluminum oxide Q ... Titanium dioxide R ... TiO ₂ series ceramics * 5: For solvent resistance, alkali resistance and shapeability,
It is evaluated by the following method and relative evaluation criteria.

-Solvent resistance A sample of 2.5 x 2.5 mm size is immersed in boiled trichlorethylene for 5 minutes and the appearance is observed.

・ Alkali resistance A sample of 2.5 × 2.5 mm size is immersed in a 3% aqueous solution of sodium hydroxide at 40 ° C for 5 minutes, and the appearance is observed.

・ Shapeability Observe the appearance of 300 × 300 mm size laminated plates when they are laminated.

・ Relative evaluation ・ Solvent resistance and alkali resistance A: No change in appearance.

 B. Only the corners dissolve.

 C ・ Dissolves in the whole.

-Regarding shapeability: A-A flat laminated plate with no cracks, cracks or warpage can be obtained.

 B ・ Partially chipped, cracked or warped.

 C ・ The whole is chipped, cracked, or warped.

(Effect of the Invention) By incorporating a crosslinkable polymer and / or monomer and a ceramic dielectric powder into polyphenylene oxide according to the present invention, excellent heat resistance, dimensional stability and chemical resistance, and excellent dielectric properties can be obtained. Further, there is provided a resin composition in which high-density miniaturized wiring, high-precision miniaturization, thin layer formation and the like can be easily performed.

[Brief description of drawings]

1 and 2 are a perspective view and a circuit diagram showing a method for measuring the relative permittivity and the dielectric loss, respectively.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shuji Maeda 1048, Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Works, Ltd. (72) Takahiro Fenceuchi, 1048, Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Works, Ltd. (72) ) Inventor Takayoshi Ozeki 1048, Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Works, Ltd. (56) References JP 62-121758 (JP, A) JP 53-138448 (JP, A) JP 61 -155456 (JP, A)

Claims (5)

[Claims] 1. A polydiphenylene oxide, a crosslinkable polymer and / or a monomer, and a ceramic dielectric powder are contained, and the ceramic dielectric powder is a metal titanate-based ceramic, a metal zirconate-based ceramic and a lead composite oxide. One or more selected from the group of ceramic series, wherein the particle size distribution of 1.0 μm to 2.5 μm occupies 60% by weight or more, and polyphenylene oxide 100
A shaped high-dielectric polyphenylene oxide resin composition, which is blended in a proportion of 2000 to 10000 parts by weight with respect to parts by weight. 2. A ceramic dielectric powder comprising barium titanate ceramics, lead titanate ceramics, calcium titanate ceramics, magnesium titanate ceramics, bismuth titanate ceramics, strontium titanate ceramics, and lead zirconate. A ceramic powder, a barium zirconate ceramic, a K ₂ O-PbO-SiO ₂ ceramic, a Ba _0.5 Pb _0.5 Nd ₂ Ti ₅ O ₁₄ ceramic powder, or a mixed powder of two or more thereof. )
The polyphenylene oxide resin composition described. 3. The polyphenylene oxide resin composition according to claim 1, wherein the crosslinkable polymer is a styrene-butadiene copolymer. 4. The crosslinkable monomer is triallyl isocyanurate or triallyl cyanurate (1).
The polyphenylene oxide resin composition described. 5. 10 to 95 parts by weight of polyphenylene oxide,
And crosslinkable polymers and / or monomers 5-90
The shapeable polyphenylene oxide-based resin composition according to claim 1, which comprises parts by weight.