JP2001326434A - Insulating board for printed wiring board and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method that can obtain an insulating board for a printed-wiring board that contains less halogen by using norbornene- based monomer for stably carrying out ring opening polymerization with high catalytic activity and formation. SOLUTION: In this method for manufacturing the insulating board for the printed-wiring board, reaction liquid concentrate containing at least the norbornene-based monomer, and a complex where a carbene compound containing a hetero atom is subjected to configuration is put into a formation die for massive polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to various communication devices,
The present invention relates to an insulating substrate for a printed wiring board used for electric equipment, electronic equipment, and the like, and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, printed boards used for various industries are manufactured by impregnating a thermosetting resin such as an epoxy resin, a phenol resin, or a polyester resin into paper or glass cloth, drying, and laminating a required number of sheets. Further, a printed circuit board is obtained by forming an electric circuit by etching or the like using a laminated plate formed by laminating and forming a copper foil as a substrate. However, this method has a problem that production steps such as impregnation, drying, lamination molding, and cutting are long and production efficiency is poor. In addition, since the polymer contains a polar group, the electric properties were insufficient such as a large dielectric constant. To overcome these problems, in the production of printed wiring boards and resin encapsulation of electronic and electrical components, the reaction injection molding method (RIM), in which ring-opening polymerization and molding of norbornene-based monomers are simultaneously performed using a metathesis polymerization catalyst. It has been proposed to apply

For example, Japanese Patent Application Laid-Open No. 62-52987 discloses reaction injection molding in which a norbornene-based monomer is polymerized using a metathesis polymerization catalyst system comprising a molybdenum-containing compound or a tungsten-containing compound and an alkyl aluminum halide. A method for manufacturing a wiring board is described. Japanese Patent Application Laid-Open No. Sho 62-105610 discloses that an electric / electronic component is made of a resin by subjecting a norbornene-based monomer to reaction injection molding using a metathesis polymerization catalyst system comprising a molybdenum-containing compound or a tungsten-containing compound and an alkyl aluminum halide. A method of sealing is disclosed.

On the other hand, JP-A-10-147633 describes, as a metathesis polymerization catalyst, a catalyst composition comprising a phosphine complex of ruthenium or osmium and an alkyne. The composition is used for metathesis polymerization and a resin (metathesis polymer) is used. ), The use of the composition for encapsulating resins for electrical or electronic components, and the like. Furthermore, Japanese Patent Application Laid-Open No. H10-14
No. 7634 describes a catalyst composition comprising a phosphine complex of ruthenium or osmium and a hydroxyl group-containing alkyne as a metathesis polymerization catalyst,
The use of the composition for the production of metathesis polymers, the use of the composition for encapsulating resins for electrical or electronic components, etc. are disclosed.

[0005]

However, the above-mentioned Japanese Patent Application Laid-Open No. 62-52987 and Japanese Patent Application Laid-Open No. 62-10561
In the method using a molybdenum-based or tungsten-based metathesis catalyst as described in Japanese Patent Publication No. 0, a resin encapsulant for a printed wiring board or an electric or electronic component is formed at a stroke without performing a post-curing reaction by a low-pressure RIM method. However, there is a problem that the metathesis catalyst is easily deactivated by moisture or oxygen in the air. Further, since a relatively large amount of halogen derived from a cocatalyst such as alkyl aluminum halide is contained in the resin,
There are also problems such as corrosion of metal parts such as copper foil and lead wires and insulation failure due to ion migration. On the other hand, Japanese Patent Application Laid-Open No. H10-1476
The phosphine complex of ruthenium or osmium as described in JP-A-33-33 and JP-A-10-147634 has an advantage of being relatively stable to a catalyst deactivating component such as moisture or oxygen, but has a merit that the catalyst Low activity
In order to obtain a molded article, there is a complicated process in which a pre-curing reaction and a post-curing reaction must be performed. An object of the present invention is to provide an insulating substrate for a printed wiring board having a significantly low halogen content, and a method for manufacturing such an insulating substrate for a printed wiring board with high productivity.

[0006]

Means for Solving the Problems The present inventors have found that a specific ruthenium complex has extremely high activity as a catalyst, and that ring-opening polymerization and molding can be carried out simultaneously in a mold using this.
The inventors have found that an insulating substrate can be obtained without performing a post-curing reaction, and that the halogen content in the obtained insulating substrate is significantly reduced, thereby completing the present invention. Thus, according to the present invention, (1) a reaction solution containing at least a norbornene-based monomer and a complex obtained by coordinating a heteroatom-containing carbene compound with ruthenium is put into a mold and subjected to bulk polymerization. (2) The method for producing an insulating substrate for a printed wiring board according to the above (1), wherein the halogen content of the insulating substrate is 100 ppm or less, (3) The method for manufacturing an insulating substrate for a printed wiring board according to the above (1) or (2), wherein the insulating substrate has a concave portion for accommodating an electronic element, (4) a mold in which the electronic element is disposed. The method for producing an insulating substrate for a printed wiring board according to any one of the above (1) to (3), wherein the undiluted reaction solution is put into the inside and subjected to bulk polymerization, and (5). Consists Li norbornene resin, printed wiring board insulating substrate halogen content is 100ppm or less, is provided.

[0007]

Embodiments of the present invention will be described below in detail. The insulating substrate for a printed wiring board according to the present invention is manufactured by putting a stock solution containing at least a norbornene-based monomer and a specific metathesis polymerization catalyst into a mold and performing bulk polymerization. (Norbornene-based monomer) The norbornene-based monomer that can be used in the present invention is a monomer having a norbornene ring structure, and is a substituted or unsubstituted polycyclic monomer having two or more rings. Specific examples thereof include norbornene, norbornadiene, methylnorbornene, dimethylnorbornene,
Bicyclic norbornenes such as ethyl norbornene, chlorinated norbornene, ethylidene norbornene, chloromethyl norbornene, trimethylsilyl norbornene, phenyl norbornene, cyano norbornene, dicyano norbornene, methoxycarbonyl norbornene, pyridyl norbornene, nadic anhydride, nadimide and the like; dicyclo Tricyclic norbornenes such as pentadiene, dihydrodicyclopentadiene and their alkyl, alkenyl, alkylidene, and aryl-substituted products; tetracyclic compounds such as dimethanohexahydronaphthalene, dimethanooctahydronaphthalene and their alkyl, alkenyl, alkylidene, and aryl-substituted products Norbornenes; pentacyclic norbornenes such as tricyclopentadiene, and hexacyclic norbornenes such as hexacycloheptadecene S; di norbornene compound bound in such hydrocarbon chain or an ester group of two norbornene rings; these alkyl, such as a compound containing a norbornene ring, such as aryl-substituted products thereof.

The above norbornene monomers may be used alone or in combination of two or more, but the use of two or more is preferred. When two or more kinds are used, they become thermoplastic resins.
When appropriately combining a monomer having two double bonds and a monomer having a plurality of double bonds to be a thermosetting resin,
Resins having various physical properties can be obtained. Further, when two or more monomers are used in combination, there is an advantage that even a monomer having a high freezing point temperature can be handled as a liquid by lowering the freezing point as compared with a case where a single monomer is used. Further, an embodiment in which 50% by weight or more of the norbornene-based monomer is copolymerized with a monocyclic cycloolefin such as cyclobutene, cyclopentene, cyclooctene, or cyclododecene or a derivative of a monocyclic cycloolefin having a substituent may be used.

(Metathesis Polymerization Catalyst) The catalyst used in the present invention is not particularly limited as long as it is a complex in which at least one heteroatom-containing carbene compound is coordinated with ruthenium. Or equation b
Is a ruthenium carbene complex represented by

[0010]

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(R ¹ and R ^{2 in} the formulas a and b are
And each independently represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom and a silicon atom. X ¹ and X
² represents any independent anionic ligand. L
¹ represents a hetero atom-containing carbene compounds, ^{L 2} is one of ^{R 1, R 2, X 1} , X 2, L 1 and ^{L 2} showing the hetero atom-containing carbene compound or an electron donor compound any neutral Two, three, four, five or six may be joined together to form a polydentate chelating ligand. In the present invention, a hetero atom is an atom belonging to Group 15 or 16 of the periodic table, and specifically includes a nitrogen atom,
Examples thereof include an oxygen atom, a phosphorus atom, a sulfur atom, an arsenic atom, and a selenium atom. Among them, a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom is preferable for obtaining a stable carbene compound, and a nitrogen atom is particularly preferable.

The carbene compound is a general term for compounds having a methylene free radical, and is a compound having an uncharged divalent carbon atom represented by (> C :). Generally, a carbene compound exists as an unstable intermediate generated during the reaction, but can be isolated as a relatively stable compound due to having a hetero atom.

Examples of the carbene compound containing a hetero atom include a compound represented by the formula (c) or (d) of the following chemical formula 2.

[0014]

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(R ³ and R ^{4 in the} above formulas c and d each independently represent a hydrogen atom, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a carbon atom having 1 to 20 carbon atoms which may contain a silicon atom. Specific examples of the formula c include 1,3-diisopropylimidazolidin-2-ylidene, 1,3-dicyclohexylimidazolidin-2-ylidene, and 1,3-di (methylphenyl) imidazo. Lysine-2-ylidene, 1,3-di (methylnaphthyl) imidazolidin-2-ylidene,
1,3-dimesitylimidazolidine-2-ylidene,
1,3-diadamantylimidazolidine-2-ylidene, 1,3-diphenylimidazolidine-2-ylidene, 1,3,4,5-tetramethylimidazolidine-2
-Ylidene and the like.

Specific examples of the formula d include 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3
-Dicyclohexyl-4-imidazoline-2-ylidene, 1,3-di (methylphenyl) -4-imidazoline-2-ylidene, 1,3-di (methylnaphthyl) -4-
Imidazoline-2-ylidene, 1,3-dimesityl-4
-Imidazoline-2-ylidene, 1,3-diadamantyl-4-imidazoline-2-ylidene, 1,3-diphenyl-4-imidazoline-2-ylidene, 1,3,4,
5-tetramethyl-4-imidazoline-2-ylidene,
1,3,4,5-tetraphenyl-4-imidazoline-
2-ylidene and the like.

In addition to the compounds represented by the formulas c and d, 1,3,4-triphenyl-2,3,4,4
5-tetrahydro-1H-1,2,4-triazole-
5-ylidene, 3- (2,6-diisopropylphenyl) -2,3,4,5-tetrahydrothiazole-2-
Ylidene, 1,3-dicyclohexylhexahydropyrimidine-2-ylidene, N, N, N ', N'-tetraisopropylformamidinylidene, 1,3,4-triphenyl-4,5-dihydro-1H-1 , 2,4-Triazole-5-ylidene, 3- (2,6-diisopropylphenyl) -2,3-dihydrothiazole-2-ylidene and the like can also be mentioned as examples of the heteroatom-containing carbene compound according to the present invention. .

A particularly preferred heteroatom-containing carbene compound is a saturated cyclic compound in which the heteroatom adjacent to the carbene has a bulky substituent, and specific examples thereof include 1,3-diisopropylimidazolidin-2-
Ilidene, 1,3-dicyclohexylimidazolidine-
2-ylidene, 1,3-di (methylphenyl) imidazolidin-2-ylidene, 1,3-di (methylnaphthyl)
Imidazolidine-2-ylidene, 1,3-dimesitylimidazolidine-2-ylidene, 1,3-diadamantylimidazolidine-2-ylidene, 1,3-diphenylimidazolidine-2-ylidene, 1,3,3 4,5-tetraphenylimidazolidine-2-ylidene, 1,3,4-
Triphenyl-2,3,4,5-tetrahydro-1H-
1,2,4-triazole-5-ylidene, 3- (2,
6-diisopropylphenyl) -2,3,4,5-tetrahydrothiazol-2-ylidene, 1,3-dicyclohexylhexahydropyrimidine-2-ylidene, and the like.

The anionic (anionic) ligands X ¹ and X ² of the above formulas a and b may be any ligands having a negative charge when separated from the central metal. . For example, fluorine atom, bromine atom, chlorine atom, halogen atom such as element atom, hydrogen, acetylacetonato group, diketonate group, substituted cyclopentadienyl group, substituted allyl group, alkenyl group, alkyl group, aryl group, alkoxy group , An aryloxy group, an alkoxycarbonyl group, a carboxyl group, an alkyl or aryl sulfonate group, an alkylthio group, an alkenylthio group, an arylthio group, an alkylsulfonyl group, and an alkylsulfinyl group. Preferably it is a halogen atom, more preferably a chlorine atom.

Further, examples of the formula a and the electron donor compound neutral regarding L ² of the formula b, ligand having a neutral charge when separated from the central metal, i.e. any if Lewis base It may be something. Specific examples thereof include oxygen, water, carbonyl, amines, pyridines,
Ethers, nitriles, esters, phosphines,
Examples include phosphinite, phosphite, stibine, sulfoxide, thioether, amide, aromatic compound, cyclic diolefin, olefin, isocyanide, thiocyanate, and the like. Preferred are phosphines, and particularly preferred are trialkylphosphines and triarylphosphines.

R ¹ and R ^{2 in} the formulas a and b are hydrogen; an alkyl group having 1 to 20 carbon atoms, an aryl group, a carboxyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an alkylsulfinyl group,
An alkylthio group, an arylthio group, an alkylsulfonyl group, or an alkylsulfinyl group; an alkenyl group, an alkynyl group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or an alkoxycarbonyl group having 2 to 20 carbon atoms;

Examples of the complex compound represented by the formula a include (1,3-dicyclohexylimidazolidine-2-ylidene) (tricyclohexylphosphine).
Benzylidene ruthenium dichloride, (1,3-dicyclohexyl-4-imidazoline-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dimesitylimimidazolidin-2-yl)
(Ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dimesitylimidazolidine-2-ylidene) (triphenylphosphine) benzylideneruthenium dichloride, (1,3-dimesityl-4-imidazoline-2-ylidene) (Tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dimesityl-4-imidazoline-2)
-Ylidene) (triphenylphosphine) benzylidene ruthenium dichloride, [1,3-di (methylphenyl) imidazolidine-2-ylidene] (tricyclohexylphosphine) benzylidene ruthenium dichloride,
[1,3-di (methylnaphthyl) imidazolidine-2-
[Ylidene] (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3,4,5-tetraphenylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, (1,3-dicyclohexylhexahydropyrimidine-2-yl) Ylidene) (tricyclohexylphosphine)
Ruthenium complex compound in which a heteroatom-containing carbene compound such as benzylidene ruthenium dichloride and a neutral electron-donating compound are coordinated; bis (1,3-diisopropylimidazolidin-2-ylidene) benzylidene ruthenium dichloride, bis (1,3- Dicyclohexylimidazolidine-2-ylidene) benzylidene ruthenium dichloride, bis (1,3-diisopropyl-4-imidazoline-2-ylidene) benzylidene ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) benzylidene ruthenium Ruthenium complex compounds in which two heteroatom-containing carbene compounds such as dichloride are coordinated are exemplified.

Examples of the complex compound represented by the above formula b include (1,3-dicyclohexylimidazolidine-2-ylidene) (tricyclohexylphosphine)
Phenylvinylidene ruthenium dichloride, (1,3-
Dimesityl imidazolidine-2-ylidene) (tricyclohexylphosphine) t-butylvinylidene ruthenium dichloride, (1,3-dimesityl-4-imidazoline-2-ylidene) (tricyclohexylphosphine)
Phenylvinylidene ruthenium dichloride, [1,3-
Di (methylphenyl) imidazolidine-2-ylidene]
(Tricyclohexylphosphine) t-butylvinylideneruthenium dichloride, [1,3-di (methylnaphthyl) imidazolidine-2-ylidene] (tricyclohexylphosphine) phenylvinylideneruthenium dichloride, (1,3,4,5-tetraphenyl Imidazolidine-2-ylidene) (tricyclohexylphosphine)
t-butylvinylidene ruthenium dichloride, (1,3
-Dicyclohexylhexahydropyrimidine-2-ylidene) (tricyclohexylphosphine) phenylvinylideneruthenium dichloride or other heteroatom-containing carbene compound and a ruthenium complex compound in which a neutral electron-donating compound is coordinated; bis (1,3-diisopropyl) Imidazolidine-2-ylidene) phenylvinylideneruthenium dichloride, bis (1,3-dicyclohexylimidazolidine-2-ylidene) t-butylvinylideneruthenium dichloride, bis (1,3-diisopropyl-
Ruthenium complex compound in which two heteroatom-containing carbene compounds such as 4-imidazoline-2-ylidene) t-butylvinylidene ruthenium dichloride and bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylidene ruthenium dichloride are coordinated And the like.

Further, the complex compound represented by the formula a or b is converted to di-μ-chlorobis [(p-cymene) chlororuthenium], di-μ-chlorobis [(p-cymene) chloroosmium], dichloro ( A dinuclear ruthenium-carbene complex compound obtained by reacting with a dinuclear metal complex such as (pentamethylcyclopentadienyl) rhodium dimer can also be mentioned. The amount of such catalyst used,
That is, the ratio of the catalyst to the norbornene monomer is
The molar ratio of the metal ruthenium to the norbornene monomer in the catalyst is usually 1: 2,000 to 2,000,000.
0, preferably 1: 5,000 to 1,000,000,
More preferably, from 1: 10,000 to 1: 500,000.
It is.

The catalyst can be used by dissolving it in a small amount of an inert solvent, if necessary. Such solvents include:
For example, chain aliphatic hydrocarbons such as pentane, hexane and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydroindene Alicyclic hydrocarbons such as cyclohexane and cyclooctane; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; aromatic hydrocarbons such as benzene, toluene and xylene; ether compounds such as diethyl ether and tetrahydrofuran; Solvents such as chlorinated hydrocarbons such as chloroform can be used.
Among these, cyclohexane, which is industrially widely used,
Preferred are toluene, tetrahydrofuran, dichloromethane, chloroform and the like.

(Manufacture of Insulated Substrate and Printed Wiring Board) In the method of manufacturing an insulating substrate for a printed wiring board according to the present invention, ring-opening polymerization and molding of the norbornene-based monomer are simultaneously performed to form an insulating substrate at a stroke. is there. After obtaining the insulating substrate in this way, a conductor circuit can be formed thereon to form a printed wiring board. The thickness of the insulating substrate of the present invention is usually 0.1 to 10.0 m.
m, preferably 0.5 to 5.0 mm. If the thickness of the insulating substrate is too small, the strength may be reduced when the electronic element is embedded. Conversely, if the thickness is too large, it is difficult to obtain a small-sized printed wiring board. On the other hand, the size of the planar area of the insulating substrate is not particularly limited. For example, the insulating substrate can be polymerized using a mold having a unit size of 8 or 12 planes, and cut into unit areas after the polymerization. The method for polymerizing a polynorbornene-based resin constituting the insulating substrate of the present invention is a method of subjecting the above-described norbornene-based monomer to metathesis polymerization. Especially resin transfer molding (RT
It is useful to carry out ring-opening polymerization of norbornene-based monomers in bulk in a mold by the M) method or the reaction injection molding (RIM) method. The mold is used to obtain a molded product having a predetermined shape. These methods need only be substantially lumpy and may include small amounts of inert solvents. In such a bulk polymerization, a reaction solution or a catalyst solution containing a monomer or a catalyst is mixed into a reaction stock solution, and a molding machine conventionally known as an RTM machine or a RIM machine is used as a device for immediately performing a polymerization reaction. be able to.

The RTM machine generally comprises a monomer mixture tank, a catalyst mixture tank, a measuring pump, a mixer and the like. By a metering pump, the monomer mixture and the catalyst mixture are sent to a mixer at a volume ratio of 1000: 1 to 10: 1 to make a reaction stock solution, which is then poured into a mold heated to a predetermined temperature, where it is immediately bulk polymerized and molded. can do. A preferred molding method using an RTM machine is a catalyst compounding solution in which a monomer compounding solution containing a norbornene-based monomer and a complex catalyst in which at least one heteroatom-containing carbene compound is coordinated with ruthenium are dissolved in a small amount of solvent. Are prepared, and these are mixed and molded.

In the RIM machine, two or more kinds of compounded liquids are sent to a mixing head and mixed by collision energy to prepare a reaction stock solution, which is then poured into a high-temperature mold, where it is immediately subjected to bulk polymerization to form a molded article. It is a machine to get. R
In a preferred molding method using an IM machine, a norbornene-based monomer is divided into two parts, and a complex catalyst in which at least one heteroatom-containing carbene compound is coordinated with ruthenium in a third liquid is dissolved in a small amount of a solvent. In this method, the three liquids are used, and the three liquids are subjected to collision mixing to prepare an undiluted reaction solution and to mold it.

In the method of the present invention, a mold having a split mold structure, that is, a mold having a core mold and a cavity mold is usually used, and a reaction stock solution comprising a monomer and a catalyst solution is injected into the gaps (cavities) to form bulk polymerization. Perform The core mold and the cavity mold are formed so as to form a void portion corresponding to the shape of a target molded product. There is no particular limitation on the shape, material and size of the mold. Since it is possible to mold at a relatively low temperature and a low pressure by using a low-viscosity reaction stock solution, not only a metal mold but also various materials such as various synthetic resins and low melting point alloys can be used.

The temperature of the reaction solution before it is fed into the cavity is preferably 20 to 80 ° C. The viscosity of the undiluted reaction solution is usually 2 to 100 at 30 ° C.
0 mPa · s, preferably 5 to 300 mPa · s. The filling pressure (injection pressure) when filling the reaction stock solution into the cavity is usually 0.01 to 10 MPa, preferably 0.02 to 5 MPa. If the filling pressure is too low, the transfer of the transfer surface formed on the inner peripheral surface of the cavity tends to be not performed well.If the filling pressure is too high, the rigidity of the mold must be increased to be economical. is not. The molding temperature is usually room temperature or higher, preferably 40 to 200 ° C,
Particularly preferably, it is 50 to 130 ° C. The mold clamping pressure is usually in the range of 0.01 to 10 MPa. The polymerization time may be appropriately selected, but is usually from 10 seconds to 20 minutes, preferably within 5 minutes.

When the undiluted reaction solution mixed by the above-mentioned RTM machine or RIM machine is injected into the cavity of the molding die, the bulk polymerization reaction is immediately started and hardened. The polymerization reaction is an exothermic reaction, and the temperature of the molded article in the mold gradually decreases as the curing time (curing time) becomes longer. The molded product obtained by bulk polymerization can be usually released from the molded body by opening the molding die while being attached to the core mold. The adhesion of the molded article to the core mold is adjusted by using the property that the higher the mold temperature or the longer the curing time, the higher the possibility of adhesion to the core mold. When the curing time is short, when the mold is opened, the molded article adheres to the cavity mold and remains. When the curing time is long, the molded product is cooled and shrinks, and thus adheres to the core mold. However, even if it adheres to the core mold, if the curing time is too long, shrinkage due to cooling of the molded product will proceed to a considerable extent. What is necessary is just to remove | release from a mold device.

In order to manufacture a printed wiring board, after a flat polynorbornene-based resin insulating substrate is formed by the above-described method, dry plating such as sputtering, electrolytic plating, electroless plating, or the like is performed on the insulating substrate. A conductor layer is formed by wet plating. The conductor circuit can be formed, for example, by forming an etching resist after performing the above-described plating on the entire surface, and etching away unnecessary portions of the plating. Further, after the plating resist film is formed, a predetermined resist pattern is formed, and electroless plating is performed only on portions not covered with the resist. In addition, after performing electroless plating on the entire surface and forming a plating resist, electroless plating is performed on portions not covered with the resist, and the electroless plating layer of the portion covered with the plating resist is removed except for the plating resist. It can be formed by etching away. The thickness of the conductor circuit is as follows.
In the case of a fineness of about 0 μm / 50 μm, a thickness of 15 μm or less is desirable.

For the electroless plating, an electroless plating of copper, nickel, tin or the like is used. As a general reducing agent, formaldehyde is used for the electroless copper plating solution, and hypophosphite ion or hydrazine is used for the electroless nickel plating solution. In the case of electrolytic plating, copper, solder,
Metals such as nickel, rhodium, and gold can be used. The method of forming the conductor circuit is not limited to the above, but a method of placing a mask on an insulating substrate, vacuum-depositing a metal, spraying a metal powder, bonding a copper foil or the like, and then etching. Methods can be used. Also, by laminating the substrates obtained in this way and drilling through holes at required places with a micro drill, applying metal plating to the inner wall of the hole to make each layer conductive, or drilling a via hole before laminating It is also possible to make the layers conductive by stacking them in a state filled with metal powder.

In the method for manufacturing an insulating substrate for a printed wiring board according to the present invention, the metathesis catalyst is hardly deactivated by moisture or oxygen in the air, so that high productivity can be stably maintained for a long period of time. This makes it possible to manufacture the insulating substrate from the liquid raw material at once with high stability and high productivity. In addition, since the method for producing an insulating substrate according to the present invention does not contain halogen, or is polymerized using a polymerization main auxiliary material containing only a very small amount, the halogen content of the insulating substrate is usually 100 ppm or less, preferably 50p
pm or less. Therefore, the insulating substrate for a printed wiring board obtained by the present invention hardly causes corrosion of a metal portion such as a copper foil or a lead wire, and hardly causes insulation failure due to ion migration, so that an extremely high-performance electric / electronic component. Can be formed. Furthermore, the insulating substrate according to the method of the present invention also has a sufficiently small dielectric constant of usually 3 or less, and is therefore useful as an insulating substrate compatible with high frequencies.

The method of manufacturing an insulating substrate for a printed wiring board according to the present invention is more advantageous when manufacturing a chip on which electronic elements such as semiconductors, resistors, and capacitors are mounted. In other words, an electronic device is formed on the upper layer of a molded product that is to be an insulating substrate by polymerizing a norbornene-based monomer using a molding die having a bulged portion inside the top of the molding die to form an insulating substrate. Since the concave portion for storing can be formed, the step of excavating the concave portion after removing the molded product as in the related art is not required, and the productivity is high. In addition, an electronic element can be provided in a molding die in advance, and then a norbornene-based monomer and a catalyst solution can be injected and subjected to bulk polymerization to produce a printed wiring insulating substrate having the electronic element at once. For this reason, it is also possible to omit the step of accommodating the electronic element in the concave portion of the insulating substrate and then sealing it with a resin, which is extremely advantageous in terms of productivity and manufacturing cost. In addition, if the step of forming the concave portion can be omitted, the printed wiring board can be downsized to a certain extent.

[0036]

EXAMPLE 1 5.1 mg of benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride was placed in a 100 ml reaction vessel.
(A halogen concentration of 7 ppm based on the total amount of the resin) and a stirrer were added, and 0.3 ml of toluene was added, followed by stirring with a magnetic stirrer to dissolve the ruthenium catalyst. 60 ml of dicyclopentadiene (containing 10% of cyclopentadiene trimer) was added thereto, and the mixture was stirred.
It was pumped into a mold kept at ° C. After polymerization for 2 minutes, the mold is opened and the length with through hole is 100mm and the width is 100m
m, a molded plate (insulating substrate) having a thickness of 1.8 mm was obtained. Next, an adhesive composed of 50 parts by weight of a phenol resin, 50 parts by weight of an acrylonitrile-butadiene copolymer, 1 part by weight of palladium chloride and 250 parts by weight of butyl cellosolve was applied to the upper and lower surfaces of the molded plate and the inner surface of the through-hole. It was applied to a thickness of 0.05 mm, and after heating, required portions were printed with a plating resist and electrolessly plated to form a printed wiring board. The dielectric constant of the obtained insulating substrate (1 MH
z, JIS C 6481) was 2.8. Also,
The chlorine content measured by atomic absorption analysis is 7.0 pp
m.

Example 2 A mold having a length of 300 mm, a width of 300 mm and a thickness of 1.
It has a rectangular cavity of 6 mm, a grid line of a grid pattern with a width of 1 mm at intervals of 30 mm in both the length direction and the width direction swells inward by 0.3 mm over the entire top surface inside the cavity, and A mold having a square pillar having a length of 1 mm and a width of 1 mm bulged inward by 1 mm in the center was used. The temperature of the mold was 90 ° C. Otherwise, the procedure was the same as in Example 1 to obtain a printed wiring board. The insulating substrate has a grid of 300 mm in length, 300 mm in width and 1.6 mm in thickness, and has a grid of 30 mm in length and 30 mm in width on the upper surface, and a concave portion of 1 mm in length, 1 mm in width and 1 mm in height at the center of each eye. It was a shape having. The dielectric constant of the insulating substrate was 2.7, and the chlorine content was 6.8 ppm.

[0038]

According to the present invention, a printed wiring board characterized in that metathesis polymerization having a high catalytic activity is stably performed using a norbornene-based monomer, and an insulating substrate having a low halogen content is produced at once from a liquid raw material. Is provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) // B29K 45:00 B29K 45:00 B29L 31:34 B29L 31:34 (72) Inventor Tomoo Sugawara Kanagawa 1-2-1, Yakko, Kawasaki-ku, Kawasaki-shi F-term (reference) in the Zeon Corporation General Development Center 4F206 AA12 AH37 JA01 JB12 4J032 CA34 CA38 CB01 CC07 CD02 CE05 CE06 CE22 CG07

Claims (5)

[Claims] 1. An insulation for a printed wiring board, wherein a reaction stock solution containing at least a norbornene-based monomer and a complex obtained by coordinating ruthenium with a heteroatom-containing carbene compound is placed in a mold and subjected to bulk polymerization. Substrate manufacturing method. 2. The method according to claim 2, wherein the insulating substrate has a halogen content of 100.
The method for producing an insulating substrate for a printed wiring board according to claim 1, wherein the amount is not more than ppm. 3. The method for manufacturing an insulating substrate for a printed wiring board according to claim 1, wherein said insulating substrate has a concave portion for accommodating an electronic element. 4. The insulation for a printed wiring board according to claim 1, wherein said undiluted reaction solution is put into a molding die in which an electronic element is disposed and bulk polymerization is performed. Substrate manufacturing method. 5. An insulating substrate for a printed wiring board, comprising a polynorbornene-based resin and having a halogen content of 100 ppm or less.