JP2003160726A - Polyphenylene oxide resin composition, its production method, prepreg, laminated board, printed wiring board and multi-layered printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyphenylene oxide resin composition improving the high-frequency characteristics of the cured product by lowering the dielectric constant and dielectric dissipation factor and also having high moldability and flame retardancy. <P>SOLUTION: The polyphenylene oxide resin composition contains a polyphenylene oxide and a triallyl isocyanurate as essential components, the number average molecular weight of the polyphenylene oxide is in the range of 2,000-12,000 and the composition contains one selected from a halogenated polyphenylene oxide, a halogenated triallyl isocyanurate and a fluorinated aliphatic resin as a flame retardant. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyphenylene oxide resin composition useful as an insulating material for printed wiring boards and the like, a method for producing the polyphenylene oxide resin composition, and a prepreg and a laminate using the polyphenylene oxide resin composition. The present invention relates to boards, printed wiring boards and multilayer printed wiring boards.

[0002]

2. Description of the Related Art In recent years, electronic equipment has made a great progress due to high integration of semiconductor devices to be mounted and refinement of packages, high density wiring and bonding of printed wiring boards, and improvement of mounting technology. In particular, the progress has been remarkable in electronic devices using high frequency bands such as mobile communication.

In the printed wiring board which constitutes this kind of electronic equipment, multilayering and fine wiring are progressing at the same time. However, in order to increase the signal transmission speed required for high-speed information processing, the dielectric property of the material is required. It is effective to reduce the rate, and it is effective to use a material having a small dielectric loss tangent (dielectric loss) in order to reduce the loss during transmission.

Polyphenylene oxide resin [polyphenylene ether (PPE)] is used as an insulating material for a printed wiring board of electronic equipment which utilizes such a high frequency band because of its excellent high frequency characteristics such as dielectric constant and dielectric loss. [Also referred to as resin] is suitable, but the heat resistance and dimensional stability were not sufficient. In addition, since the polyphenylene oxide resin has a high melting point, the prepreg used for manufacturing a normal multilayer printed wiring board has a high melt viscosity, and defects such as voids and faints occur during multilayer molding, and the reliability is high. It wasn't enough.

[0005]

Therefore, the applicant of the present invention is
JP-A-8-231847 proposes a polyphenylene oxide resin composition having improved heat resistance and dimensional stability, a prepreg using the polyphenylene oxide resin composition, and a laminated board using the prepreg. is doing. That is, polyphenylene oxide, triallyl isocyanurate, a polyphenylene oxide resin composition containing a non-reactive brominated compound is prepared, a prepreg using this polyphenylene oxide resin composition, and a laminate using this prepreg. It is intended to make a plate.

However, when such a resin composition is used, polyphenylene oxide itself has a high melting point, and therefore, in order to fill the inner layer conductor pattern as a multilayer printed wiring board, the viscosity at the time of melting at a normal pressing temperature is high. high,
It was difficult to make multiple layers.

[0007] Therefore, the present applicant has further filed a patent application 2001-
68857, the number average molecular weight of the polyphenylene oxide in the polyphenylene oxide resin composition was 2
By setting the viscosity in the range of 000 to 12000, a technique is proposed in which the viscosity at the time of melting at a normal press temperature (melt viscosity) is lowered, and a multilayer structure is possible, and in this application, a flame retardant is included. However, if flame retardancy is added by adding flame retardancy, it becomes difficult to sufficiently reduce the dielectric constant and dielectric loss tangent. It has been difficult to cope with the increase in the signal transmission speed required for the increase in speed.

The present invention has been made in view of the above points, and is a polyphenylene oxide resin composition having a high moldability and flame retardancy as well as improved high frequency characteristics by reducing the dielectric constant and dielectric loss tangent of a cured product. It is an object of the present invention to provide a product, a method for producing the polyphenylene oxide resin composition, and a prepreg, a laminate, a printed wiring board, and a multilayer printed wiring board using the polyphenylene oxide resin composition.

[0009]

The polyphenylene oxide resin composition according to claim 1 of the present invention contains polyphenylene oxide and triallyl isocyanurate as essential components, and the polyphenylene oxide has a number average molecular weight of 2000 to 12000. It is within the range and contains halogenated polyphenylene oxide as a flame retardant as a part or all of polyphenylene oxide.

The invention of claim 2 is characterized in that, in claim 1, the halogenated polyphenylene oxide is one in which all or some of the hydroxyl groups at the terminal of the molecule have been lost by esterification. Is.

The invention of claim 3 is characterized in that, in claim 1 or 2, brominated polyphenylene oxide is contained as the halogenated polyphenylene oxide.

A fourth aspect of the present invention is characterized in that, in the third aspect, the brominated polyphenylene oxide has a bromination rate of 45% by mass or more and less than 85% by mass.

A polyphenylene oxide resin composition according to a fifth aspect of the present invention contains polyphenylene oxide and triallyl isocyanurate as essential components, and the polyphenylene oxide has a number average molecular weight of 2
It is in the range of 000 to 12000 and contains a triallyl isocyanurate halide as a flame retardant as part or all of triallyl isocyanurate.

The invention of claim 6 is characterized in that in claim 5, the halogenated triallyl isocyanurate is brominated triallyl isocyanurate.

The polyphenylene oxide resin composition according to claim 7 of the present invention contains polyphenylene oxide and triallyl isocyanurate as essential components, and the polyphenylene oxide has a number average molecular weight of 2
It is in the range of 000 to 12,000 and is characterized by containing a fluorinated aliphatic resin as a flame retardant.

[0016] The invention of claim 8 is based on claim 7, wherein the fluorinated aliphatic resin is a tetrafluoroethylene resin, a tetrafluoroethylene hexafluoropropylene copolymer resin, or a tetrafluoroethylene-perfluoroalkyl vinyl ether. And at least one of ethylene tetrafluoride-ethylene copolymer resin.

Further, the invention of claim 9 is the method according to any one of claims 1 to 8, wherein the total content of halogen in the solid content of the resin composition is 8% with respect to the total weight of the non-solvent organic components in the resin composition. It is characterized in that it is blended so as to be ˜40% by mass.

The invention of claim 10 relates to claims 1 to 9.
In any of the above, an inorganic filler is added.

In the method for producing a polyphenylene oxide resin composition according to claim 11 of the present invention, beads are used as a compounding component in preparing the polyphenylene oxide resin composition according to any one of claims 1 to 10. It is characterized in that it is dispersed and mixed by a disperser.

A prepreg according to a twelfth aspect of the present invention is characterized in that a substrate is impregnated with the polyphenylene oxide resin composition according to any one of the first to tenth aspects, and is heated and dried to be semi-cured. It is what

The thirteenth aspect of the present invention is characterized in that, in the twelfth aspect, the base material has a relative dielectric constant of 5.0 or less as a constituent material.

A laminated board according to claim 14 of the present invention is
A predetermined number of prepregs according to claim 12 or 13 are heat-pressed and laminated to form a laminate.

A printed wiring board according to a fifteenth aspect of the present invention is characterized in that a conductor pattern is formed on the surface of the laminated board according to the fourteenth aspect.

According to a sixteenth aspect of the present invention, a multilayer printed wiring board has a conductor pattern formed on the surface of the laminated board according to the fourteenth aspect and a predetermined number of prepregs according to the twelfth or thirteenth aspect. It is characterized in that it is formed by laminating and molding by heating and pressing.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below.

The polyphenylene oxide (hereinafter referred to as PPO) used in the present invention is also referred to as polyphenylene ether (PPE), and is a resin having a chemical structural formula represented by, for example, the following general formula (1).

[0027]

[Chemical 1]

An example of the PPO represented by the above general formula (1) is poly (2,6-dimethyl-1,4-phenylene oxide) represented by the following formula (2). .

[0029]

[Chemical 2]

As such PPO, for example, those synthesized by the method disclosed in US Pat. No. 4,059,568 can be used, and the PPO is not particularly limited. (Mw) is 4
6000-53000, the ratio with the number average molecular weight (Mn), that is, the molecular weight distribution (Mw / Mn) is 4.0-
It is preferably 4.5. However, as it is, PPO
Because of its high melting point and melt viscosity, this resin composition containing PPO has a high melt viscosity, and when used as a material such as a prepreg for producing a multilayer printed wiring board, there is a problem in terms of moldability. Therefore, in the present invention, the melt viscosity of the resin composition is reduced and the moldability is improved by reducing the molecular weight of PPO.

As a method of reducing the molecular weight of PPO,
Reacting PPO with phenolic species "The Journal of O
rganic Chemistry, 34, 297-303 (1969) ”can be used. Examples of the phenol species used in this reaction include phenol, cresol, xylenol, hydroquinone, bisphenol A, 2,6-dimethylphenol, and 4,4′-dihydroxydiphenyl ether. It is more preferable to use a bifunctional or higher functional phenolic species for the purpose of improvement. Further, as an initiator of this reaction, benzoyl peroxide, 3,3 ', 5,5'-tetramethyl-
It is preferable to use an oxidizing agent such as 1,4-diphenoquinone, chloranil, 2,4,6-tri-t-butylphenoxyl, t-butylperoxyisopropyl monocarbonate, azobisisobutyronitrile, and if necessary. This reaction can be promoted with a carboxylic acid metal salt or the like. In addition, an initiator that generates a highly volatile component such as a low molecular weight alcohol as a component after the reaction can suppress an increase in the dielectric constant, and thus is more preferable. The number average molecular weight of the PPO obtained by reacting a phenolic species to lower the molecular weight in this way is preferably in the range of 2000 to 12000. If the number average molecular weight is higher than this range, the melt viscosity is high and the moldability cannot be improved, and if the number average molecular weight is lower than this range, the glass transition point is lowered or the molecular weight is too low. It is difficult to obtain heat resistance.

In the present invention, triallyl isocyanurate (hereinafter referred to as TAIC) is added to PPO in order to improve heat resistance and dimensional stability. TAIC is
Either one of the monomer (hereinafter referred to as m-TAIC) and the prepolymer (hereinafter referred to as p-TAIC) may be used, or both may be used in combination.

Here, in the PPO resin composition of the present invention, PPO and TAIC are 20 to 60 parts by mass of PPO,
It is preferable to contain TAIC in a ratio of 25 to 60 parts by mass. That is, if PPO is less than 20 parts by mass, TAIC
When it is more than 60 parts by mass, the laminate produced using the PPO resin composition tends to be fragile, and it becomes difficult to sufficiently reduce the dielectric constant and the dielectric loss tangent, and the PPO is 60 parts by mass. And the TAIC is less than 25 parts by mass, the viscosity and melt viscosity of the PPO resin composition will be high and the resin fluidity at the time of molding will be insufficient. May have poor moldability.

Further, at least one selected from the group consisting of styrene / butadiene block copolymer, styrene / isoprene block copolymer, 1,2-polybutadiene, 1,4-polybutadiene, malein-modified polybutadiene, acrylic-modified polybutadiene, and epoxy-modified polybutadiene. A compatibilizer can be added. The content of the compatibilizer is preferably 10% by mass or less based on the resin content. If the content of the compatibilizer exceeds this range, the heat resistance may decrease, which is not preferable.

A flame retardant is added to the PPO resin composition. A halogen-based compound is used as the flame retardant. If the halogen-based compound has a large dielectric constant or dielectric loss tangent, even if the dielectric constant or dielectric loss tangent of the base resin PPO or TAIC is small, the dielectric constant or dielectric loss tangent is small. The effect of reducing is reduced. Therefore, in the present invention, as the flame retardant,
By blending any one of halogenated polyphenylene oxide, halogenated triallyl isocyanurate and fluorinated aliphatic resin, the flame retardancy is improved and the dielectric constant and dielectric loss tangent are sufficiently reduced.

The halogenated polyphenylene oxide is P
It is blended as a part or all of PPO in the PO resin composition.

As the halogenated polyphenylene oxide, a halogenated polyphenylene oxide obtained by reacting a halogenated polyphenylene oxide with an acid anhydride such as acetic anhydride by heating is used. By eliminating all or some of the hydroxyl groups at the terminal of the molecule, the dielectric constant is reduced as compared with the usual halogenated polyphenylene oxide.

When halogenated polyphenylene oxide, especially brominated polyphenylene oxide, is added, flame retardancy can be obtained even with a small amount of halogen added, and the dielectric constant and dielectric loss tangent can be sufficiently reduced.
When the brominated polyphenylene oxide is blended in this way, the bromination rate (bromine atom content rate) is preferably 45% by mass or more and less than 85% by mass, and the bromination rate is less than 45% by mass. Therefore, in order to obtain sufficient flame retardancy, the blended amount of brominated polyphenylene oxide is increased, which may cause adverse effects on properties such as a decrease in Tg. Further, when the bromination rate is 85% by mass or more,
In the molecule of brominated polyphenylene oxide, the amount of bromine not directly bonded to the benzene ring increases, which may cause a problem in heat resistance.

The triallyl isocyanurate halide is incorporated as a part or the whole of TAIC in the PPO resin composition. When brominated triallyl isocyanurate is blended as the halogenated triallyl isocyanurate, flame retardancy is obtained even with a small amount of halogen added, and the dielectric constant and dielectric loss tangent are sufficiently reduced.

When a fluorinated aliphatic resin is blended, it is particularly preferable to use a tetrafluoroethylene resin, a tetrafluoroethylene hexafluoropropylene copolymer resin, a tetrafluoroethylene-perfluoroalkyl vinyl ether, a tetrafluoride. It is preferable to use at least one of ethylene-ethylene copolymer resins, and these have a particularly low dielectric constant even in an organic compound, and greatly contribute to the reduction of the dielectric constant of the PPO resin composition. .

In these flame retardants, the total halogen content in the solid content of the PPO resin composition is 8 to the total amount of organic components (all non-solvent organic components) excluding volatile components in the resin composition.
It is preferable to add 40% by mass. If this total halogen content is less than 8% by mass, it will be 9 of the UL standard.
It is difficult to secure the flame retardancy at a level of 4V-0, and if it exceeds 40% by mass, halogen tends to dissociate during heating and the heat resistance tends to decrease.

These flame retardants include those that dissolve in the resin component or solvent in the PPO resin composition, and those that react with the resin component, and those that do not react with the resin component. However, when using a flame retardant that does not dissolve in the resin component or solvent in the PPO resin composition,
As will be described later, the use of a disperser using beads results in more uniform dispersion, prevents uneven appearance after molding, and provides uniformity in properties such as flame retardancy.

If necessary, an inorganic filler may be added to the composition. By compounding the inorganic filler, it is possible to reduce the coefficient of thermal expansion of the laminate obtained by using the PPO resin composition, reduce the dimensional change rate during heating, and strengthen the laminate. The reliability of the laminated plate can be improved.

The inorganic filler is not particularly limited, but silica, boron nitride, wollastonite, talc,
Examples thereof include metal oxides such as kaolin, clay, mica, alumina, zirconia, and titania, nitrides, silicides, borides, and the like, and these can be used alone or in combination of two or more kinds. In particular, in order to lower the dielectric constant of the composition, it is preferable to use a low dielectric constant filler such as silica or boron nitride as the inorganic filler. The content of the inorganic filler is preferably 5 to 50 parts by mass with respect to 100 parts by mass of all the non-solvent organic components in the resin composition, and the thermal expansion of the resin can be achieved by mixing in this range. The coefficient can be reduced and the strength can be improved.

Since the PPO resin composition thus obtained does not impair the properties of PPO and uses a flame retardant having a low dielectric constant, it has excellent high frequency properties such as dielectric properties, and , Excellent in water resistance, moisture resistance, moisture absorption heat resistance and glass transition point.

A prepreg can be prepared using the PPO resin composition as described above. First, in order to obtain a prepreg by impregnating a substrate with the PPO resin composition, first of all, PP is used.
A PPO resin varnish is prepared by mixing O, TAIC, a flame retardant, a compatibilizer added as necessary, and the like with an organic solvent.

The organic solvent is not particularly limited as long as it dissolves the resin component and does not adversely influence the reaction, and examples thereof include ketones such as methyl ethyl ketone, ethers such as dibutyl ether, esters such as ethyl acetate. , Amides such as dimethylformamide, benzene,
Suitable organic solvents such as aromatic hydrocarbons such as toluene and xylene and chlorinated hydrocarbons such as trichloroethylene are used alone or in combination of two or more. The concentration of the resin solid content of the varnish may be appropriately adjusted according to the work of impregnating the base material with the varnish, and for example, 20 to 80% by mass is suitable. It is common to add an inorganic filler such as silica to this varnish with stirring, if necessary.

If necessary, the varnish is dispersed and mixed with a disperser using beads to uniformly disperse the flame retardant and the like. The disperser using beads is, for example, commonly called a sand mill, a basket mill, a bead mill, and a Glen mill, which is a facility for dispersing fine beads as a medium. Here, the beads are a spherical substance having a diameter of several cm to several tens of μm, and are generally made of ceramics such as glass and zirconia, and it is considered that the higher the hardness, the greater the dispersion effect.

The order of compounding these resins and the order of steps are not particularly specified.

The PPO resin composition thus obtained has a low varnish viscosity and a low melt viscosity, and the molded and cured product has good moldability because voids and scratches are suppressed.
It also has a high glass transition point and forms an interpenetrating network structure with excellent heat resistance.

In addition, although the flame retardant is added to improve the flame retardancy, the dielectric constant and the dielectric loss tangent are sufficiently reduced without impairing the characteristics of PPO.

Then, a prepreg can be obtained by impregnating the base material with the varnish prepared as described above, further drying by heating to evaporate the organic solvent. As the base material, a woven or non-woven fabric of organic fibers or glass fibers can be used.

The amount of varnish impregnated into the base material is preferably such that the weight ratio of the resin solids in the prepreg is 35% by mass or more. Generally, the dielectric constant of the base material is higher than that of the resin, so in order to reduce the dielectric constant of the laminated plate obtained by using this prepreg, the content of the resin solid content in the prepreg is made larger than the above mass ratio. Is desirable. For example, in a prepreg using an E glass cloth as a base material, a dielectric constant of 3.7 or less can be achieved with a resin solid content of 37% by mass or more. The prepreg used had a dielectric constant of 3. with a resin solid content of 45% by mass or more.
4 or less can be achieved.

In particular, when a woven or non-woven fabric of glass fiber made of a low dielectric constant glass having a dielectric constant of 5 or less, which is the constituent material, is used as the base material of the prepreg, the prepreg is used. It is possible to further reduce the dielectric constant of the laminated plate or the like obtained as described above.

The lower the permittivity of the constituent material of the base material, the lower the permittivity of the laminated plate can be achieved, but the lower limit of the permittivity of the constituent material that can be actually used is currently industrialized. The value is 3.0.

The thus obtained prepreg has a low melt viscosity, the molded and cured product has good moldability by suppressing the generation of voids and scratches, has a high glass transition point, and has a mutual glass transition point. It forms an intrusion network structure and has excellent heat resistance.

Further, although the flame retardant is added to improve the flame retardancy, the dielectric constant and the dielectric loss tangent are sufficiently reduced without impairing the properties of PPO.

In the present invention, a laminated board can be produced using the prepreg obtained as described above. That is, one or a plurality of the above prepregs are stacked, metal foil such as copper foil is further stacked on both upper and lower surfaces or one surface thereof, and heat and pressure molding is performed to laminate and integrate them to form a double-sided metal foil. It is possible to produce a laminated sheet having one side covered with metal foil.

By forming a circuit by etching the metal foil on the surface of the laminate thus produced, a printed wiring board having a conductor pattern as a circuit on the surface of the laminate can be obtained. It is a thing. The thus-obtained printed wiring board is formed using the above-mentioned laminated board, and thus has a low dielectric constant and excellent electrical characteristics.

Further, after using this printed wiring board as a printed wiring board for an inner layer and subjecting a metal foil of a conductor pattern to a surface treatment, a plurality of printed wiring boards are stacked via the prepreg obtained in the present invention, A multilayer printed wiring board can be produced by stacking a metal foil on the outermost layer through the prepreg obtained in the present invention, heat-pressing it, and stacking and integrating it. When molding a multilayer printed wiring board in this way, PPO
Since the molecular weight of PPO of the resin composition is as low as 2000 to 12000, the melt viscosity is low, and the fluidity is good, the molding is satisfactorily performed without the occurrence of voids and scrapes, and the resin is sufficiently filled between the conductor patterns. It is possible to obtain a multilayer printed wiring board having high circuit reliability and excellent electrical characteristics.

The above-mentioned respective molding conditions differ depending on the compounding ratio of the respective raw materials of the PPO resin composition and are not particularly limited, but generally a temperature of 170 ° C. or higher 2
It is preferable to heat and pressurize at a temperature of 30 ° C. or less and a pressure of 0.98 MPa or more and 5.9 MPa or less (10 kg / cm ² or more and 60 kg / cm ² or less) for an appropriate time.

The laminated board, the printed wiring board and the multilayer printed wiring board obtained in this manner have suppressed generation of voids and scratches, have a high glass transition point, and form an interpenetrating network structure. It has excellent heat resistance. Further, properties such as water resistance, moisture resistance, and heat resistance after moisture absorption can be further improved.

In addition, although the flame retardant is blended to improve the flame retardancy, the dielectric constant and dielectric loss tangent are sufficiently reduced without impairing the properties of PPO, and the high frequency properties are excellent. is there.

[0064]

EXAMPLES The present invention will be specifically described below with reference to examples.

(Example 1) PPO (manufactured by GE Plastics Co., Ltd .: trade name "Noryl PX9701",
36 parts by weight of a number average molecular weight of 14000), 0.36 parts by weight of bisphenol A as a phenol species, and 0.27 of t-butylperoxyisopropyl monocarbonate (manufactured by NOF Corporation: trade name "Perbutyl I") as an initiator. By mixing 90 parts by mass of toluene and 90 parts by mass of toluene as a solvent, and mixing for 1 hour at 80 ° C. to disperse / dissolve and react them, the molecular weight of PPO The adjustment process was performed. The PPO of the transparent PPO solution obtained after this treatment was 7,800 when the number average molecular weight was measured by gel permeation chromatography (GPC).

The number average molecular weight of 7800 thus obtained
M-TAIC (manufactured by Nippon Kasei Co., Ltd.)
50 parts by mass of styrene / butadiene / compatibilizer
19 parts by mass of a block copolymer (manufactured by Asahi Kasei Kogyo Co., Ltd .: trade name Toughprene A), brominated PPO which is a brominated organic compound as a flame retardant (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .: trade name “Pyroguard SR460B”, Br content 64). % By mass, and α, α ′ bis (t
-Butylperoxy-m-isopropyl) benzene (manufactured by NOF CORPORATION: trade name "Perbutyl-P") was mixed in an amount of 3 parts by mass, and the mixture was mixed in toluene as a solvent.
A varnish of the PPO resin composition was obtained by dispersing and dissolving.

(Examples 2 to 18, Comparative Examples 1 to 4) PPO
The molecular weight was adjusted by setting the type of phenol and the type and amount of initiator as shown in Tables 1 and 2 (however, in Examples 5 and 1).
7, the molecular weight is not adjusted in Comparative Example 2), and the type and amount of TAIC, compatibilizer, flame retardant, and initiator are set in the PPO solution as shown in Tables 1 and 2 and blended. A varnish of the PPO resin composition was obtained by mixing in toluene as a solvent, dispersing and dissolving.

Further, in Examples 11 to 13, the inorganic filler was added, and at this time, the inorganic filler was added after blending the initiator and dispersed with a high-speed stirrer such as a disper.

In Examples 12 and 13, the prepared varnish was subjected to a dispersion treatment using a disperser using beads.

The details of the flame retardant, the inorganic filler, the dispersion treatment (mill treatment) by the disperser using beads, and the base material in the table are as shown in Table 3.

(Evaluation Test) The base materials shown in the table were impregnated with the varnishes of the respective Examples and Comparative Examples, and then dried by heating at a temperature of 120 ° C. for 5 minutes, and the solvent was removed to obtain a resin content of about 50.
A mass% prepreg was obtained.

Copper foil (ST foil) having a thickness of 35 μm is arranged on both sides of this one prepreg, and the temperature is 180 ° C. and the pressure is 2.9.
It was heated and pressed under a molding condition of MPa (30 kg / cm ² ) for 180 minutes to obtain a double-sided copper-clad laminate for an inner layer printed wiring board.

A pattern was formed on this double-sided copper-clad laminate for the inner layer printed wiring board, and the copper foil surface was subjected to blackening treatment to form cores. Two cores were used, one on each side of the core. The prepregs are stacked one by one, and 18 μm thick copper foil (ST foil) is stacked on the upper and lower sides of the prepreg and the temperature is set to 18
0 ° C., pressure 2.9 MPa (30 kg / cm ² ), 180
Heat and pressure were applied under molding conditions of 1 minute to obtain a 6-layer copper-clad laminate for a printed wiring board.

The resulting 6-layer copper-clad laminate was cut into 50 mm ×
After cutting to 50 mm, the outer layer copper foil was removed by etching to obtain a sample for evaluating the formability of a 6-layer board. The moldability was evaluated by comparing the presence or absence of voids (voids) between the inner layer patterns and the transparency after molding (the visibility of the inner layer circuit).

Further, five prepregs were stacked, copper foil (ST foil) having a thickness of 18 μm was stacked on the upper and lower sides thereof, and the temperature was 1
80 ° C., pressure 4.9 MPa (50 kg / cm ² ), 18
It was heated and pressed under a molding condition of 0 minutes to obtain a double-sided copper-clad laminate for a printed wiring board.

The copper foil on the surface of the obtained double-sided copper-clad laminate was removed by etching and cut into 50 mm × 50 mm to obtain a sample for moisture absorption evaluation. Moisture absorption rate is E-
It was measured at 24/50 + C-24 / 60/95. That is, the moisture absorption rate was measured by drying at 50 ° C. for 24 hours and controlling the humidity at 23 ° C. for 24 hours, relative humidity 95% and 60 ° C. for 24 hours.

A double-sided copper-clad laminate is 125 mm × 13 m
Flame resistance was evaluated by a UL method (subject 94) vertical combustion test after cutting into m.

Further, the double-sided copper-clad laminate was cut into an appropriate size, and the dielectric constant and dielectric loss tangent of the laminate at 10 MHz, the glass transition point Tg (viscoelasticity spectrometer tan δ method), and the substrate thickness direction were measured. The thermal expansion coefficient was measured and is shown in Tables 1 and 2. Here, the dielectric constant and the dielectric loss tangent are J
It was measured according to IS C 6481.

[0079]

[Table 1]

[0080]

[Table 2]

[0081]

[Table 3]

From the above results, each of the examples has a high glass transition point, good flame retardancy, low dielectric constant and dielectric loss tangent, and good moldability. Particularly, the total halogen content in the PPO resin composition is 8% with respect to the total weight of the non-solvent organic components in the resin composition.
In Examples 1 to 18, which are in the range of 40 mass%,
It had excellent flame retardancy.

On the other hand, in Comparative Example 1 in which decabromodiphenylethane was used as the flame retardant, the dielectric constant and dielectric loss tangent were not sufficiently reduced, and in Comparative Example 2 in which the number average molecular weight of PPO was large, the moldability was high. Inferior, the flame retardancy was not obtained in Comparative Example 3 containing no flame retardant,
In Comparative Example 4 in which the number average molecular weight was too small, the glass transition point was lowered.

[0084]

The polyphenylene oxide resin composition according to claim 1 of the present invention contains polyphenylene oxide and triallyl isocyanurate as essential components,
The polyphenylene oxide has a number average molecular weight of 200.
The range is from 0 to 12000, and since the halogenated polyphenylene oxide is contained as a flame retardant as a part or all of the polyphenylene oxide, it has good moldability, and the cured product has a high glass transition point, and further a flame retardant. In spite of giving flame retardancy by blending,
The dielectric constant and the dielectric loss tangent can be sufficiently reduced.

The invention of claim 2 uses the halogenated polyphenylene oxide according to claim 1, which has lost all or part of the hydroxyl groups at the terminal of the molecule due to esterification, so that the dielectric constant is further reduced. Is something that can be done.

The invention of claim 3 is the same as in claim 1 or 2, since it contains brominated polyphenylene oxide as the halogenated polyphenylene oxide, flame retardancy is obtained even with a small amount of the flame retardant added, and the dielectric constant and The dielectric loss tangent is sufficiently reduced.

Further, the invention of claim 4 is that in claim 3, since the brominated polyphenylene oxide has a bromination rate of 45% by mass or more and less than 85% by mass, a decrease in glass transition point is prevented and high heat resistance is obtained. It is something that can be maintained.

The polyphenylene oxide resin composition according to claim 5 of the present invention contains polyphenylene oxide and triallyl isocyanurate as essential components, and the polyphenylene oxide has a number average molecular weight of 2
2,000 to 12,000, and since it contains a triallyl isocyanurate halide as a flame retardant as part or all of triallyl isocyanurate, it has good moldability and the cured product has a high glass transition point. Further, the dielectric constant and the dielectric loss tangent can be sufficiently reduced even though the flame retardant is added by adding a flame retardant.

The invention of claim 6 is that in claim 5, since the halogenated triallyl isocyanurate is brominated triallyl isocyanurate, flame retardancy is obtained even with a small amount of the flame retardant added, and the dielectric The index and the dielectric loss tangent are sufficiently reduced.

The polyphenylene oxide resin composition according to claim 7 of the present invention contains polyphenylene oxide and triallyl isocyanurate as essential components, and the polyphenylene oxide has a number average molecular weight of 2
It is in the range of 000 to 12000 and contains a fluorinated aliphatic resin as a flame retardant, so that it has good moldability and the cured product has a high glass transition point. However, the dielectric constant and the dielectric loss tangent can be sufficiently reduced despite the addition of

The invention of claim 8 is the same as in claim 7, wherein the fluorinated aliphatic resin is tetrafluoroethylene resin, tetrafluoroethylene hexafluoropropylene copolymer resin, tetrafluoroethylene-perfluoroalkyl vinyl ether. Since it is at least one of the tetrafluoroethylene-ethylene copolymer resin, the dielectric constant can be further reduced.

Further, the invention according to claim 9 is the method according to any one of claims 1 to 8, wherein the total content of halogen in the solid content of the resin composition is 8% with respect to the total weight of the non-solvent organic components in the resin composition. Since it is blended in an amount of -40% by mass, flame retardancy and heat resistance can be improved in a well-balanced manner.

Further, the invention of claim 10 relates to claims 1 to 9.
In any one of the above, since an inorganic filler is added, the coefficient of thermal expansion of the cured product can be reduced to reduce the dimensional change rate during heating and toughen it, and a highly reliable laminated plate can be obtained. It is possible.

In the method for producing a polyphenylene oxide resin composition according to claim 11 of the present invention, beads are used as a compounding component in preparing the polyphenylene oxide resin composition according to any one of claims 1 to 10. Since the mixture is dispersed and mixed by a disperser, it is possible to prevent unevenness in appearance after molding and to homogenize properties such as flame retardancy, especially when a flame retardant that does not dissolve in a resin component or a solvent is used. is there.

A prepreg according to a twelfth aspect of the present invention is excellent in molding because the base material is impregnated with the polyphenylene oxide resin composition according to any one of the first to tenth aspects and is dried by heating to be semi-cured. In addition to the properties, the cured product has a high glass transition point, and it is possible to sufficiently reduce the dielectric constant and the dielectric loss tangent in spite of adding a flame retardant to impart flame retardancy. Is.

According to a thirteenth aspect of the present invention, in the twelfth aspect, since the constituent material of the substrate has a relative dielectric constant of 5.0 or less, the dielectric constant of the laminated plate obtained by molding the prepreg is It can be further reduced.

The laminated plate according to claim 14 of the present invention is
Since a predetermined number of prepregs according to claim 12 or 13 are laminated by heating and pressurizing, the occurrence of defects such as voids and scrapes is suppressed, the glass transition point is high, and it is difficult to mix a flame retardant. Despite imparting flammability, the dielectric constant and the dielectric loss tangent can be sufficiently reduced.

In the printed wiring board according to the fifteenth aspect of the present invention, since the conductor pattern is formed on the surface of the laminated board according to the fourteenth aspect, the occurrence of defects such as voids and scrapes is suppressed, and the glass transition is high. Despite the fact that it has a point and a flame retardant is added to impart flame retardancy, the dielectric constant and the dielectric loss tangent can be sufficiently reduced, and the high frequency loss is low.

According to a sixteenth aspect of the present invention, in a multi-layer printed wiring board, a conductive pattern is formed on the surface of the laminated board according to the fourteenth aspect, and a predetermined number of prepregs according to the twelfth or thirteenth aspect. In order to laminate molding by heating and pressurizing, the occurrence of defects such as voids and scrapes is suppressed, and also has a high glass transition point, in spite of adding a flame retardant to impart flame retardancy, The dielectric constant and the dielectric loss tangent can be sufficiently reduced, and the high frequency loss is low.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05K 1/03 610 H05K 1/03 610H 610T 630 630B 3/46 3/46 GT (72) Inventor Fukuya Kenichi Osaka Prefecture Kadoma City 1048 Kadoma, Matsushita Electric Works Co., Ltd. (72) Inventor Eiichiro Saito Osaka Kadoma City Kadoma 1048, Matsushita Electric Works Co., Ltd. (72) Inventor Hiroaki Fujiwara Kadoma City, Kadoma 1048 Address Matsushita Electric Works Co., Ltd. (72) Inventor Mao Yamaguchi 1048, Kadoma, Kadoma-shi, Osaka Prefecture Matsushita Electric Works Co., Ltd. F-Term (Reference) 4F072 AA07 AB09 AB28 AB29 AD42 AE07 AE08 AF15 AF32 AG03 AH02 AH21 AJ04 AK06 AL13 4J002 BD132 BJ003 CH071 EU196 FD136 GF00 GQ01 5E346 AA12 AA54 CC08 CC32 DD12 EE09 EE14 HH13

Claims (16)

[Claims] 1. A polyphenylene oxide and triallyl isocyanurate are contained as essential components, and the polyphenylene oxide has a number average molecular weight of 2000 to 120.
And a halogenated polyphenylene oxide as a flame retardant as a part or all of the polyphenylene oxide. 2. The polyphenylene oxide resin composition according to claim 1, wherein the halogenated polyphenylene oxide is one in which all or some of the terminal hydroxyl groups of the molecule have been lost by esterification. 3. The polyphenylene oxide resin composition according to claim 1, which contains brominated polyphenylene oxide as the halogenated polyphenylene oxide. 4. The polyphenylene oxide resin composition according to claim 3, wherein the brominated polyphenylene oxide has a bromination rate of 45% by mass or more and less than 85% by mass. 5. Polyphenylene oxide and triallyl isocyanurate are contained as essential components, and the polyphenylene oxide has a number average molecular weight of 2000 to 120.
And a halogenated triallyl isocyanurate as a flame retardant as part or all of the triallyl isocyanurate, the polyphenylene oxide resin composition. 6. The polyphenylene oxide resin composition according to claim 5, wherein the halogenated triallyl isocyanurate is brominated triallyl isocyanurate. 7. Polyphenylene oxide and triallyl isocyanurate are contained as essential components, and the polyphenylene oxide has a number average molecular weight of 2000 to 120.
And a fluorinated aliphatic resin as a flame retardant, and a polyphenylene oxide resin composition. 8. The fluorinated aliphatic resin is a tetrafluoroethylene resin, a tetrafluoroethylene hexafluoropropylene copolymer resin, a tetrafluoroethylene-perfluoroalkyl vinyl ether or a tetrafluoroethylene-ethylene copolymer resin. The polyphenylene oxide resin composition according to claim 7, which is at least one of the above. 9. The total halogen content in the resin composition solids is 8% based on the total weight of the non-solvent organic components in the resin composition.
The polyphenylene oxide resin composition according to any one of claims 1 to 8, wherein the polyphenylene oxide resin composition is blended in an amount of -40% by mass. 10. The polyphenylene oxide resin composition according to claim 1, wherein an inorganic filler is added. 11. A polyphenylene oxide resin composition, characterized in that, when preparing the polyphenylene oxide resin composition according to any one of claims 1 to 10, the compounding ingredients are dispersed and mixed by a disperser using beads. Manufacturing method. 12. A substrate is impregnated with the polyphenylene oxide resin composition according to claim 1,
A prepreg characterized by being heat-dried and semi-cured. 13. The prepreg according to claim 12, wherein the base material is one whose constituent material has a relative dielectric constant of 5.0 or less. 14. A laminated board formed by laminating and molding a predetermined number of the prepregs according to claim 12 or 13 by heating and pressing. 15. A printed wiring board formed by forming a conductor pattern on the surface of the laminated board according to claim 14. 16. The laminated plate according to claim 14, wherein a conductor pattern is formed on the surface of the laminated plate, and the predetermined number of prepregs according to claim 12 or 13 are heated and pressed to form a laminate. And multilayer printed wiring board.