JPH11124451A - Modified cyanate ester-based resin film and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare the subject film having excellent heat resistance, resistance to solvents and resistance to chemicals, and suitable for a build-up lamination method and having excellent dielectric properties in a high-frequency wave zone by containing a specific cyanate esters compound, a specific phenolic compound, a polyphenylene ether resin and a metallic reaction catalyst, and making the resultant modified cyanate ester-based composition (semi) cure. SOLUTION: This film is obtained by (semi) curing a modified cyanate ester- based curable resin composition comprising (A) a cyanate esters compound e.g. 2,2-bis(4-cyanatophenyl)propane} expressed by formula I (R1 is CH2 , etc.; R2 and R3 are each H or methyl), (B) a monofunctional phenolic compound (e.g. p-tert-octylphenol) expressed by formula II (R4 is CH2 CH3 , etc.), (C) a polyphenylene ether resin e.g. an alloy polymer of poly(2,6-dimethyl-1,4- phenylene) ether with polystyrene} and (D) a metallic reaction catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified cyanate ester resin film used for forming an insulating layer on a printed wiring board and the like, and a method for producing the same.

[0002]

2. Description of the Related Art As electronic devices have become smaller and more sophisticated, there has been a demand for thinner, lighter, and higher-density substrate materials for printed wiring boards. In recent years, a build-up laminate type printed wiring board having an IVH structure, which has a small diameter and connects only necessary layers with non-through holes, has been developed and rapidly spread. The insulating layer of the build-up lamination type printed wiring board is made of a heat-resistant resin not containing a base material such as a glass cloth, and the hole for the IVH is made of photolithography using a photosensitive resin or a thermosetting resin. It is formed by a method such as thermal decomposition by a laser processing machine.

In recent years, the frequency of signals has been increasing in computers and information equipment terminals in order to process a large amount of data at a high speed. However, the higher the frequency, the greater the transmission loss of electric signals. There is a strong demand for the development of printed wiring boards that can handle high frequencies. Transmission loss in a high-frequency circuit is greatly affected by dielectric loss determined by the dielectric properties of an insulating layer (dielectric) around the wiring, and the low dielectric constant and low dielectric loss tangent (t) of the printed wiring board substrate (especially insulating resin)
anδ) is required. For example, in mobile communication related equipment, the quasi-microwave band (1-3G)
(Hz), a substrate having a low dielectric loss tangent is strongly demanded.

Further, electronic information devices such as computers have been equipped with high-speed microprocessors whose operating frequency exceeds 200 MHz, and the delay of high-speed pulse signals on printed wiring boards has become a problem. Since the signal delay time increases in the printed wiring board in proportion to the square root of the dielectric constant εr of the insulator around the wiring, a high-speed computer or the like requires a wiring board substrate having a low dielectric constant.

In response to the above-mentioned technical trends of printed wiring boards, heat-resistant insulating films having low dielectric constant and dielectric loss tangent in a high frequency band and suitable for manufacturing a build-up laminated printed wiring board have been developed. Did not.

Conventionally, as a film material having good dielectric properties, polyphenylene ether (PPO or PP) of a heat-resistant thermoplastic resin (engineering plastics) has been used.
E) Although a resin is known, in order to apply it to an insulating material for a printed wiring board, it is necessary to have a heat resistance that can withstand the solder connection process at the time of mounting and a solvent resistance in other processes at the time of manufacturing the printed wiring board. Improvements in properties and chemical resistance were required.

As a method for improving the heat resistance and the solvent resistance, a method has been proposed in which a polyphenylene ether resin is modified with a thermosetting resin. For example, as a resin film using a cyanate ester resin having the lowest dielectric constant among thermosetting resins, a curable resin prepared by blending a cyanate ester resin with a polyphenylene ether resin as shown in JP-B-1-53700. There is a polyphenylene ether resin-based film using a resin composition. Similarly, as a resin composition using a cyanate ester-based modified resin, a resin composition of a bismaleimide / cyanate ester-modified resin and a polyphenylene ether resin disclosed in JP-B-63-33506 and JP-A-5-33506
There is a resin composition of a modified phenol resin / cyanate ester-based resin and a polyphenylene ether resin disclosed in Japanese Patent No. 311071.

[0008] Further, as a material for imparting thermosetting properties to a polyphenylene ether-based resin which is a thermoplastic resin to improve heat resistance and solvent resistance, crosslinking with a polyphenylene ether resin disclosed in Japanese Patent Publication No. 5-77705 has been proposed. And a film obtained by appropriately cross-linking a specific curable polyphenylene ether resin having an unsaturated group as disclosed in JP-A-7-188362.

[0009]

[Problems to be Solved by the Invention]
The film made of a resin composition in which a cyanate ester resin is blended with a polyphenylene ether resin shown in Japanese Patent Application Laid-Open Publication No. H10-154, has a problem that the compatibility between the resins is poor, and because a cyanate ester is used alone as a curable resin. As for the dielectric properties of the cured resin, although the dielectric constant is relatively better than other compositions described later, the dielectric loss tangent tends to be higher than the value of the dielectric constant. ) Was insufficient.
JP-B-63-33506 and JP-A-5-311071
According to the method disclosed in Japanese Patent Application Laid-Open Publication No. H11-150, the thermosetting resin that modifies the polyphenylene ether resin is a bismaleimide / cyanate ester-modified resin or a modified phenol resin / cyanate ester-based resin, so that the compatibility with the polyphenylene ether resin is slightly better. However, since it contains a thermosetting resin other than the cyanate ester resin, the dielectric properties of the cured resin are worse than the resin modified with the cyanate resin alone, and as a result, the high frequency properties are further insufficient. There was a problem.

[0010] The method disclosed in Japanese Patent Publication No. 5-77705 discloses a method in which a crosslinkable polymer such as polytriallyl isocyanurate and styrene butadiene copolymer and a crosslinkable monomer such as triallyl isocyanurate are blended into a polyphenylene ether resin. Thermosetting (radical polymerizable)
However, since the crosslinkable polymer and monomer are highly polar compounds, there has been a problem that the dielectric properties of the cured resin are deteriorated by the unreacted small components remaining.

The method disclosed in JP-A-7-188362 uses a polymer in which an unsaturated group such as an allyl group is introduced into the polyphenylene ether resin itself. However, polyphenylene ether, which is a thermoplastic resin originally, is used. Because the derivatives are mainly used, the melt viscosity is originally high, and the radical polymerization of unsaturated groups is used, so the curing progresses at once in a chain reaction. In addition, it has the property that the rise rate of the melt viscosity is large, and as a result, the resin cannot be fluidized sufficiently during press molding, resulting in voids and insufficient circuit filling properties, and control of the pressing conditions in the multilayer bonding process There has been a problem that the moldability is poor such as a narrow width.

In view of such a situation, the present inventors have previously proposed a method of using a composition obtained by modifying a specific cyanate ester resin with a monohydric phenol compound as a resin composition for a printed wiring board (Japanese Patent Application No. Hei 9 (1994) -108,197). No. -80033). According to this method, a specific cyanate ester resin can be modified with a monohydric phenol compound to obtain a resin composition having a low dielectric property in a high frequency (GHz) band, particularly a low dielectric loss tangent. There is a problem that the cyanate ester resin is special and expensive.

The present invention is an insulating film having good heat resistance, solvent resistance, and chemical resistance, and suitable for a build-up lamination method which is effective for reducing the thickness, weight, and density of a printed wiring board. It is an object of the present invention to provide a modified cyanate ester-based resin film having a low dielectric constant and a low dielectric loss tangent in a high-frequency band, a low loss property of a high-frequency circuit, and a good moldability such as a circuit filling property, and a method for producing the same. did.

[0014]

The present invention relates to (A) a cyanate ester compound represented by the formula (1), (B)
A modified cyanate ester-based curable resin composition containing, as essential components, a monohydric phenol compound represented by the formula (2), (C) a polyphenylene ether resin, and (D) a metal-based reaction catalyst is semi-cured or cured. It is a modified cyanate ester resin film. Also, the present invention
The modified cyanate ester-based curable resin composition,
(A) With respect to 100 parts by weight of the cyanate ester compound represented by the formula (1), (B) 1 represented by the formula (2)
A curable composition containing 4 to 30 parts by weight of a polyhydric phenol compound, 5 to 500 parts by weight of (C) a polyphenylene ether resin, and 1 to 300 ppm of (D) a metal-based reaction catalyst per 1 g of (A) a cyanate ester compound. The modified cyanate ester-based resin film is preferably a resin composition. Further, (A) a cyanate ester compound and (B) a modified cyanate ester resin obtained by reacting part or all of a monohydric phenol compound, (C) a polyphenylene ale resin, and (D) a metal-based reaction catalyst are essential. The modified cyanate ester-based resin film is preferably a modified cyanate ester-based curable resin composition contained as a component. The present invention provides a modified cyanate ester-based resin film in which a varnish containing the modified cyanate ester-based curable resin composition and a solvent is cast and applied to one surface of a support substrate, and the solvent is removed by heating and drying to form a film. It is a manufacturing method of. Further, in the modified cyanate ester-based curable resin composition, (A) a cyanate ester compound and (B) a monohydric phenol compound were reacted in a solvent solution of a polyphenylene ether resin. It is preferable to prepare a film using a varnish. Further, in an aromatic hydrocarbon solvent solution of (C) a polyphenylene ether resin, (A) a cyanate ester compound and (B) a monohydric phenol compound are reacted to form a varnish. And (C) a solution of the polyphenylene ether resin in an aromatic hydrocarbon solvent,
It is preferable to prepare a varnish by reacting (A) a cyanate ester compound with (B) a monohydric phenol compound, and further blend a ketone-based solvent. The varnish is cast onto one surface of a supporting substrate, and heated. This is a method for producing a modified cyanate ester-based resin film in which a solvent is removed by drying to form a film.

[0015]

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[0016]

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[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is intended to improve the dielectric properties by blending a modified cyanate ester resin having a good dielectric property with a polyphenylene ether resin (C) which is a thermoplastic resin having a good dielectric property. A cyanate ester resin and a polyphenylene ether resin, which are originally incompatible and difficult to obtain a uniform resin,
(C) In a solvent solution of polyphenylene ether resin,
The reaction of (A) a cyanate ester compound and (B) a monohydric phenol compound, so-called “semi-IPN”
A uniform resin varnish for films is produced by the method of conversion, and it is cast and applied to one side of a copper foil or carrier film as a supporting base material, and the resin is made compatible by removing the solvent by heating and drying. A method for producing a modified cyanate ester-based resin film for obtaining a film and a modified cyanate ester-based resin film.

The dielectric properties of polymer materials and the like are greatly affected by the orientation polarization of the dipole. Therefore, the dielectric constant can be reduced by reducing the number of polar groups in the molecule, and the dielectric loss tangent can be reduced by suppressing the mobility of the polar groups. Can be reduced. The cyanate ester resin has a strong polar cyanato group, but generates a symmetric and rigid triazine structure during curing, so that a cured product having the lowest dielectric constant and dielectric loss tangent as a thermosetting resin can be obtained. There is.

However, in the actual curing reaction, it is impossible that all the cyanato groups in the cyanate ester resin react to form a triazine structure, and as the curing reaction proceeds, the reaction system becomes more fluid. And remains in the system as an unreacted cyanato group.
As a result, with the conventional cyanate ester resin, only a cured product having a higher dielectric constant and a higher dielectric tangent than the properties that the original cured product should exhibit can be obtained.

On the other hand, in the resin composition of the present invention,
(B) An appropriate amount of a monohydric phenol compound is mixed with (A) a cyanate ester compound to convert an unreacted cyanato group into imide carbonate to reduce its polarity, thereby reducing the dielectric constant and dielectric loss tangent of the cured product. Is reduced to the original value. As a material used for this purpose, a compound having high reactivity with a cyanato group, a monofunctional compound having a relatively low molecular weight, and having good compatibility with a cyanate ester compound (having similarity in molecular structure) is used. Deemed suitable. The monohydric phenol compound used in the resin composition of the present invention is a compound specified for such a reason.

Conventionally, as a cocatalyst for a trimerization reaction (formation of a triazine ring) of a cyanate ester compound, about 1 to 2 parts by weight of a phenol compound such as nonylphenol is used per 100 parts by weight of the cyanate ester compound. there were. However, since the compounding amount was a catalytic amount, the effect of reducing the polarity by reacting with the unreacted cyanato group as described above was not recognized. However, as a result of the present inventors examining the blending amount of the phenol compound,
It was found that when the phenol compound was added in a larger amount than the conventional catalyst amount, the dielectric constant and the dielectric loss tangent of the cured product were reduced, and when a specific monohydric phenol compound was used, the heat resistance was increased by increasing the compounding amount. Has been found to be able to suppress a decrease in the temperature. Therefore, according to the method of the present invention, a cured product of a conventional cyanate ester resin alone, a conventional epoxy resin or a polyhydric phenol (one of the hydroxyl groups is likely to remain as an unreacted group, so that the dielectric properties are rather deteriorated) and A cured product having a lower dielectric constant and a lower dielectric loss tangent than a cured product of a resin containing bismaleimide or the like can be obtained.

Therefore, in the resin composition of the present invention, the amount of the monohydric phenol compound is important. That is,
If the compounding amount is small, it reacts with all the cyanato groups remaining as unreacted and cannot be reduced in polarity, and if the compounding amount is larger than the required amount, it itself remains unreacted and its own hydroxyl group This is because the polarity deteriorates the dielectric properties of the cured product.

The modified cyanate ester-based curable resin composition used in the modified cyanate ester-based resin film of the present invention comprises (A) a cyanate ester compound represented by the formula (1) and (B) a compound represented by the formula (2). (C) polyphenylene ether resin and (D) a metal-based reaction catalyst as essential components.

The cyanate ester compound (A) in the present invention is a cyanate ester compound having two cyanato groups in one molecule as shown by the formula (1).
Examples of the compound represented by the formula (1) include, for example, bis (4
-Cyanatophenyl) ethane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2-bis (4-cy Anatophenyl) -1,1,1,3,3,3-
Examples thereof include hexafluoropropane, α, α′-bis (4-cyanatophenyl) -m-diisopropylbenzene, and a cyanate ester of a phenol-added dicyclopentadiene polymer. Among them, 2,2-bis (4
-Cyanatophenyl) propane and 2,2-bis (3,
5-Dimethyl-4-cyanatophenyl) methane is preferred because the balance between the dielectric properties and the curability of the cured product is particularly good. Further, (A) the cyanate ester compound is 1
The types may be used alone or as a mixture of two or more types.

The (B) monohydric phenol compound in the present invention is a monohydric phenol represented by the formula (2):
Compounds having good heat resistance are preferred. Examples of the compound represented by the formula (2) include p-tert-butylphenol and p-tert-butylphenol.
-Tert-amylphenol and p-tert-octylphenol, among which p-tert-
Octylphenol is more preferred. As the monohydric phenol compound (B), any one of the above compounds may be used alone, or two or more of them may be used in combination.

In the present invention, the compounding amount of the (B) monohydric phenol compound is (A) the cyanate ester compound 1
The amount is preferably 4 to 30 parts by weight, more preferably 5 to 25 parts by weight, and more preferably 5 to 2 parts by weight with respect to 00 parts by weight.
It is particularly preferable to use 0 parts by weight. If the amount of the (B) monohydric phenol compound is less than 4 parts by weight, sufficient dielectric properties cannot be obtained, and the dielectric loss tangent particularly in a high frequency band tends not to be sufficiently low. If it exceeds 30 parts by weight, the dielectric loss tangent tends to be rather high, which is not desirable. Therefore, in order to obtain a modified cyanate ester-based resin film having a low dielectric loss tangent in a high frequency band,
It is necessary to use (B) a monohydric phenol compound in an appropriate amount with respect to (A) the cyanate ester compound.

The cyanate ester compound (A) and the monohydric phenol compound (B) in the present invention are generally used as a modified cyanate ester resin obtained by reacting each. That is, it is used as an imide carbonate-modified resin in which (A) a cyanate ester compound is prepolymerized and (B) a monohydric phenol compound is added to (A) a cyanate ester compound.

When reacting (A) a cyanate ester compound with (B) a monohydric phenol compound,
(B) A modified cyanate ester resin may be prepared by charging the monohydric phenolic compound from the initial stage of the reaction and then reacting by adding all of the above proper amount, or a part of the above proper amount may be reacted at the beginning of the reaction, After cooling, the remaining (B) monohydric phenol compound may be charged and reacted at the time of B-stage or at the time of curing to obtain a modified cyanate ester resin.

The polyphenylene ether resin (C) in the present invention includes, for example, poly (2,6-dimethyl-
Alloyed polymer of 1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene) ether and polystyrene, poly (2,6-dimethyl-1,4-phenylene) ether and styrene-butadiene copolymer And the like. Among them, poly (2,6)
-Dimethyl-1,4-phenylene) ether and polystyrene alloy and poly (2,6-dimethyl-)
Alloyed polymers of (1,4-phenylene) ether and styrene-butadiene copolymer are preferred. (C) Poly (2,6-dimethyl-) in polyphenylene ether resin
The component amount of 1,4-phenylene) ether is 50% by weight.
The polymer containing the above is preferable because the dielectric properties of the cured product are good, but the polymer containing more than 65% by weight is more preferable.

The amount of the polyphenylene ether resin (C) in the present invention is preferably 5 to 500 parts by weight, more preferably 10 to 300 parts by weight, based on 100 parts by weight of the cyanate ester compound (A). More preferably, it is particularly preferably 15 to 200 parts by weight.
If the compounding amount of the (C) polyphenylene ether resin is less than 5 parts by weight, sufficient dielectric properties tend not to be obtained,
When the amount exceeds 500 parts by weight, the reactivity of the cyanate ester resin (A), which is a thermosetting component, becomes poor due to the dilution effect of the polyphenylene ether resin (C), and the heat resistance and solvent resistance of the obtained resin film deteriorate. Problems arise.

The metal-based reaction catalyst (D) of the present invention comprises (A)
A reaction catalyst for producing a modified cyanate ester-based curable resin composition and a curing accelerator for curing a resin film, which promotes a reaction between a cyanate ester compound and (B) a monohydric phenol compound. Used as As the metal-based reaction catalyst, metal catalysts such as manganese, iron, cobalt, nickel, copper, and zinc are used. Specifically, organic metal salt compounds such as 2-ethylhexanoate and naphthenate and acetylacetone It is used as an organometallic complex such as a complex. The same metal-based reaction catalyst may be used alone as the reaction accelerator for producing the modified cyanate ester-based curable resin composition and the curing accelerator for producing the laminated board, or two or more different each. May be used.

In the present invention, the amount of the metal-based reaction catalyst (D) is preferably 1 to 300 ppm, more preferably 1 to 200 ppm, per 1 g of the cyanate ester compound (A).
ppm is more preferable, and 2 to 150 ppm is particularly preferable. (D) If the amount of the metal-based reaction catalyst is less than 1 ppm, the reactivity and curability tend to be insufficient. If the amount exceeds 300 ppm, the control of the reaction becomes difficult, and the curing becomes too fast, resulting in poor fluidity. And the moldability tends to be poor. In addition, the compounding time of the metal-based reaction catalyst (D) in the present invention may be such that the amounts required as a reaction accelerator and a curing accelerator in the production of the modified cyanate ester-based curable resin composition are simultaneously combined. When using a modified cyanate ester-based curable resin composition, the amount necessary for promoting the modification reaction is used, and after the reaction is completed, the remaining catalyst or another metal-based catalyst is added and mixed as a curing accelerator. Is also good.

The composition used for the modified cyanate ester-based resin film of the present invention may contain, if necessary, a flame retardant, an inorganic filler and other additives in addition to the above essential components. Examples of the flame retardant include brominated phenols such as tribromophenol and tetrabromobisphenol A, brominated epoxy resins such as tetrabromobisphenol A type epoxy resin and brominated novolak type epoxy resin, brominated polystyrene and brominated. Brominated thermoplastic resin such as polycarbonate, polybromodiphenyl ether represented by decabromodiphenyl ether, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclohexane, tetrabromocyclooctane and hexa Brominated hydrocarbon flame retardants such as bromocyclododecane; and brominated triphenyl cyanurate flame retardants such as 2,4,6-tris (tribromophenoxy) -1,3,5-triazine. Among them, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane and 2,4,6-
Flame retardants such as tris (tribromophenoxy) -1,3,5-triazine are preferred because they have no reactivity with cyanate ester compounds and thus have good dielectric properties of the resulting cured product.

In the present invention, the compounding amount of the flame retardant is (A)
Total amount of cyanate ester compound, (B) monohydric phenol compound and (C) polyphenylene ether resin is 1
It is preferably 5 to 50 parts by weight, more preferably 5 to 40 parts by weight, and more preferably 10 to 100 parts by weight.
Particularly preferred is 30 parts by weight. If the amount of the flame retardant is less than 5 parts by weight, the flame resistance tends to be insufficient,
If the amount exceeds 50 parts by weight, the heat resistance of the resin tends to decrease.

As the inorganic filler, silica, alumina,
Aluminum hydroxide, calcium carbonate, clay, talc, silicon nitride, boron nitride, titanium oxide, barium titanate, lead titanate, strontium titanate and the like can be used. The amount is preferably 300 parts by weight or less based on 100 parts by weight of the total amount of the resin composition of the present invention so that the modified cyanate ester-based resin film of the present invention can obtain uniform and good handleability. Preferred.

To produce the modified cyanate ester-based resin film of the present invention, the modified cyanate ester-based curable resin composition described above is dissolved in
A varnish of weight% is cast on one surface of the supporting substrate using a bar coater or a roll coater, and the solvent is removed by heating and drying to form a film (film formation).

Specific examples of the solvent used for producing the above varnish include aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as trichloroethylene and chlorobenzene, and N, N-dimethylformamide. Amides such as N, N, N-dimethylacetamide and nitrogen solvents such as N-methylpyrrolidone. In particular, aromatic hydrocarbons (aromatic hydrocarbon solvents) such as benzene, toluene, and xylene are more preferable.
These solvents may be used alone or as a mixture of two or more. The amount of the aromatic hydrocarbon solvent is 1 to 100 parts by weight of the total amount of the resin composition.
The amount is preferably from 00 to 900 parts by weight, more preferably from 100 to 600 parts by weight, and particularly preferably from 150 to 400 parts by weight.

When ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone are used in combination with aromatic hydrocarbon solvents, the varnish becomes a suspension solution, but the advantage is that a higher concentration solution can be obtained. is there. However, if the amount of the ketone is too large, the resin composition may separate and settle. Therefore, the amount of the ketone solvent is 25 parts by weight based on 100 parts by weight of the aromatic hydrocarbon solvent.
It is preferably 0 parts by weight or less.

As the supporting substrate used in the present invention, a metal foil such as copper or aluminum, a resin film such as polyester or polyimide, or a resin film coated with a release agent on the surface thereof can be used. When a copper foil is used as the supporting base material, there is an advantage that the copper foil can be used as it is as a circuit conductor, and when the supporting base material is subjected to a release agent treatment, the modified cyanate ester is removed from the supporting base material. It is preferable from the viewpoint of improving workability when peeling the base resin film or when peeling off only the support substrate after laminating the film with the support substrate on the substrate.

The modified cyanate ester-based resin film in which the insulating resin layer is formed on one surface of the supporting base material can be used for the production of a printed wiring board by the following method. For example, a modified cyanate obtained by laminating one or a plurality of film-shaped resins from which a supporting base material has been removed, placing copper foil on the upper and lower sides of the resin and press-forming, or applying a varnish to the copper foil as a supporting base material An ester-based resin film is bonded so that the films are bonded together, and if necessary, a modified cyanate ester-based resin film from which the resin film base material has been removed is press-formed with one or more interposed therebetween to form a printed circuit board. Copper clad laminates can be manufactured.

Further, after forming a circuit on the conventional copper-clad laminate of a glass cloth substrate or the above-mentioned copper-clad laminate, one or more modified cyanate ester-based resin films from which the supporting substrate has been removed are laminated, and A substrate for a multilayer wiring board by arranging a copper foil or a circuit forming substrate thereon and press-forming, or arranging a modified cyanate ester-based resin film coated on a copper foil as a supporting base material and press-molding the same. Can be manufactured.

A conventional method can be applied to the formation of the circuit. For example, a perforated or non-perforated hole is formed in the copper clad laminate or the multilayer wiring board substrate as necessary, and then the inner wall of the hole is made conductive by electroless plating or electroplating as necessary. A circuit can be formed by processes such as protection of the substrate, formation of an etching resist, and removal of copper in a non-wiring portion by etching.

Further, in the modified cyanate ester-based resin film of the present invention, drilling and laser processing can be employed as a method for drilling through or non-through holes. In the case of laser processing, laser drilling can be performed by a direct imaging method in which holes are directly formed by laser shots or a conformal mask method using a metal mask, but the modified cyanate ester shown in the present invention is used. When a copper foil, which is an example of a system resin film, is used as a supporting base material, laser drilling can be performed using a copper foil in which a portion where a through or non-through hole is to be formed is removed by etching as a mask.

[0044]

The present invention will be described more specifically with reference to the following examples. A modified cyanate ester-based curable resin composition varnish was produced according to the compounding amounts shown in Table 1, and a semi-cured resin film was produced.

Example 1 450 g of toluene and nonyl PKN4752 as a (C) polyphenylene ether resin (manufactured by Nippon GE Plastics Co., Ltd.) were placed in a 1-liter four-neck separable flask equipped with a thermometer, a cooling pipe, and a stirrer. (Product name) 120 g was charged, heated to 80 ° C., and dissolved by stirring. Next, (A) 2,2-bis (4-cyanatophenyl) propane (ArocyB-10, trade name, manufactured by Asahi Ciba Co., Ltd.) 60 as a cyanate ester compound
g, (B) p-tert as a monohydric phenol compound
-Octylphenol (Wako Pure Chemical Industries, Ltd.) 5 g
After adding and dissolving, (D) 0.8 g of a 10% by weight toluene dilute solution of cobalt naphthenate (Co content = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) was added as a metal-based reaction catalyst, and the mixture was refluxed for 1 hour. Reacted. After cooling to room temperature, a modified cyanate ester-based curable resin composition varnish (solid content = 31% by weight) was produced.

The varnish was coated with a 50 μm-thick polyethylene terephthalate (PET) film (Purex A-63, manufactured by Teijin Co., Ltd.) with a release agent having a thickness of 50 μm using a comma type coater (a type of bar coater, manufactured by Hirano Techseed Co., Ltd.) Co., Ltd.) and dried (130 ° C.) to produce a resin film with a PET film having a resin layer thickness of 30 to 33 μm. The resulting modified cyanate ester-based resin film was excellent in handleability without resin cracking or powder dropping even when cut with a cutter knife.

Example 2 240 g of toluene and a polyphenylene ether resin (nonyl P) were placed in a 1-liter four-neck separable flask equipped with a thermometer, a cooling pipe, and a stirrer.
160 g of KN4752 (trade name, manufactured by Nippon GE Plastics Co., Ltd.) was added, and the mixture was heated to 80 ° C. and dissolved by stirring. Next, 2,2-bis (4-cyanatophenyl) propane (ArocyB-10, trade name, manufactured by Asahi Ciba Co., Ltd.) 8
After dissolving 0 g and 2 g of p-tert-octylphenol (manufactured by Wako Pure Chemical Industries, Ltd.), a 10 wt% toluene diluted solution of manganese naphthenate (Mn content = 8 wt%, manufactured by Nippon Chemical Industry Co., Ltd.) was added. 3 g was added and reacted at reflux temperature for 3 hours. Then, the reaction solution was cooled and the internal temperature was 9
When the temperature reaches 0 ° C, 300 g of methyl ethyl ketone (MEK)
Was added with stirring to suspend. After further cooling to room temperature, 5 g of p-tert-butylphenol (manufactured by Wako Pure Chemical Industries) and 0.2 g of a 10% by weight toluene diluted solution of zinc naphthenate (Zn content = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) were added. The solution was charged and dissolved to produce a modified cyanate ester-based curable resin composition varnish (solid content = 31% by weight).

Using this varnish, a resin film with a PET film having a resin layer thickness of 30 to 33 μm was prepared in the same manner as in Example 1. The resin film obtained was excellent in handleability without resin cracking or powder dropping even when cut with a cutter knife.

Example 3 450 g of toluene and a polyphenylene ether resin (nonyl P) were placed in a 1-liter four-neck separable flask equipped with a thermometer, a cooling pipe, and a stirrer.
105 g of KN4752 (trade name, manufactured by Nippon GE Plastics Co., Ltd.) was charged, heated to 80 ° C., and dissolved by stirring. Next, 2,2-bis (4-cyanatophenyl) propane (ArocyB-10, trade name, manufactured by Asahi Ciba Co., Ltd.) 7
5 g, 15 g of p-tert-octylphenol (manufactured by Wako Pure Chemical Industries, Ltd.), 10% by weight of cobalt naphthenate (Co content = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.)
0.7 g of a diluted toluene solution was added, and the mixture was reacted at a reflux temperature for 2 hours. After cooling the reaction solution to room temperature, zinc naphthenate (Zn content = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.)
Then, 0.1 g of a 10% by weight toluene-diluted solution was added and dissolved by stirring to prepare a modified cyanate ester-based curable resin composition varnish (solid concentration = 31% by weight).

Using this varnish, a resin film with a PET film having a resin layer thickness of 30 to 33 μm was produced in the same manner as in Example 1. The resin film obtained was excellent in handleability without resin cracking or powder dropping even when cut with a cutter knife.

Example 4 450 g of toluene and a polyphenylene ether resin (nonyl P) were placed in a 1-liter four-neck separable flask equipped with a thermometer, a cooling pipe, and a stirrer.
90 g of KN4752 (trade name, manufactured by Nippon GE Plastics Co., Ltd.) was charged, heated to 80 ° C., and dissolved by stirring. Next, 2,2-bis (4-cyanatophenyl) propane (ArocyB-10, trade name, manufactured by Asahi Ciba Co., Ltd.) 9
0 g and 11 g of p-tert-octylphenol (manufactured by Wako Pure Chemical Industries, Ltd.) were added and dissolved. Manganese naphthenate (Mn content = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.)
Was added thereto and reacted at reflux temperature for 6 hours. Then, the mixture was cooled to room temperature to produce a modified cyanate ester-based curable resin composition varnish (solid content concentration = 30% by weight).

Using this varnish, a resin film with a PET film having a resin layer thickness of 30 to 33 μm was produced in the same manner as in Example 1. The resin film obtained was excellent in handleability without resin cracking or powder dropping even when cut with a cutter knife.

Example 5 450 g of toluene and a polyphenylene ether resin (nonyl P) were placed in a 1-liter four-neck separable flask equipped with a thermometer, a condenser, and a stirrer.
60 g of KN4752 (trade name, manufactured by Nippon GE Plastics Co., Ltd.) was charged, and the mixture was heated to 80 ° C. and dissolved by stirring. Next, 120 g of bis (3,5-dimethyl-4-cyanatophenyl) methane (ArocyM-10, trade name of Asahi Ciba Co., Ltd.) and 6 g of p-tert-amylphenol (Wako Pure Chemical Industries, Ltd.) are charged. After dissolution, 0.4 g of a 10% by weight toluene diluted solution of manganese naphthenate (Mn content = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) was added, and the mixture was reacted at reflux temperature for 6 hours. Then, after cooling the reaction solution to room temperature, 0.2 g of a 10% by weight toluene diluted solution of cobalt naphthenate (Co content = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) was added, and the mixture was stirred and dissolved to obtain a modified cyanate ester system. A curable resin composition varnish (solid content = 29% by weight) was produced.

Using this varnish, a resin film with a PET film having a thickness of 30 to 33 μm was prepared in the same manner as in Example 1. The resin film obtained was excellent in handleability without resin cracking or powder dropping even when cut with a cutter knife.

(Comparative Example 1) 360 g of toluene and a polyphenylene ether resin (nonyl P) were placed in a 1-liter four-neck separable flask equipped with a thermometer, a cooling pipe, and a stirrer.
120 g of KN4752 (trade name, manufactured by Nippon GE Plastics Co., Ltd.) was charged, and the mixture was heated to 80 ° C. and dissolved by stirring to produce a varnish (solid content = 25% by weight). Using this varnish, in the same manner as in Example 1, the resin layer thickness 3
A resin film with a PET film of 0 to 33 μm was produced. The resin film obtained was excellent in handleability without resin cracking or powder dropping even when cut with a cutter knife.

Comparative Example 2 In a 1-liter four-neck separable flask equipped with a thermometer, a condenser, and a stirrer, 240 g of methyl ethyl ketone (MEK) and 2,2-bis (4
-Cyanatophenyl) propane (ArocyB-10,
120 g of p-tert-octylphenol (manufactured by Wako Pure Chemical Industries, Ltd.) and 120 g of p-tert-octylphenol were added and dissolved by stirring. Cobalt naphthenate (Co content = 8)
1.2% of a 10% by weight toluene solution of 10% by weight (manufactured by Nippon Chemical Industry Co., Ltd.) was added and reacted at reflux temperature for 2 hours.
Was manufactured. Using this varnish, a resin film with a PET film having a resin layer thickness of 30 to 33 μm was produced in the same manner as in Example 1, but when the obtained resin film was cut with a cutter knife, resin cracking and powder dropping occurred. Occurs, PE
When the T film was peeled off, it could not be handled by the resin film alone.

(Comparative Example 3) In Example 4, 450 g of toluene was added to a polyphenylene ether resin (nonyl PKN).
4752, Nippon GE Plastics Co., Ltd. (90 g) was charged, heated to 80 ° C. and dissolved by stirring, and then 2,2-bis (4-cyanatophenyl) propane (Ar
90 g of the oligomer (ArocyB-30, trade name, manufactured by Asahi Ciba Co., Ltd.) was placed instead of ocyB-10, trade name, manufactured by Asahi Ciba Co., Ltd., and the mixture was heated and melted at 80 ° C. for 1 hour. Then, the mixture was cooled to room temperature, 1 g of nonylphenol (manufactured by Mitsui Toatsu Chemicals, Inc.) instead of p-tert-octylphenol (manufactured by Wako Pure Chemical Industries, Ltd.), and cobalt naphthenate (Co content = 8) instead of manganese naphthenate. 1% of a 10% by weight toluene solution of 10% by weight of Nippon Chemical Industry Co., Ltd.
9% by weight). However, this varnish was observed agglomerated separation of polyphenylene ether resin after one day,
As a result, a resin film could not be produced.

[0058]

[Table 1] Item (A) Cyanate ester (B) Monohydric phenol / polyphenylene ether (D) Metal-based reaction catalyst Example 1 B-10 60 parts POP 5 parts PPO 120 parts Co 0.8 part Example 2 B-10 80 parts POP 2 parts PPO 160 part Mn 0.3 part PBP 5 part Zn 0.2 part Example 3 B-10 75 part POP 15 part PPO 105 part Co 0.7 part Zn 0.1 part Example 4 B-10 90 part POP 11 part PPO 90 part Mn 0.7 part Example 5 M-10 120 parts PAP 6 parts PPO 60 parts Mn 0.4 part Co 0.2 parts Comparative Example 1--PPO 120 parts- Comparative Example 2 B-10 120 parts POP 2 parts-Co 1.2 parts Comparative Example 3 B-30 90 Part NP 1 part PPO 90 part Co 1.0 part Comparative example 4 B-10 60 part BPA 1 part PPO 120 part Co 0.8 part Comparative example 5 B-10 90 part NP 2 part PPO 90 part Mn 0.7 part

(A) B-10 (trade name, manufactured by Asahi Ciba Co., Ltd.);
2-bis (4-cyanatophenyl) propane M-10 (trade name, manufactured by Asahi Ciba Co., Ltd.); bis (3,5-dimethyl
-4-cyanatophenyl) methane B-30 (trade name, manufactured by Asahi Ciba Co., Ltd.); an oligomer of 2,2-bis (4-cyanatophenyl) propane (B) PBP (manufactured by Wako Pure Chemical Industries, Ltd.); p-tert
-Butylphenol PAP (manufactured by Wako Pure Chemical Industries, Ltd.); p-tert-amylphenol POP (manufactured by Wako Pure Chemical Industries, Ltd.); p-tert-octylphenol NP (manufactured by Mitsui Toatsu Chemicals, Inc.); Nonylphenol BPA (Mitsui Bisphenol A, 2,2-bis (4-hydroxyphenyl) propane (C) PPO (Nonyl PKN4752, trade name, manufactured by Nippon GE Plastics Co., Ltd.); Polyphenylene ether resin (D) Co; 10% by weight toluene diluted solution of cobalt naphthenate (Co = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) Zn; 10% by weight toluene diluted solution of zinc naphthenate (Zn = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) Mn: 10% by weight toluene of manganese naphthenate (Mn = 8% by weight, manufactured by Nippon Chemical Industry Co., Ltd.) Interpretation solution

Next, with respect to the resin films with a PET film of Examples 1 to 5, the handleability of the resin film alone and the solvent resistance of the cured film were evaluated. Example 1
The PET film was peeled from the resin film with the PET film, and the obtained 12 resin films were stacked on top and bottom of each other using the mirror surface of the electrolytic copper foil as a peeling surface.
Press molding at 1.5 MPa for 1 hour, thickness about 0.4
A cured film of a modified cyanate ester resin having a thickness of 2 mm was prepared. Similarly, the resin films of Examples 2 to 5 were press-molded to produce cured films of the respective resins. Moreover, about the resin film with a PET film of the comparative example 1, the resin film was peeled off from the PET film, and the 12 sheets were superimposed on top and bottom using the mirror surface of the electrolytic copper foil as a peeling surface, and 200 ° C., 1.5 MPa for 1 hour. Pressing was performed to produce a resin molded film having a thickness of about 0.4 mm. Comparative Example 2
The same procedure was carried out for the resin film with a PET film of the above. However, since the resin film with a PET film of Comparative Example 2 was a film of a cyanate ester resin alone, PET was used.
When the film was to be peeled, the resin film itself was brittle and was broken, so that the film could not be handled alone. As a result, a cured resin film could not be produced.

The above cured resin film was cut into 50 mm square, immersed in toluene, and left at room temperature for 60 minutes. The resin cured films of Examples 1 to 5 did not show any swelling or change in appearance. In addition, Examples 1 to 1 prepared separately
5 was rubbed several times with a cloth impregnated with toluene or methyl ethyl ketone (MEK) to observe the film surface for abnormalities. In the resin cured films of Examples 1 to 5, No abnormalities were seen. From the above, it was confirmed that the resin cured films of Examples 1 to 5 had good solvent resistance.

Similarly, the resin molded film of Comparative Example 1
When cut into 0 mm square, immersed in toluene and allowed to stand at room temperature for 60 minutes, it swelled and partially dissolved because it was a resin molded film of polyphenylene ether alone. When the surface of another resin molded film was rubbed several times with a cloth containing toluene, the surface of the film was melted and sticky occurred. When the surface of another resin molded film was rubbed several times with a cloth impregnated with methyl ethyl ketone (MEK), the film was cracked (cracked), and finally a hole was made and broken. From the above results, it was confirmed that the modified cyanate ester-based resin film of the present invention can be handled by the film alone and has good solvent resistance.

Next, a resin film to which an inorganic filler was added was prepared using the modified cyanate ester-based curable resin composition varnishes of Examples 2 to 5, and the dielectric properties and glass transition of the cured product in the GHz band were obtained. The temperature and tensile modulus were measured.

Example 6 To 170 g of the modified cyanate ester-based curable resin composition varnish of Example 2, 25 g of fused silica powder having an average particle size of 5 μm was added as an inorganic filler.
Further, 200 g of ceramic beads having a diameter of 1.0 mm were put thereinto, and 1500 rpm using a bead mill manufactured by AIMEX.
For 1 hour. After kneading, the varnish from which the beads were filtered out was applied to a thickness of 5 mm using a comma type coater which is a type of bar coater.
Polyethylene terephthalate with a release agent of 0 μm (P
ET) Film (Purex A-63, trade name, manufactured by Teijin Limited) was coated and dried (130 ° C) to produce a resin film with a PET film and a filler having a thickness of 55 to 60 µm with a resin layer (with a filler). . The obtained resin film with a filler was excellent in handleability without resin cracking or powder dropping even when cut with a cutter knife.

Example 7 A resin layer (with filler) having a thickness of 55 to 60 μm was prepared in the same manner as in Example 6 except that the modified cyanate ester-based curable resin composition varnish of Example 3 was used.
m, a resin-filled resin film with a PET film was prepared. The obtained resin film with a filler was excellent in handleability without resin cracking or powder dropping even when cut with a cutter knife.

(Example 8) To 170 g of the modified cyanate ester-based curable resin composition varnish of Example 4, 40 g of fused silica powder having an average particle size of 5 µm was added as an inorganic filler.
Further, 200 g of ceramic beads having a diameter of 1.0 mm were put thereinto, and 1500 rpm using a bead mill manufactured by AIMEX.
For 1 hour. After kneading, the varnish from which the beads were filtered out was applied to a thickness of 5 mm using a comma type coater which is a type of bar coater.
0 μm release agent-treated PET film (Purex A
-63, Teijin Co., Ltd.), and dried (130
° C), and PET with a filler-containing resin layer thickness of 50 to 55 µm
A resin film containing a filler with a film was produced. The obtained resin film with a filler was excellent in handleability without resin cracking or powder dropping even when cut with a cutter knife.

(Example 9) A filler-containing resin film having a thickness of 55 to 60 µm in the same manner as in Example 8 except that the modified cyanate ester-based curable resin composition varnish of Example 5 was used. Was prepared. The obtained resin film with a filler was excellent in handleability without resin cracking or powder dropping even when cut with a cutter knife.

(Comparative Example 4) In Example 1, p-te
Instead of rt-octylphenol, 2,2-bis (4
-Hydroxyphenyl) propane (BPA; bisphenol A, a modified cyanate ester-based curable resin composition varnish (solid content = 29) was reacted in the same manner as in Example 1 except that 1 g of bisphenol A, manufactured by Mitsui Toatsu Chemicals, Inc. was used. % By weight). Using this varnish, kneading and coating with a fused silica powder were carried out in the same manner as in Example 6 to obtain a filler-containing resin layer having a thickness of 5 mm.
A resin film with a filler having a PET film of 5 to 60 μm was produced. The resin film obtained was excellent in handleability without resin cracking or powder dropping even when cut with a cutter knife.

(Comparative Example 5) In Example 4, p-te
The same reaction as in Example 4 was carried out except that 2 g of nonylphenol (manufactured by Mitsui Toatsu Chemicals, Inc.) was used instead of rt-octylphenol, and a modified cyanate ester-based curable resin composition varnish (solid content concentration: 30% by weight) Was manufactured. Using this varnish, kneading and coating were performed with fused silica powder in the same manner as in Example 6, and the filler-containing resin layer thickness 55 to 6
A resin film with a filler having a PET film of 0 μm was prepared. The resin film obtained was excellent in handleability without resin cracking or powder dropping even when cut with a cutter knife.

The PET film was peeled off from the filler-containing resin film with the PET film of Example 6, and the resulting 12 resin-filled resin films and a thickness of 18 μm above and below them.
Electrolytic copper foil was overlaid and press-molded at 200 ° C. and 1.5 MPa for 1 hour to prepare a cured product of double-sided copper-clad resin having a thickness of about 0.6 mm. In the same manner, the resin films with fillers with PET films of Examples 7 to 9 and Comparative Examples 4 and 5 were press-formed with an 18 μm-thick electrolytic copper foil to produce cured double-sided copper-clad resins.

Next, a triplate line resonator having a line length of about 200 mm was manufactured from the cured product of the double-sided copper-clad resin by chemical etching, and the transmission loss in the 1 GHz band was measured using a network analyzer.
The dielectric constant and the dielectric loss tangent at z were determined. In addition, the copper foil was entirely removed by chemical etching, a test piece was cut out from the cured resin containing filler, and a tensile mode (frequency: 10; using a wide area viscoelasticity measuring device (DVE manufactured by Rheology Co., Ltd.)) was used.
Hz, temperature rise; 5 ° C./min), glass transition temperature (Tg)
And tensile modulus / 40 ° C. were measured. Table 2 shows the results.
It was shown to.

[0072]

[Table 2] Item Dielectric properties (1 GHz) Glass transition temperature Tensile modulus Dielectric constant Dielectric loss tangent (° C.) (MPa) Example 6 2.7 0.0044 172 4740 Example 7 2.7 0.0053 174 4780 Example 8 2.8 0.0041 180 5440 Example 9 2.8 0.0045 186 5560 Comparative Example 4 3.3 0.0110 186 4840 Comparative Example 5 3.5 0.0120 170 4220

From Table 2, it can be seen that the filler-containing resin film using the modified cyanate ester-based resin film of the present invention reacts a cyanate ester compound with a specific monohydric phenol to obtain a dielectric property in the GHz band. In particular, it was confirmed that the dielectric loss tangent was low, and that the glass transition temperature and mechanical properties, which serve as a measure of heat resistance, were also good.

Next, a resin film with a copper foil was prepared using each of the varnishes of the modified cyanate ester-based curable resin compositions of Examples 2 to 4, and the properties as multilayer materials for printed wiring boards were evaluated.

(Examples 10 to 12) The modified cyanate ester-based curable resin composition varnishes of Examples 2 to 4 were coated with a comma-type coater, which is a type of bar coater, to a thickness of 18 μm.
Was applied to the roughened surface of the electrolytic copper foil and dried (130 ° C.) to prepare a resin film with a copper foil having a resin layer thickness of 60 to 70 μm for each varnish. The resin film obtained was excellent in handleability without resin cracking or powder dropping even when cut with a cutter knife.

Next, an epoxy resin copper-clad laminate of glass cloth base material (base material thickness: 0.1 mm) on which a conductive circuit was formed was used as an inner layer circuit board (copper foil thickness for circuit; 18 μm), and the test was performed on both surfaces thereof. The resin films with copper foil of Examples 10 to 12 were overlaid so that the resin layer was in contact with the inner layer circuit, and 200 ° C., 2.5MP
Press molding was performed under the conditions of a for 60 minutes to produce a four-layer wiring board.

Comparative Example 6 Using the varnish of Comparative Example 5,
As in Examples 10 to 12, resin layer thickness 60 to 70 μm
Was prepared, and then a four-layer wiring board was prepared in the same manner.

(Comparative Example 7) The same glass cloth base material as used in Examples 10 to 12 was used as the inner layer circuit board, and on both sides thereof, a glass cloth base material for a multilayer wiring board having a nominal thickness of 70 μm. One layer of epoxy resin prepreg (FR-4 grade) and 18 μm thick electrolytic copper foil are laminated,
Press molding was performed at 2.5 ° C. for 60 minutes to prepare a four-layer wiring board.

With respect to the four-layer printed wiring boards of Examples 10 to 12 and Comparative Examples 6 and 7, the moldability (the presence or absence of voids and blurring), solder heat resistance and copper foil peel strength were evaluated by the following methods. Table 3 shows the results.

<Characteristics Evaluation Method> Formability: The outer layer copper foil of the four-layer wiring board was completely removed by chemical etching, and the filling property of resin into the inner layer circuit (the presence or absence of voids and blurring) was visually evaluated.・ Solder heat resistance: Two 50mm square 4-layer plates with outer copper foil
Floating on the molten solder at 60 ° C., and the time until blistering was measured. -Copper foil peel strength: Measured according to JIS-C-6481. -Flame resistance: FR-4 grade 0.2 mm thick copper foil was etched over its entire surface, and a test piece was prepared by pressing both sides of the resin film with copper foil of the example or the comparative example, and UL-94 vertical. It was measured according to the test method.

[0081]

[Table 3] Item Moldability Solder heat resistance (sec) Peel strength (KN / m) Example 10 Wheel, no blur> 180 1.5 Example 11 wheel, no blur> 180 1.5 Example 12 wheel, no blur> 180 1.6 Comparative Example 6 White, no blur 59 1.2 Comparative Example 7 White, no blur> 180 1.5

As apparent from Table 3, Examples 10 to 1
The resin film with a copper foil of No. 2 has good moldability as a multilayer wiring board material, and the resin film with a copper foil of the present invention was used by reacting a modified cyanate ester-based resin with a specific monohydric phenol compound. It was confirmed that the four-layer wiring board had good soldering heat resistance, and had the same properties as the adhesive prepreg using the conventional glass cloth as the base material.

[0083]

The modified cyanate ester-based resin film of the present invention can be handled by itself and has excellent solvent resistance, and the cured product has a low dielectric constant and dielectric loss tangent in a high frequency band, and has a glass transition. High temperature and elastic modulus, and good moldability, solder heat resistance, copper foil peel strength, etc. as a multilayer wiring board material, so printing used in equipment that handles high-speed digital signals and high-frequency signals related to wireless communication It is an insulating resin film suitable for manufacturing a wiring board, particularly by a build-up lamination method. By using the resin film of the present invention, it becomes possible to easily manufacture a printed wiring board suitable for increasing the speed of a computer and reducing the loss of high-frequency related equipment.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Harumi Negishi 1500 Ogawa Oji, Shimodate City, Ibaraki Pref.Hitachi Chemical Industry Co., Ltd.

Claims (11)

[Claims] (A) a cyanate ester compound represented by the formula (1), (B) a monohydric phenol compound represented by the formula (2), (C) a polyphenylene ether resin, and (D) a metal-based reaction. A modified cyanate ester-based resin film obtained by semi-curing or curing a modified cyanate ester-based curable resin composition containing a catalyst as an essential component. Embedded image Embedded image 2. The modified cyanate ester-based curable resin composition is prepared by adding (B) a monohydric phenol compound to 4 to 3 parts by weight of 100 parts by weight of (A) a cyanate ester compound.
0 parts by weight, (C) 5 to 50 polyphenylene ether resin
The modified cyanate ester resin film according to claim 1, wherein the curable resin composition is a curable resin composition in which 0 parts by weight and (D) 1 to 300 ppm of a metal reaction catalyst (A) are added to 1 g of the cyanate ester compound. 3. The modified cyanate ester-based curable resin composition comprises (A) a cyanate ester compound and (B) 1
Cyanate ester-based curable resin composition containing (C) polyphenylene ale resin and (D) metal-based reaction catalyst as essential components The modified cyanate ester-based resin film according to claim 1 or 2, wherein 4. The method according to claim 1, wherein (A) the cyanate ester compound is
4. The method according to claim 1, wherein the compound is at least one of 2,2-bis (4-cyanatophenyl) propane and 2,2-bis (3,5-dimethyl-4-cyanatophenyl) methane. A modified cyanate ester-based resin film as described in the above item. 5. The method according to claim 1, wherein (B) the monohydric phenol compound is p-
The modified cyanate ester-based resin film according to any one of claims 1 to 4, wherein the modified cyanate ester-based resin film is at least one of tert-butylphenol, p-tert-amylphenol, and p-tert-octylphenol. 6. The polyphenylene ether resin (C),
An alloyed polymer of poly (2,6-dimethyl-1,4-phenyler) ether and polystyrene or styrene-butadiene copolymer, wherein poly (2,6-dimethyl-1,4-phenyler) ether is 50% by weight. The modified cyanate ester-based resin film according to any one of claims 1 to 5, which contains the above. 7. (D) The metal-based reaction catalyst is manganese,
7. The modified cyanate ester-based resin film according to claim 1, which is at least one selected from 2-ethylhexanoate, naphthenate and acetylacetone complex of iron, cobalt, nickel, copper or zinc. . 8. A varnish containing the modified cyanate ester-based curable resin composition according to claim 1 and a solvent is applied to one surface of a supporting substrate by casting, and the solvent is removed by heating and drying. A method for producing a modified cyanate ester-based resin film, comprising forming a film. 9. The modified cyanate ester-based curable resin composition according to any one of claims 1 to 7, wherein (A) a cyanate ester compound and (A) a solvent solution of a polyphenylene ether resin. B) Manufacture of a modified cyanate ester resin film characterized by reacting a monohydric phenol compound to produce a varnish, casting and applying the varnish to one surface of a support substrate, removing the solvent by heating and drying, and forming a film. Method. 10. The modified cyanate ester-based curable resin composition according to any one of claims 1 to 7, wherein (A) cyanate in a solution of the polyphenylene ether resin in an aromatic hydrocarbon solvent. The method for producing a modified cyanate ester-based resin film according to claim 9 or 10, wherein a varnish is produced by reacting the ester compound with the (B) monohydric phenol compound. 11. The modified cyanate ester-based curable resin composition according to any one of claims 1 to 7, wherein (C) a cyanate ester solution in a solution of a polyphenylene ether resin in an aromatic hydrocarbon solvent. The production of the modified cyanate ester resin film according to any one of claims 8 to 10, wherein the ester compound is reacted with the (B) monohydric phenol compound, and a varnish is prepared by further mixing a ketone solvent. Method.