JPH05415B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) This invention relates to a highly dielectric thermosetting composition that can be shaped. More specifically, the present invention relates to a highly dielectric thermosetting resin composition that can be shaped by molding and is useful for manufacturing dielectrics for various capacitors used in electrical and electronic equipment. (Prior Art) Various types of capacitors, such as film capacitors, electrolytic capacitors, and ceramic capacitors, have been widely used in electrical and electronic equipment such as electronic computers and communication devices. Particularly in recent years, ceramic capacitors have been increasingly used as chip capacitors whose usage has increased significantly. (Problems to be Solved by the Invention) However, conventional ceramic capacitors or ceramic capacitor blocks cannot sufficiently meet the recent demands for miniaturization, high density, and high precision miniaturization of electrical and electronic devices. is the current situation. For example, as the density of wiring increases, it is becoming essential for capacitors used in wiring boards to be thinner and smaller. However, since conventional ceramic capacitors are easily broken, it is not possible to sufficiently reduce the thickness and size of the product. Furthermore, since ceramic capacitors are formed by sintering, the dimensions of conventional capacitors change during sintering, making it impossible to fully meet the demand for higher precision wiring. . For this reason, there is a strong desire to develop a new dielectric material for capacitors that has the required dielectric constant and can also make the product thinner and more compact with good dimensional accuracy, and to create products using it. was. This invention was made in order to solve the conventional problems as described above, and it is possible to obtain various dielectric products including multilayer ceramic capacitors having a required dielectric constant.
Moreover, it is an object of the present invention to provide a shapeable composition that can be easily formed into small and thin layers with high density and high precision. (Means for Solving the Problems) In order to achieve the above object, the present invention provides polyphenylene oxide and a crosslinkable polymer and/or monomer in a weight ratio of 9/1 to 1/9.
A highly dielectric thermosetting material that can be shaped and is characterized by being blended with 60 to 90% by volume of inorganic powder with a relative dielectric constant of 10 or more and an average particle size of 1 to 6 μm. A composition is provided. Polyphenylene oxide, which is one of the thermosetting resins used in the composition of this invention, is a thermosetting resin with a relatively high glass transition point, low dielectric constant, and low dielectric loss, and is also inexpensive. This is something that has been attracting attention in recent years. However, until now, it has not been possible to control the dielectric constant to a desired value from a low dielectric constant to a high dielectric constant, and to improve the formability so that it can be molded into a desired shape. However, in this invention, the polyphenylene oxide resin composition has a high dielectric constant by adding 60 to 90% by weight of inorganic powder with a dielectric constant of 10 or more and an average particle size of 1 to 6 μm. , and can be made into a shapeable composition. In addition, when incorporating inorganic dielectric powder into polyphenylene oxide, if a crosslinkable polymer and/or monomer is included, the resin will have excellent heat resistance, chemical resistance, processability, and dimensional stability. I also discovered that. Examples of polyphenylene oxides that can be used in the formable composition of the present invention include 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.), and an example thereof is poly(2,6- dimethyl-1,4-phenylene oxide). Although the molecular weight is not particularly limited, it is preferable, for example, that the weight average molecular weight (Mw) is 50,000 and the molecular weight distribution Mw/Mn=4.2 (Mn is the number average molecular weight). Examples of crosslinkable polymers include 1,2-
Examples include polybutadiene, 1,4-polybutadiene, styrene-butadiene copolymer, modified 1,2-polybutadiene (malein-modified, acrylic-modified, epoxy-modified), rubbers, etc., and each can be used alone or in combination of two or more. .
These polymers may be in the form of elastomers or rubbers. In addition, examples of crosslinking monomers include, for example,
Acrylates such as ester acrylates, epoxy acrylates, urethane acrylates, ether acrylates, melamine acrylates, alkyd acrylates, silicone acrylates, triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, divinylbenzene, Examples include polyfunctional monomers such as diallyl phthalate, monofunctional monomers such as vinyltoluene, ethylvinylbenzene, styrene, and paramethylstyrene, and polyfunctional epoxies, and each can be used alone or in combination of two or more. Among these, triallyl cyanurate and/or triallyl isocyanurate are preferably compatible with polyphenylene oxide and improve film-forming properties, crosslinking properties, heat resistance, and dielectric properties. Triallyl cyanurate and triallyl isocyanurate are chemically structurally isomers and have almost the same film-forming properties, compatibility, solubility, reactivity, etc. Both can be used equally. The above crosslinkable polymers and crosslinkable monomers may be used alone or in combination, but their combined use is more effective in improving properties. The crosslinkable polymer and/or monomer as described above to be mixed with the polyphenylene oxide is 10 to 90 parts by weight of the polyphenylene oxide and 10 to 90 parts by weight of the crosslinkable polymer and/or monomer, that is, the weight ratio thereof. As 9/1~1/
Blend in a ratio of 9. Inorganic powders with a dielectric constant of 10 or more used in this invention include, for example, aluminum oxide ceramics, titanium dioxide ceramics, barium titanate ceramics, lead titanate ceramics, calcium titanate ceramics, and magnesium titanate ceramics. An inorganic powder containing at least one of ceramic, bismuth titanate ceramic, strontium titanate ceramic, and lead zirconate ceramic, or a powder obtained by sintering and pulverizing two or more of these can be used. These inorganic powders have an average particle size of 1 to 6μ
m is used, and more preferably, the maximum particle size distribution is in the range of 1 to 5.5 μm.
Use a 6μm one. This inorganic powder with an average particle size of 1 to 6 μm and a relative dielectric constant of 10 or more is
It is blended in an amount of 60 to 90% by volume based on the total composition. If the average particle diameter is less than 1 μm or more than 6 μm, the shapeability is not good and it is not possible to improve heat resistance, dimensional stability, etc. The same applies when the amount is less than 60% by volume or more than 90% by volume.
High dielectric performance and chemical resistance will also be impaired. Note that the above-mentioned inorganic powder is preferably obtained by pulverizing after sintering. When the above-mentioned crosslinkable polymer and/or monomer and inorganic powder are incorporated into a composition of a highly dielectric thermosetting resin such as polyphenylene oxide, an initiator can be further used. As the initiator, ultraviolet curing type or thermosetting type can be used alone or in combination, but the initiator is not limited thereto. It goes without saying that the shapeable highly dielectric thermosetting composition of the present invention can contain, in addition to the above-mentioned initiator, various additives as long as they do not impair its properties. For example, brominated polyphenylene oxide, brominated bisphenol type polycarbonate, etc. can be contained as a flame retardant. The shapeable resin composition of the present invention as described above is usually dissolved and dispersed in a solvent and mixed. Solvents include halogenated hydrocarbons such as trichloroethylene, trichloroethane, trichloroform, methylene chloride, and chlorobenzene, benzene,
Aromatic hydrocarbons such as toluene and xylene, acetone, carbon tetrachloride, etc. can be used, and trichloroethylene is particularly preferred. These can be used alone or in combination of two or more. The composition of this invention can be easily shaped by heat molding, and can be made into various shapes. The temperature during heat forming is, for example, 160 to 300℃.
It is preferable to keep it within a range of about The molding pressure can be, for example, about 30 to 70 kg/cm ² . (Function) The shapeable highly dielectric thermosetting composition of the present invention has a desired high dielectric constant while maintaining the excellent heat resistance, dimensional stability, and chemical resistance of polyphenylene oxide and the like. and exhibits excellent formability. Therefore, a molded article using the composition of the present invention has the characteristics of high precision, easy miniaturization, excellent dimensional stability, and resistance to cracking. Next, Examples will be shown to further explain the composition of the present invention. Example 1 Add polyphenylene oxide to the universal mixer of 2.
50g, styrene-butadiene polymer (Asahi Kasei Corporation: Solprene T406), 100g triallyl isocyanurate (Nippon Kasei Corporation: TAIC), 10g dicumyl peroxide, and trichlorethylene (Toagosei Chemical Industry Co., Ltd.: Triclean) 750
g and stirred thoroughly until a homogeneous solution was obtained.
Thereafter, 2,600 g of aluminum oxide powder having an average particle size of 1 to 2 μm was added and further stirred to uniformly disperse the mixture. This was then defoamed to obtain a polyphenylene oxide resin composition solution. Dry this at 100℃ for about 30 minutes using a dryer.
Trichlorethylene was completely removed to obtain a powder consisting of a polyphenylene oxide composition. Put this powder into a mold, 190℃, 50Kg/cm ²
The plate was completely cured by applying pressure for 30 minutes under the following conditions to produce a plate-shaped body. A molded article with excellent dielectric properties, solvent resistance, and alkali resistance was obtained. Examples 2 to 7 The formulations of polyphenylene oxide resin compositions were as shown in Table 1, six types of resin compositions were prepared in the same manner, and plate-shaped bodies were produced. A molded article with excellent dielectric properties, solvent resistance, and alkali resistance was obtained. Comparative Examples 1 to 2 A polyphenylene oxide resin composition was prepared without containing powder, and the composition was as shown in Table 1, and the resin composition was used to form a plate-like body. Molded. The characteristics were not good. As shown in Table 1, each PPO of Examples 1 to 7
The plate-shaped body made of the resin composition has a low dielectric loss, a high relative dielectric constant, and is excellent in heat resistance and dimensional stability. When the inorganic powders are the same, the relative dielectric constant increases as the blending ratio increases. Titanium dioxide is more effective in increasing the dielectric constant than aluminum oxide. In this way, by changing the type and amount of the inorganic powder, it is possible to give the PPO resin composition a wide range of dielectric constants. Note that both Examples 4 and 5 were mixtures of two types of inorganic powders.

【table】

[Table] Example 8 Add 100 g of PPO to the multipurpose mixer of 2, and add styrene-butadiene copolymer (Asahi Kasei Corporation: Solprene).
T406) 30g, triallyl isocyanurate (Nippon Kasei Co., Ltd.: TAIC) 70g, 2,5-dimethyl-
Add 2 g of 2,5-di-(tert-butylperoxy)hexyne-3 (Nippon Oil & Fats Co., Ltd.: Perhexine 25B) and further add 750 g of trichlorethylene (Toagosei Chemical Co., Ltd.: Trichlene) to form a homogeneous solution. Stir thoroughly until . After this, the average particle size is 1~
1,800 g of 2 μm barium titanate (BaTiO ₃ ) ceramic powder was added and stirred in a ball mill for about 24 hours to uniformly disperse the mixture. Thereafter, defoaming was performed, and the obtained PPO-based resin composition solution was dried using a dryer at 100° C. for 30 minutes to completely remove trichlorethylene to obtain a powder made of a PPO-based resin composition. Put this powder into a mold and heat it at 200℃, 50℃.
It was pressurized for 30 minutes under the conditions of Kg/cm ² to completely cure, and a plate-shaped body was produced. Examples 9 to 27, Comparative Example 3 Molded plates were produced in the same manner as in Example 8, except that the formulations and amounts of trichlorethylene were as shown in Table 2. Each of the inorganic powders in Examples 12, 13, and 14 was a mixture of two or more types of ceramics. As shown in Table 2, each PPO of Examples 8 to 27
The molded plate using the resin composition can have a specific dielectric constant that can be changed depending on the amount of inorganic powder added, and
It has excellent solvent resistance (trichlorethylene resistance) and low dielectric loss. Moreover, each of the inorganic fillers of Examples 1 to 27 was obtained by firing under the conditions shown in Table 3. The average particle size, particle size distribution, and type of each inorganic filler are also shown in Table 3.

【table】

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[Table] Examples 28 to 32 Molded plates were produced in the same manner as in Example 8 using the formulations shown in Table 4. It was confirmed that the excipient composition had similarly excellent performance. Comparative Examples 4 to 6 are also shown in Table 4.

[Table] (Effects of the Invention) The shapeable highly dielectric thermosetting composition of the present invention has excellent heat resistance, dimensional stability, and chemical resistance by containing an inorganic dielectric powder.
A resin composition having a desired dielectric constant and exhibiting excellent shapeability can be obtained.

[Brief explanation of the drawing]

FIG. 1 and FIG. 2 are a perspective view and a circuit layout diagram showing a method for measuring relative dielectric constant and dielectric loss.

Claims (1)

[Claims] 1. Polyphenylene oxide and crosslinkable polymer and/or monomer in a weight ratio of 9/1 to 9/1.
60 to 90% by volume of inorganic powder with a ratio of 1/9 and a relative dielectric constant of 10 or more and an average particle size of 1 to 6 μm.
A highly dielectric thermosetting composition that can be shaped and is characterized by being formulated with: 2. The curable composition according to claim 1, wherein the crosslinkable polymer is one or more selected from the group consisting of styrene-butadiene copolymer, 1,2-polybutadiene, 1,4-polybutadiene, and modified polybutadiene. 3. The curable composition according to claim 1, wherein the crosslinking monomer is triallyl isocyanurate or triallyl cyanurate. 4 The inorganic powder with a dielectric constant of 10 or more is aluminum oxide ceramic, titanium dioxide ceramic,
Inorganic powder containing at least one of barium titanate ceramic, lead titanate ceramic, calcium titanate ceramic, magnesium titanate ceramic, bismuth titanate ceramic, strontium titanate ceramic, and lead zirconate ceramic and/or the curable composition according to claim 1, which is a powder obtained by sintering and/or pulverizing at least two or more of these.