JPH01246709A - Polyphenylene oxide group resin substrate - Google Patents

Abstract

PURPOSE:To provide improvement in desired attributes by having a specified vehicular polyphenylene oxide group resin composition formed or contained in a basic material to manufacture a substrate. CONSTITUTION:This involves forming a vehicular polyphenylene oxide group resin composition containing a cross-liked polymer, monomer, ceramic dielectric powder and fiber-reinforced material or impregnating said resin composition into a basic material to produce a polyphenylene oxide group resin substrate which provides improvement in thermal resistance, stabilized dimension and chemicalproofness, so that a variety of capacitors and the like can be micronized in the form of high density, miniaturized in high precision relationship and thinly layered.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polyphenylene oxide resin substrate.

More specifically, the present invention relates to a polyphenylene oxide resin substrate that allows dielectric products such as various capacitors used in electrical equipment, electronic equipment, etc. to be manufactured with high precision in small and thin layers.

(Prior art) Various dielectric products ranging from low dielectric constant to high dielectric constant are used as band pass filters, low pass filters, bypass filters, etc. in electrical equipment and electronic equipment such as precision instruments, electronic computers, and communication devices. It is used.

Further, as such dielectric products, ceramic capacitors or ceramic capacitor blocks have been widely used. .

(Problems to be Solved by the Invention) However, conventional ceramic capacitors or ceramic capacitor blocks are not suitable for use with multi-layered wiring boards and high-precision fine-grained wiring boards in response to recent demands for miniaturization and higher density of electrical and electronic equipment. The reality is that it is not possible to fully respond to the demands of globalization. .

For example, as the density of wiring increases, it becomes essential that dielectric products used in wiring boards become thinner and smaller. However, conventional ceramic capacitors are easily broken, so it is necessary to make the product thinner.
It is not possible to make it smaller.

Additionally, ceramic capacitors are formed by firing, and the dimensions of the product change during firing.
It is also not possible to sufficiently meet the demand for higher precision wiring.

For this reason, we are developing and using new dielectric materials that have a desired dielectric constant ranging from low to high dielectric constants, and that can precisely realize thinner and smaller products. There was a strong desire to realize a product that

This invention was made in order to solve the problems of conventional ceramic capacitors as described above, and it provides a dielectric product having a desired dielectric constant ranging from a low dielectric constant to a high dielectric constant, Furthermore, the aim is to provide a moldable resin composition that can be manufactured into a highly precise, small, thin layer form suitable for high-density and fine wiring, and furthermore, the purpose is to provide molded products, sheets, and metal cladding compositions using the resin composition. The purpose is to provide laminates.

(Means for Solving the Problems) In order to achieve the above object, the present invention provides a shapeable polyphenylene oxide resin composition containing a crosslinkable polymer and/or monomer, a ceramic dielectric powder, and a fibrous reinforcing material. To provide a polyphenylene oxanide resin substrate, which is formed by molding or impregnating a substrate with a polyphenylene oxanide resin substrate.

The polyphenylene oxide used in the shapeable polyphenylene oxide resin composition of the present invention is a thermosetting resin with a relatively high glass transition point, low dielectric constant, and low dielectric loss, and has attracted attention in recent years because it is inexpensive. It is something that exists. 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 formed into a desired shape. It has not yet been put to practical use as a resin material for dielectrics used in multilayer wiring.

However, in this invention, by adding ceramic dielectric powder to a polyphenylene oxide resin composition, it is possible to shape the polyphenylene oxide resin composition while controlling its dielectric constant to a desired value. A new resin substrate with good properties and dielectric properties has been realized. This substrate also has excellent heat resistance, chemical resistance, processability, and dimensional stability of the resin.

The shapeable polyphenylene oxide resin composition contains polyphenylene oxide, a crosslinkable polymer and/or a crosslinkable monomer, and a ceramic dielectric powder. The polyphenylene oxide used has, 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. Examples thereof include poly(2 ，
6-dimethyl-1,4-phenylene oxide).

Although the molecular weight is not particularly limited, for example,
ff1Ji average molecule Ji (M w > Ka50,00
0, molecular weight distribution Mw/M n =4.2 (M n is number average molecular weight).

Examples of crosslinkable polymers include ■. Examples include 2-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. be able to.

These polymers may be in the form of elastomers or rubbers.

However, when the sheet of the present invention is manufactured by the casting method described below, it is preferable to use polystyrene having a relatively high molecular weight in order to improve the film-forming properties of the sheet.

In addition, examples of crosslinking monomers include: ■ Acrylates such as ester acrylates, epoxy acrylates, urethane acrylate necks, ether acrylate necks, melamine acrylates, alkyd acrylates, and silicone acrylates, ■ Triallyl cyanurate, and Examples include polyfunctional monomers such as allyl isocyanurate, ethylene glycol dimethacrylate, divinylbenzene, diallyl phthalate, monofunctional monomers such as vinyltoluene, ethylvinylbenzene, styrene, paramethylstyrene, and polyfunctional epoxies. , can be used alone or in combination of two or more. Of these, triallyl cyanurate and/or
Alternatively, triallylisocyanurate is preferred because it has good compatibility with polyphenylene oxide and improves film formability, crosslinkability, heat resistance, and dielectric properties.

Triallyl cyanurate and triallyl isocyanurate are chemically structurally isomers and have similar film-forming properties, compatibility, solubility, reactivity, etc. Or both can be used equally.

The above crosslinkable polymers and crosslinkable monomers are
Either one may be used alone or in combination, but the combination is more effective in improving characteristics.

As the ceramic dielectric powder used in the present invention, one having a relative dielectric constant of about several (Htlz) to 10,000 (MHz) is used as appropriate depending on the dielectric properties to be imparted to the product. Examples of such ceramic dielectric powders include aluminum oxide ceramics, titanium dioxide ceramics, barium titanate ceramics, and titanate ceramics.
9 series ceramic, calcium titanate ceramic, magnesium titanate ceramic, bismuth titanate ceramic, strontium titanate ceramic, zirconium oxide ceramic, lead zirconate ceramic, barium zirconate ceramic, K2O-PbO
SiO2 ceramic, Bao, s Pbo, s Ndw 'T”fs 0+4
ceramic or Da (Zn+7.Nb2ys)
O* ceramic powder or a mixed powder of two or more of these can be used.

In this invention, in addition to such ceramic dielectric powder, a fibrous reinforcing material is further contained. As a result, even when containing a large amount of ceramic dielectric powder,
It is possible to prevent the resin molded body from becoming brittle.

As the fibrous reinforcing material, a wide range of materials that are generally used as reinforcing fibers for resins can be used as long as they prevent embrittlement of the resin molded product and provide good shaping properties.For example, glass fibers or Aramid fiber etc. can be used.

Crosslinkable polymers and/or monomers as described above,
An initiator may also be used when incorporating the ceramic dielectric powder and the fibrous reinforcing material into the polyphenylene oxide.

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

Further, an initiator using ultraviolet rays and an initiator using heat may be used in combination.

It goes without saying that the excipient polyphenylene oxide resin composition can contain, in addition to the above-mentioned initiator, various additives as long as they do not impair its properties, such as bromine as a flame release agent. brominated polyphenylene oxide, brominated bisphenol type polycarbonate, etc.

The proportion of the ceramic dielectric powder contained in the shapeable polyphenylene oxide resin composition is not particularly limited as long as it can impart the desired shapeability to the resin composition according to the molding method. For example, when forming a sheet by the casting method described below, it is preferable to mix 1,000 to 10,000 parts by weight of ceramic dielectric powder to 100 parts by weight of polyphenylene oxide.

Further, the blending ratio of the fibrous reinforcing material can be adjusted as appropriate depending on the blending ratio of the ceramic dielectric powder, etc., but it is usually preferable to contain 20 to 40 parts by weight per 100 parts by weight of the resin contained.

Furthermore, the blending ratio of crosslinkable polymer and/or monomer is usually 1/1 of polyphenylene oxide.
Preferably, the amount is 0 to 95 parts by weight, and the crosslinkable polymer/monomer is 5 to 90 parts by weight.

The proportion of the initiator to be included in addition to such a formulation is preferably 0.1 to 5 parts by weight (more preferably 0.1 to 3 parts by weight). If it is less than the above range, the polyphenylene oxide resin composition may not be sufficiently cured, and if it exceeds the above range, the physical properties after curing may be adversely affected.

The excipient polyphenylene oxide resin composition is usually dissolved in a solvent, dispersed, and mixed. As a solvent, trichlorethylene, trichloroethane, chloroform,
Salt 1 Halogenated carbon such as himethylene and chlorobenzene f
Arsenic hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and xylene, acetone, and carbon tetrachloride can be used, and trichlorethylene is particularly preferred. Each of these can be used alone or in combination of two or more.

Such a shapeable polyphenylene oxide resin composition can be easily produced by thermoforming, and can be shaped into various desired shapes including sheets. "Also, it can be formed into a laminate. In that case, a sheet substrate is formed in advance from the resin composition of the present invention, or a prepreg is formed by impregnating the resin composition into a base material, and if necessary, these sheets, A core material etc. can be produced from the prepreg, and then multilayered and laminated together with other base materials, films, prepregs, metal foils, etc. according to conventional methods.

The shapeable polyphenylene oxide resin composition can be formed into a sheet by, for example, a casting method.

The casting method is a method in which a resin mixed with a solvent is formed into a thin layer by casting or coating, and then the solvent is removed to form a cured product.

According to the casting method, a cured product can be obtained at a low temperature without using the costly calendar method. To explain this casting method more specifically, the excipient polyphenylene oxide resin composition mixed in a solvent is placed on a mirror-treated footboard or a carrier film for casting, etc. , 5 to 500) μm in thickness, and the sheet substrate is obtained by thoroughly drying to remove the solvent.

The carrier film for casting is not particularly limited, but polyethylene terephthalate (
It is preferable to use a film that is insoluble in the above-mentioned solvents, such as a film (hereinafter abbreviated as "PET"), a polyethylene film, a polypropylene film, a polyester film, or a polyimide film, and preferably one that has been subjected to mold release treatment.

Drying is performed by air drying or hot air drying, etc. The upper limit of the temperature range in this case must be lower than the boiling point of the solvent or lower than the heat-resistant temperature of the carrier film for casting (drying on the carrier film for casting) ) is preferred.

The lower limit shall be determined based on drying time, processability, etc. For example, if trichlorethylene is used as a solvent and PET
When the film is used as a carrier film for casting, it is preferably kept at a temperature in the range from room temperature to 80°C, and if the temperature is raised within this range, the drying time can be shortened.

When manufacturing a prepreg by impregnating a base material with a shapeable polyphenylene oxide resin composition, the following method can generally be used.

That is, the base material is dipped in a solvent dispersion of the shapeable polyphenylene oxide resin composition to impregnate and adhere the shapeable polyphenylene oxide resin composition to the base material. Then, the solvent is removed by drying or the like, or semi-cured to bring it to the B stage. In this case, the impregnation area of the shapeable polyphenylene oxide resin composition is not particularly limited, but it is preferably 30 to 80 weight or less. The base material may be glass cloth, aramid cloth, polyester cloth, nylon cloth, etc. Resin-impregnable or loss-like materials, mat-like materials made of these materials and/or fibrous materials such as non-woven fabrics, papers such as kraft paper and linter paper, etc. can be used, and
If a prepreg is produced in this way, which is not limited to these methods, there is no need to melt the resin, so it can be easily carried out at a relatively low temperature.

When forming a metal-clad laminate, a wide variety of metal foils used for ordinary wiring boards can be used as the metal foil for forming the circuit. For example, metal foil such as copper foil or aluminum foil can be used. In this case, it is preferable that the metal foil has a smooth adhesion surface and good conductivity in order to improve dielectric properties.

Such metal foil can be formed by vapor deposition, etc., but it can also be formed into a desired conductor (circuit, electrode, etc.) by subtractive method, additive method (full additive method, semi-additive method), etc. You can.

When manufacturing a laminate using a core material, sheet, or prepreg manufactured from a shapeable polyphenylene oxide resin composition, the sheet and/or prepreg that has been dried appropriately is dried to a predetermined design thickness. Combine the specified sheets, and if necessary, combine and laminate metal foil,
The sheets are bonded together by melting the resin by heating and pressing, etc.
Sheet and prepreg or core material, prepreg to prepreg,
A sheet and metal foil, and a prepreg and metal foil are bonded together to form a laminate. Strong adhesion is obtained by this fusion, but even stronger adhesion can be obtained if the heating at this time causes a crosslinking reaction by a radical initiator.

Such a crosslinking reaction is performed by photocrosslinking such as ultraviolet irradiation, thermal crosslinking, crosslinking by radiation irradiation, etc. Note that such adhesion may be performed in combination with an adhesive.

Here, the combination of sheets, prepregs, and core materials used together is not particularly limited, but it is preferable to use vertically symmetrical combinations in order to prevent warping after molding and secondary processing (etching, etc.). Furthermore, it is preferable to combine the sheets so that they are placed at the adhesive interface with the metal foil, since the adhesive force can be improved.

The temperature during heat pressing depends on the combination of metal foil and sheet or prepreg, but for example, the heat fusion properties of the sheet can be used to bond metal foil and sheet, so the lamination pressing temperature depends on the glass of the sheet. Above the transition point, about 16
The temperature is preferably in the range of about 0 to 300'C.

In addition, when crosslinking is carried out by heating in a dryer, etc., the crosslinking reaction depends on the reaction temperature of the initiator used, etc., so the heating temperature and heating time are selected depending on the type of initiator. For example, temperature 150-300'C1C1
It takes 10 to 10 hours.

Pressing is performed to bond sheets to each other, sheets to prepreg, prepregs to each other, metal foil to sheet, metal foil to prepreg, etc., and to adjust the thickness of the laminate, so press conditions should be selected as necessary. .

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

In the heat pressing as described above, a predetermined number of the films and/or prepregs are heated and laminated in advance, and
A metal foil may be superimposed on one or both sides of this and heat-pressed again.

(Function) The shapeable polyphenylene oxide resin substrate of the present invention has a desired dielectric constant while maintaining the excellent heat resistance, dimensional stability, and chemical resistance of the polyphenylene oxide resin composition. Demonstrates excellent formability without making the molded object brittle.

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

Next, examples will be shown to further explain the present invention.

21 pressure reducing device f = in a reactor, 25 g of polyphenylene oxide, 25 g of styrene-butadiene copolymer (Asahi Ichisei Kogyo (■: Solprene T406)), 100+r of triallyl isocyanurate (Nippon Kasei ■: TAIC), 1 og of dicumyl peroxide. Then, 2,500 g of trichlorethylene (Toagosei Kagaku Kogyo - Nitrichlene) was added and thoroughly stirred until a homogeneous solution was obtained. After that, 860 g of aluminum oxide powder with an average particle size of 1 to 2 μt as ceramic dielectric powder and a fibrous reinforcing material were added. as diameter 6μl
, glass fibers having a length of 311 were added and further stirred to uniformly disperse the fibers. This was then defoamed to obtain a shapeable polyphenylene oxide resin composition solution.

Next, the obtained excipient polyphenylene oxide resin composition solution was applied onto the PET film using a coating machine to a thickness of 500 μl.

After drying this at 50°C for about 10 minutes, the resulting film was
The mold was released from the ET film and dried at 120° C. for an additional 10 minutes to completely remove trichlorethylene to obtain a sheet made of a shapeable polyphenylene oxide resin composition. The thickness of this sheet was approximately 150 μm.

Stack 4 of these sheets at 190℃ and weigh 50 kg.
/ d for 30 minutes to completely cure the sheet, and as shown in FIG. 1, a laminate consisting of four sheets laminated together was produced.

Examples 2 to 7 Six types of resin laminates were produced using the formulations shown in Table 1 in the same manner as in Example rIA1.

Comparative Example 1 A laminate was produced in the same manner as in Example 1 using the formulation shown in Table 1 without containing ceramic dielectric powder and fibrous reinforcing material in the polyphenylene oxide resin composition.6 Examples 8 to 26 Shaping Nineteen types of resin compositions were produced in the same manner as in Example 1, using the formulations of polyphenylene oxide resin compositions as shown in Table 1, and using a ball mill for stirring if necessary.

A sheet and a laminate were similarly produced using this resin composition. However, drying after releasing from the pET film was carried out at 170°C for 20 minutes, and the pressure h* conditions when stacking four sheets of Sea I to completely harden them was 220°C.
The temperature was 150 kg/cd at °C for 30 minutes. Comparative Example 2 Sheets and laminates were produced in the same manner as in Examples 8 to 26 above using the formulations shown in Table 1 without containing the ceramic dielectric powder and the fibrous reinforcement in the polyphenylene oxide resin composition.

Example 27 A glass cloth was impregnated with the excipient polyphenylene oxide resin composition obtained in Example 8, and then heated at 50°C for about 1
Trichlorethylene was removed by drying at 130° C. for about 20 minutes to prepare Gripreg.

Two of these prepregs and three sheets obtained in Example 8 were laminated in the order of sheet and prepreg, and heat-pressed to produce a laminate.

The physical properties of the laminates obtained in Examples 1 to 27 and Comparative Example 1.2 were investigated in terms of dielectric constant, dielectric loss, solvent resistance, and alkali resistance. The results are shown in Table 1. The dielectric constant and dielectric loss were measured by the method shown in FIGS. 1 and 2. (a) shows the substrate, and (b) shows the conductive metal.

Further, Table 2 shows the particle size, firing conditions, etc. of the various ceramic dielectric powders used.

Example 28 Four sheets of the prepreg obtained in Example 27 were stacked together, and electrolytic copper foil with a thickness of 18 μm was stacked on both sides, and heated at 200°C.
The laminate was pressed at 50 kg/cd for 30 minutes to produce a metal-clad laminate.

Table 1 (Part 3) (Notes to Table 1) Zero 1: Styrene-butadiene copolymer J2 Nitrialyl isocyanurate J3: A...Dicumyl peroxide B...2
゜5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3 J4:A...Aluminum oxide (average particle size 1-2 μm
)B...Titanium dioxide (average particle size l~2μm)C...
- Aluminum oxide (average particle size 5-6 μm) bow: Changes in appearance were observed after being immersed in boiling trichlorethylene for 5 minutes.

(Effects of the Invention) According to the present invention, by incorporating a crosslinkable polymer and/or monomer, ceramic dielectric powder, and fibrous reinforcing material into polyphenylene oxide, the desired heat resistance, dimensional stability, and chemical resistance can be achieved. It is possible to obtain a resin substrate having a dielectric constant of , and which is capable of high-density miniaturization, high-precision miniaturization, thinning, etc.

[Brief explanation of the drawing]

FIG. 1 and FIG. 2 are a perspective view and a circuit diagram, respectively, showing a method for measuring relative dielectric constant and dielectric loss. Agent Patent Attorney Toshio Nishizawa

Claims (11)

[Claims] (1) Polyphenylene produced by molding or impregnating a base material with a shapeable polyphenylene oxide resin composition containing a crosslinkable polymer and/or monomer, ceramic dielectric powder, and fibrous reinforcing material Oxide resin substrate. (2) Ceramic dielectric powder includes aluminum oxide ceramic, titanium dioxide ceramic, barium titanate ceramic, lead titanate ceramic, calcium titanate ceramic, magnesium titanate ceramic, bismuth titanate ceramic, and titanate ceramic. Strontium ceramic, zirconium oxide ceramic,
Lead zirconate ceramic, barium zirconate ceramic, K_2O-PbO-SiO_2 ceramic,
Ba_0_. _5Pb_0_. _5Nd_2Ti_5O
_1_4 ceramic or Ba(Zn_1_/_3
The polyphenylene oxide resin substrate according to claim 1, which is a Nb_2_/_3)O_3 ceramic powder or a mixed powder of two or more thereof. (3) The polyphenylene oxide resin substrate according to claim (1), wherein the fibrous reinforcing material is glass fiber or aramid fiber. (4) The polyphenylene oxide resin substrate according to claim (1), wherein the crosslinkable polymer is a styrene-butadiene copolymer. (5) The polyphenylene oxide resin substrate according to claim (1), wherein the crosslinking monomer is triallyl isocyanurate or triallyl cyanurate. (6) The polyphenylene oxide resin substrate according to claim (1), which contains 1,000 to 10,000 parts by weight of ceramic dielectric powder per 100 parts by weight of polyphenylene oxide. (7) 2 parts by weight of fibrous reinforcing material per 100 parts by weight of resin
The polyphenylene oxide resin substrate according to claim 1, containing 0 to 40 parts by weight. (8) 10 to 95 parts by weight of polyphenylene oxide, and 5 to 90 parts by weight of crosslinkable polymer and/or monomer
The polyphenylene oxide resin substrate according to claim 1, which contains parts by weight. (9) A shapeable polyphenylene oxide resin substrate, characterized in that the shapeable polyphenylene oxide resin composition according to claim (1) is thermoformed and further laminated. (10) A polyphenylene oxide resin substrate, characterized in that the shapeable polyphenylene oxide resin composition according to claim (1) is formed into a sheet by a casting method or further laminated. (11) A polyphenylene product obtained by forming a sheet and/or prepreg from the shapeable polyphenylene oxide resin composition according to claim (1), and laminating and integrating the sheet and/or prepreg with metal foil. Oxide resin metal clad laminate.