JPH01190448A - Thermoset polyphenylene oxide resin multilayered plate - Google Patents

Abstract

PURPOSE:To provide excellent heat resistance, processing properties and dimension stability, and low permittivity, to make multilayers easily and to carry out stabilized high speed signal treatment, by forming a sheet out of a polyphenylene oxide resin formation containing a crosslinking polymer and/or a monomer and an initiator and having the same impregnated in a base. CONSTITUTION:A crosslinking polymer and/or a crosslinking monomer and an initiator are contained in polyphenylene oxide to form a formation used for forming a sheet and impregnating a base. As for the crosslinking polymer, for example, 1,2-polybutadiene, rubber or the like is used, and as a crosslinking monomer, ester acrylate group, multifunctional epoxy group or the like is used, while ultraviolet curing type benzoin, benzyl heat curing type dicumyl peroxide or the like can be used as an initiator. The sheet layer 1, a prepreg layer 2 and metallic foil layers 3 thus prepared are laminated. A multilayer plate thus manufactured is of superior heat resistance, resistance to chemicals and dimension stability and also with low permittivity and dielectric loss.

Description

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

More specifically, the present invention provides heat resistance, workability, and
This invention relates to a polyphenylene oxide resin multilayer board that has excellent dimensional stability and low dielectric constant characteristics.

(Prior art) For wiring boards used in precision instruments, electronic computers, communication devices, etc., there is an increasing demand for higher processing speeds and higher circuit densities, and in order to meet these demands, Multilayer wiring boards are rapidly becoming more multilayered.

Conventionally, epoxy resins, polyimide resins, and low dielectric constant resins such as fluorine resins and polybutadiene resins have been used for the resins that make up these multilayer boards, and efforts are being made to improve their properties. progress has been made.

(Problems to be Solved by the Invention) However, such conventional resins for multilayer boards have not been able to fully satisfy various characteristics required of multilayer wiring boards.

For example, when using epoxy resins and polyimide resins as resins for multilayer boards, although they have excellent processability, both the dielectric constant and dielectric loss are large, so they cannot support increased signal processing speeds. On the other hand, although fluororesins and polybutadiene resins have low dielectric constants, they have the disadvantages of poor processability, difficulty in through-hole plating, and poor dimensional stability. Furthermore, these resins have the problem of high cost.

For this reason, there is a strong need for a new resin for multilayer boards that has heat resistance, processability, dimensional stability, easy multilayering, low dielectric constant, and stable high-speed signal processing, and the creation of multilayer boards using this resin. It was wanted.

(Means for Solving the Problems) The present invention has been made to solve the problems of conventional multilayer boards as described above, and has improved heat resistance, dimensional stability,
It is an object of the present invention to provide a multilayer board using a resin having good workability and a low dielectric constant.

To achieve this objective, the present invention involves forming a sheet from or impregnating a substrate with a polyphenylene oxide resin composition containing polyphenylene oxide, a crosslinkable polymer and/or monomer, and an initiator. Provided is a thermosetting polyphenylene oxide resin multilayer board characterized by being multilayer laminated and having a body color.

The polyphenylene oxide used for impregnating the base material in the multilayer board of this invention has an extremely high glass transition point, a low dielectric constant,
It is a resin with low dielectric loss and has been attracting attention in recent years. However, until now, there was still room for improvement in heat resistance, chemical resistance, physical strength (rigidity, dimensional stability), etc., and it had not been put into practical use. However, by having a specific composition, that is, by adding a crosslinking agent such as a crosslinkable polymer or a crosslinkable monomer, the heat resistance, chemical resistance, processability,
It was found that dimensional stability was dramatically improved, and based on this knowledge, the present invention improved heat resistance, chemical resistance,
In order to impart properties such as processability and dimensional stability, polyphenylene oxide is mixed with a crosslinkable polymer and/or a crosslinkable monomer and an initiator and used as a resin composition for sheet formation and substrate impregnation. .

The polyphenylene oxide used in this invention is, for example, one represented by the following maximum (R is hydrogen or carbonization of 1 kl to 3 carbon), and examples thereof include poly(2,6-dimethyl-1 , 4-7 dinilene oxide).

Although the molecular weight is not particularly limited, for example,
It is preferable that the weight average molecular weight (Mw) is so, ooo, and the molecular weight distribution Mw/Mn=4.2 (Mn is the number average molecular weight).

Such polyphenylene oxide, for example, the above-mentioned poly(2,6-dimethyl-1,4-)unicine oxide), is produced by mixing 2,6-Ir5i1yol with an oxygen-containing gas and methanol in the presence of a catalyst. It can be obtained by carrying out an oxidative coupling reaction. Here, the catalyst includes a copper(I) compound, N,N'-di-tert-butylethylenediamine, butyldimethylamine, and hydrogen bromide, and methanol is used in an amount of 2 to 15% by weight based on this. Add water to the reaction mixture,
The total amount of methanol and water used is 5 to 25% by weight of the polymerization solvent.

Examples of crosslinkable polymers include 1,2-polybutadiene, 1,4-polybutadiene, styrene-butadiene copolymer, modified 1,2-polybutadiene (malein-modified, acrylic-modified, epoxy-modified), rubbers, etc. , can be used alone or in combination of two or more.

The polymer state may be elastomer or rubber; however, when manufacturing the multilayer board of the invention using a film formed by the casting method described below, a relatively high-quality polymer may be used in order to improve the film formability of the film. Preferably, molecular weight polystyrene is used.

In addition, examples of crosslinking monomers include: ■Acrylates such as ester acrylates, epoxy acrylates, urethane acrylates, ether acrylates, melamine acrylates, alkyd acrylates, and silicone acrylates, ■Triaryl cyanurate, and These include multifunctional polymers such as allyl isocyanurate, ethylene glycol dimethacrylate, divinylbenzene, and diallyl phthalate; monofunctional monomers such as vinyltoluene, ethylvinylbenzene, styrene, and paramethylstyrene; and multifunctional epoxies. , can be used alone or in combination of two or more. Of these, triallyl cyanurate and/or
Triallyl isocyanurate is preferable because it has good compatibility with polyphenylene oxide and has good film-forming properties, crosslinking properties, 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 of them may be used alone or they may be used in combination, but the combination is more effective in improving the characteristics.

In addition, an initiator is used in the polyphenylene oxide resin composition used in this invention. [As the initiator, the following two types can be selected depending on whether the polyphenylene oxide resin composition is an ultraviolet curing type or a thermosetting type, but the initiator is not limited to these.

Examples of the ultraviolet curing photoinitiator (that is, one that generates radicals by ultraviolet irradiation) include benzoin, benzyl, allyldiazonium fluorobalate, benzyl methyl ketal, 2,2-jethoxyacetophenone, benzoyl isobutyl ether, p-tert-butyltrichloroacetophenone, benzyl(0-ethoxycarbonyl)-α-monoxime, biacetyl, acetophenone, benzophenone, Michler's ketone, tetramethylthiuram sulfide, azobisisobutyronitrile, and the like can be used. Additionally, thermosetting initiators (i.e.
Examples of substances that generate radicals by heat include dicumyl peroxide, tert-butylcumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-di(t).
ert-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(tert-butylperoxy)
Hexane, α.

α′-bis< tert-butylperoxy-m-isopropyl)benzene (1,4 (or 1.3)-bis(
peroxides such as tert-butylperoxyisopropyl (also called benzene), 1-hydroxycyclohexylphenyl edone, 2-hydroxy-2-methyl-1-
Phenylpropan-1-one, 1-(4-isopropylphenyl)-2-droxy-2-methylpropane-1
-one, 2-chlorothioxanthone, methylbenzoyl formate, 4,4-bisdimethylaminobenzophenone (mirror ketone), benzoin methyl ether,
Methyl-0-benzoylbenzoate, α-aziroxime ester, NOF's biscumyl, and the like can be used. These initiators may be used alone or in combination of two or more.

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

The blending ratio of the above polyphenylene oxide, crosslinkable polymer and/or monomer, and initiator is as follows:
Usually, it is preferable to use 10 to 95 parts by weight of polyphenylene oxide, 1 to 90 parts by weight of crosslinkable polymer/monomer, and 0.1 to 5 parts by weight of initiator. If the proportion of initiator is below the above range, The curing of the polyphenylene oxide resin composition may be insufficient, and if it exceeds the above range, the physical properties after curing may be adversely affected.

The polyphenylene oxide resin used for sheet formation or base material impregnation in the present invention not only has low dielectric constant and low dielectric loss properties, but also improves its properties by adding various inorganic fillers. can be easily changed. Examples of such inorganic fillers include titanium dioxide-based ceramics, barium titanate-based ceramics, lead titanate-based ceramics, strontium titanate-based ceramics, calcium titanate-based ceramics, lead zirconate-based ceramics, etc., singly or in combination. Can be used together.

The polyphenylene oxide resin composition as described above is
Usually, they are dissolved in a solvent, dispersed, and mixed.

In this case, the amount of solvent used is preferably such that it is a 5 to 50% by weight solution of the polyphenylene oxide resin composition (or the resin solid content is in the range of 10 to 30% by weight based on the solvent). Solvents include trichloroethylene, trichloroethane, chloroform, methylene chloride,
Halogenated hydrocarbons such as chlorobenzene, benzene,
Aromatic hydrocarbons such as toluene and xylene, acetone,
Carbon tetrachloride and the like can be used, and trichlorethylene is particularly preferred, and these can be used alone or in combination of two or more.

The multilayer board of the present invention is produced by forming a sheet from such a polyphenylene oxide resin composition or impregnating it into a base material to produce prepreg, core material, etc., and then applying it to other base materials, films, etc. in accordance with conventional methods. It can be manufactured by laminating multiple layers together with prepreg, metal foil, etc.

For example, a casting method can be used to form a polyphenylene oxide resin composition sheet.

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.

To explain this casting method more specifically, a polyphenylene oxide resin mixed with a solvent is placed on a mirror-treated iron plate or a carrier film for casting, for example, with a coating of 5 to 700 (preferably 5
~500) A sheet is obtained by casting (or coating) to the thickness of the mu intestine and 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 rPETJ), a polyethylene film, a polypropylene film, a polyester film, a polyimide film, and a film that has been subjected to a 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, and the lower limit shall be determined depending on drying time, processability, etc. For example, when trichlorethylene is used as a solvent and PET film is used as a carrier film for casting, the temperature range is from room temperature to 80°C. is preferable.

Note that by increasing the temperature within this range, the drying time can be shortened.

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

That is, by dipping the base material in a solvent dispersion of the polyphenylene oxide resin composition,
These polyphenylene oxide resin compositions are impregnated and adhered to a base material. Then, the solvent is removed by drying or the like, or semi-cured to bring it to the B stage. The amount of the polyphenylene oxide resin composition impregnated in this case is not particularly limited, but it is preferably 30 to 80% by weight. The prepreg can be produced using materials such as, but not limited to, mat-like materials and/or fibrous materials such as non-woven fabrics made of these materials, and papers such as kraft paper and linter paper. In this case, the resin does not need to be melted, so it can be carried out more easily at a relatively low temperature.

As the metal foil for circuit formation used in the multilayer board of the present invention, a wide variety of metal foils commonly used for wiring boards can be used. 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 the subtractive method, additive method (full additive method, semi-additive method), etc. You may.

As a method for manufacturing a multilayer board using a core material, sheet, or prepreg manufactured from a polyphenylene oxide resin composition, the following method can be used, for example.

That is, the above-mentioned properly dried films and/or prepregs are combined in a predetermined manner so as to have a predetermined design thickness, and if necessary, metal foil is also combined and laminated.
The sheets are bonded together by melting the resin by heating and pressing, etc.
Sheet and prepreg or core material, prepreg to prepreg,
A laminate is obtained by bonding the sheet and metal foil, and the prepreg and metal foil to each other. 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 carried out 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 sheet, prepreg, and core material when used together is not particularly limited, but it is preferable to use a symmetrical combination of the top and bottom to prevent warping after molding and secondary processing (etching, etc.). It is preferable to combine the sheets in such a way that they are placed on the adhesive interface with the gold Jl foil, since this can improve the adhesive strength.

The temperature during heat-pressing depends on the combination of metal foil and film or prepreg, but for example, the heat-sealing properties of the sheet can be used to bond metal foil and sheet, so the lamination-pressing temperature depends on the glass transition of the sheet. More than 1 point, about 1
The temperature is preferably in the range of about 60 to 300°C.

In addition, when crosslinking the polyphenylene oxide resin composition of the present invention by placing it in a dryer and heating it, the crosslinking reaction depends on the reaction temperature of the initiator used, so the heating temperature and heating time are For example, temperature 150-300℃, time 10-60℃.
It takes about a minute.

Pressing is performed to bond sheets to each other, sheets to prepreg, prepregs to prepreg, metal foil to sheet, metal foil to prepreg, etc., and to adjust the thickness of the laminate, so press conditions are selected as necessary. For example, the pressure can be set to about 50 kt/a11.

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 then heated and pressed again.

(Function) The multilayer board of the present invention has good heat resistance, dimensional stability, and chemical resistance, and by using a polyphenylene oxide W resin composition with a low dielectric constant, it can be processed with high precision as a multilayer board. This makes the multilayer board with high characteristics suitable for high-speed signal processing.

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

(Example) (i) Preparation of polyphenylene oxide resin sheet and laminate (a) 100 g of polyphenylene oxide, 40 g of styrene-butadiene copolymer (Asahi Kasei Kogyo (TL: Solprene T406), triallyl isocyanurate, in a 27 reactor equipped with a pressure reduction device) (Nippon Kasei ■: TAIC) and 2 g of dicumyl peroxide were added, followed by 750 g of trichlorethylene (Toagosei Kagaku Kogyo ■: Trichlene) and stirred thoroughly until a homogeneous solution was obtained.

Thereafter, defoaming was performed, and the resulting polyphenylene oxide resin composition solution was coated 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 further dried at 120° C. for 30 minutes to completely remove trichlorethylene to obtain a sheet made of a polyphenylene oxide resin composition. The thickness of this sheet was approximately 150 μm.

Furthermore, five types of sheets were produced in the same manner using the formulation of the resin composition and the film forming conditions as shown in Table 1.

Table 1 (A) Asahi Kasei ■ Toughden 2003 (B) Asahi Kasei ■ Solrun 1206 (C) TAIC: Nippon Kasei ■ (G) Triclean (b) Also, thickness 150 manufactured by the above (a)
4 μm sheets stacked, 190℃, 50 pupils/a
It was pressed under the conditions of J for 30 minutes to completely cure, and a laminate was produced.

(11) Preparation of polyphenylene oxide resin-impregnated prepreg and laminate (a) 40 t of polyphenylene oxide and 40 g of styrene-butadiene copolymer were placed in 800 g of trichlorethylene (Toagosei Kagaku Kogyo - Nitriclene) placed in a 2J reactor equipped with a pressure reduction device. , triallyl isocyanurate 1
20 g, 2,5-dimethyl-2,5-di(tert-
6 g of (butylperoxy)hexyne-3 (Nippon Oil & Fats Ltd.'s Perhexine 25B) was added, and the mixture was sufficiently stirred until a homogeneous solution was obtained.

A glass cloth (100 g/n
f) to impregnate it with this solution, then take it out, and
It was dried at 0°C for about 1 minute and at 80°C for about 5 minutes to obtain a prepreg. In the same manner, glass cloth was impregnated with the resin composition, changing the blending amount as shown in Table 2. Eleven types of prepregs were produced.

(b) Additionally, four sheets of the obtained prepreg were laminated and molded using a molding press at 195° C. and 10 kg/aJ for 60 minutes to obtain a laminate.

(+ r r ): Forming of rA material, multilayer board forming 1st
As shown in the figure and Fig. 2, the above (i) and (ii)
a sheet layer (1) consisting of the required number of resin sheets obtained in
A core material laminate was manufactured by laminating similar prepreg layers (2) and metal foils (3).

The lamination conditions in this case were the same as those in (i) and (ii) above.

The core material circuit was formed by etching by conventional methods.

In addition, as shown in FIG. 3, the above (i) (ii) (ii)
Polyphenylene oxide resin sheet (1) obtained in i)
and prepreg layer (2) impregnated with this resin, core material (4)
) and metal foil (3) were laminated and integrated to produce a multilayer board.

This multilayer board was subjected to processing such as etching, through-hole processing, and plating using conventional methods to obtain a multilayer circuit board.

The multilayer board obtained in this way has excellent heat resistance, chemical resistance, and dimensional stability, as well as low dielectric constant and dielectric loss.When this multilayer board was put to practical use as a wiring board for a high-speed signal processing circuit, Signal delay was suppressed and good results were obtained.

(Effects of the Invention) According to the present invention, by using a polyphenylene oxide resin composition, a multilayer board having a low dielectric constant and excellent heat resistance, dimensional stability, and chemical resistance and good workability can be obtained.

It has excellent heat resistance and chemical resistance during mounting, and is further advantageous as a multilayer wiring board for high-speed signal processing.

[Brief explanation of the drawing]

FIGS. 1, 2, and 3 are cross-sectional views of embodiments of the invention, respectively. 1... Sheet layer, 2... Prepreg layer, 3...
Metal foil, 4... Core material. Agent Patent Attorney Toshio Nishizawa No. 1
Figure 2 Figure 3

Claims (4)

[Claims] (1) A sheet is formed from a polyphenylene oxide resin composition containing polyphenylene oxide, a crosslinkable polymer and/or monomer, and an initiator, or the sheet is impregnated into a base material and integrated into a multilayer laminate. A thermosetting polyphenylene oxide resin multilayer board. (2) A composition comprising 10 to 95 parts by weight of polyphenylene oxide, 1 to 90 parts by weight of a crosslinkable polymer and/or monomer, and 0.1 to 5 parts by weight of an initiator. Thermosetting polyphenylene oxide resin multilayer board as described in item 1). (3) The thermosetting polyphenylene oxide resin multilayer board according to claim (1), wherein the crosslinkable polymer is a styrene-butadiene copolymer. (4) The crosslinking monomer is triallyl isocyanurate or triallyl cyanurate (
Thermosetting polyphenylene oxide resin multilayer board as described in item 1).