JP3319116B2 - Crosslinkable norbornene-based resin composition and molded article comprising the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crosslinkable norbornene-based resin composition having excellent electrical insulation, a crosslinkable molded article comprising the same, and a crosslinked molded article.

[0002]

2. Description of the Related Art Circuits for precision equipment such as electronic calculators and communication devices have been required to have higher speed, higher reliability and higher density of arithmetic processing with the advancement of technology.
High performance such as high precision and miniaturization is progressing.

Hitherto, such a circuit board has been made of phenol resin, epoxy resin, polyimide resin, fluororesin, polybutadiene resin, etc., and is being improved in accordance with the progress of technology (Japanese Patent Laid-Open No. 60-1985).
-84317, JP-A-60-258233, JP-A-60-202130, JP-A-3-37256, JP-A-3-55237, JP-A-3-166256, JP-A-3-275760 and the like.

However, phenolic resins, epoxy resins,
Thermosetting resins such as polyimide resins usually have a high dielectric constant of 4.0 or more and a dielectric loss tangent of 0.01 or more, and therefore have difficulty in electrical characteristics. It has been difficult to increase processing speed and increase reliability. On the other hand, a prepreg laminate using a thermoplastic resin such as a fluororesin or a polybutadiene resin is inferior in heat resistance.Therefore, cracking or peeling may occur at the time of soldering, and dimensional stability is poor. Was difficult.

Recently, there has been proposed a method for improving heat resistance, solvent resistance, and the like by cross-linking a thermoplastic norbornene resin with an organic peroxide. For example, Japanese Patent Application Laid-Open
No. 34924 discloses a method in which a resin and a crosslinking aid are kneaded, then pulverized, impregnated with an organic peroxide solution, and the solvent is removed, followed by press molding and crosslinking. . However, such a procedure has problems that the steps are complicated, the efficiency is low, and the organic peroxide is not always uniformly dispersed. Further, the thermoplastic norbornene-based resin disclosed in the publication is a copolymer of a norbornene-based monomer and ethylene, and an undisclosed hydrogenated ring-opened norbornene-based resin is crosslinked with an organic peroxide by this method. Attempts have often been made to reduce the molecular weight due to decomposition of the polymer, and it has been found that heat resistance required for soldering or the like cannot be obtained.

Japanese Patent Application Laid-Open No. 2-255848 discloses that a thermoplastic norbornene resin including a hydrogenated ring-opened norbornene resin includes an amorphous or low-crystalline α-olefin copolymer and an amorphous resin. Alternatively, it is disclosed that a resin composition containing a low-crystalline styrene copolymer is crosslinked using an organic peroxide, but hydrogenated ring-opened norbornene resins are specifically crosslinked. There is no disclosure of crosslinking a hydrogenated ring-opened norbornene-based resin containing no such special resin using an organic peroxide. Further, in this publication, a method of blending such a resin composition with an organic peroxide, a crosslinking aid, and a flame retardant to perform crosslinking, and blending a resin and an organic peroxide and then blending a flame retardant after blending. However, in the method of blending the flame retardant after crosslinking, when used in a prepreg laminate or the like, there is a problem that the flame retardant is difficult to uniformly disperse and is not practical. When compounding a flame retardant,
When only a hydrogenated ring-opened norbornene resin is used as the resin, the flame retardants exemplified in the publication do not uniformly disperse because they are modified with an organic peroxide and cannot obtain sufficient flame retardancy. There was a problem that there was something.

[0007]

The inventors of the present invention have conducted intensive studies on the development of a molded article made of a resin having excellent heat resistance, a low dielectric constant and a low dielectric loss tangent. The inventors have found that when an organic peroxide and a crosslinking agent are uniformly dispersed in a norbornene-based resin, crosslinking can be performed without decomposing the polymerization zone, and the present invention has been completed.

[0008]

Thus, according to the present invention, 0.001 to 30 parts by weight of an organic peroxide and 1 part by weight of an organic peroxide are added to 100 parts by weight of a thermoplastic hydrogenated ring-opened norbornene resin. Uniform crosslinkable norbornene-based resin composition in which 0.1 to 10 parts by weight of a crosslinking assistant is dispersed per part, crosslinkable molded article comprising the crosslinkable norbornene-based resin composition, and the crosslinkable molded article To provide a cross-linked molded article obtained by heating and cross-linking.

(Thermoplastic hydrogenated ring-opened norbornene resin) The thermoplastic hydrogenated ring-opened norbornene resin used in the present invention is disclosed in JP-A-3-14882 or JP-A-3-12.
It is a resin known in, for example, No. 2137, and specifically, a hydrogenated product of a ring-opened polymer of a norbornene-based monomer.

The norbornene-based monomer is also a monomer known in the above publication, JP-A-2-227424, JP-A-2-276842, etc., for example, norbornene, its alkyl, alkylidene, aromatic-substituted derivatives. And halogens, hydroxyl groups of these substituted or unsubstituted olefins,
Polar group substituents such as an ester group, an alkoxy group, a cyano group, an amide group, an imide group, and a silyl group, for example, 2-norbornene, 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, 5- Ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-
2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-phenyl-2-norbornene, 5-phenyl-5-methyl- 2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-octadecyl-2-norbornene, and the like; a monomer obtained by adding one or more cyclopentadiene to norbornene, and a derivative similar to the above. And substituents, for example, 1,4: 5,8-dimethano-1,2,3,4,4a, 5,8,8a-2,3-cyclopentadienonenaphthalene, 6-methyl-1,4: 5,
8-Dimethano-1,4,4a, 5,6,7,8,8a-
Octahydronaphthalene, 1,4: 5,10: 6,9-
Trimethano-1,2,3,4,4a, 5,5a, 6
9,9a, 10,10a-Dodecahydro-2,3-cyclopentadienoanthracene and the like; a monomer having a polycyclic structure which is a multimer of cyclopentadiene, and derivatives and substituents similar to those described above, for example, dicyclopentadiene Pentadiene, a few
-Dihydrodicyclopentadiene and the like; adducts of cyclopentadiene with tetrahydroindene and the like, derivatives and substituents similar to those described above, for example, 1,4-methano-1,
4,4a, 4b, 5,8,8a, 9a-octahydrofluorene, 5,8-methano-1,2,3,4,4a,
5,8,8a-octahydro-2,3-cyclopentadienonaphthalene and the like.

The ring-opening polymerization of the norbornene-based monomer may be carried out by a known method, and if necessary, may be copolymerized with another copolymerizable monomer. The polymer was converted into an α, β-unsaturated carboxylic acid and / or
Alternatively, it may be modified using a derivative thereof, a styrene-based hydrocarbon, an organosilicon compound having an olefin-based unsaturated bond and a hydrolyzable group, or an unsaturated epoxy monomer.
By hydrogenating these resins, thermoplastic hydrogenated ring-opened norbornene resins are obtained. The resin may be modified after hydrogenation.

The molecular weight of the hydrogenated ring-opened norbornene resin is from 10,000 to 200,000, preferably from 20,000 to 20,000 in terms of polystyrene as measured by GPC (gel purging chromatography) using cyclohexane as a solvent. 100,000, more preferably 25,
000 to 50,000. If the number average molecular weight is too small, the mechanical strength will be poor, and if it is too large, the moldability will be poor. The hydrogenation rate is 90% or more, preferably 95% or more, and more preferably 99% or more, in order to improve the heat deterioration resistance and the light deterioration resistance.

In the hydrogenated ring-opened norbornene resin used in the present invention, a phenol-based or phosphorus-based antioxidant; a phenol-based thermal deterioration inhibitor; a benzophenone-based compound, as long as it can be uniformly dispersed. UV stabilizers; amine-based antistatic agents; lubricants such as aliphatic alcohol esters, polyhydric alcohol partial esters and partial ethers; and the like.

(Organic peroxide) The organic peroxide used in the present invention is not particularly limited, and may be those known in JP-A-62-34924, for example, t-butyl hydroperoxide and p-butyl peroxide. -Hydroperoxides such as menthane hydroperoxide and cumene hydroperoxide; dicumin peroxide, t-butyl cumin peroxide,
dialkyl peroxides such as α, α′-bis (t-butylperoxy-m-isopropyl) benzene; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; 2,5-dimethyl-2,5
-Di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-
3,1,3-di (t-butylperoxyisopropyl)
Peroxy ketals such as benzene; Peroxy esters such as t-butyl peroxy acetate and t-butyl peroxy benzoate; Peroxy carbonates such as t-butyl peroxy isopropyl carbonate and di (isopropyl peroxy) dicarbonate Ketone peroxides; and the like.

(Crosslinking Aid) The crosslinking aid used in the present invention also comprises
There is no particular limitation, and those known in JP-A-62-34924 and the like may be used, and oxime / nitroso-based crosslinking assistants such as quinone dioxime, benzoquinone dioxime, p-nitrosophenol, etc .; N, Nm-phenylene Maleimide-based crosslinking assistants such as bismaleimide; diallyl phthalate,
Allyl-based crosslinking aids such as triallyl cyanurate and triallyl isocyanurate; methacrylate-based crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; vinyl-based crosslinking aids such as vinyl toluene, ethyl vinyl benzene, and divinyl benzene And the like. Among them, allyl-based cross-linking assistants and methacrylate-based cross-linking assistants are preferable because they are easily dispersed uniformly.

(Crosslinkable Norbornene Resin Composition) The crosslinkable norbornene resin composition of the present invention has a uniform composition obtained by adding an organic peroxide and a crosslinking assistant to a thermoplastic hydrogenated ring-opened norbornene resin. Things.

If the amount of the organic peroxide is too small, crosslinking is difficult to occur. Therefore, 0.001 part by weight or more, preferably 0.01 part by weight, per 100 parts by weight of the thermoplastic hydrogenated ring-opened norbornene resin. Parts or more, more preferably 0.05 parts by weight or more, particularly preferably 1 part by weight or more of an organic peroxide. Further, if the added amount of the organic peroxide is too large, the electrical properties, water resistance, moisture resistance, etc. of the crosslinked resin are reduced, so that 30 parts by weight based on 100 parts by weight of the thermoplastic hydrogenated ring-opened norbornene resin, The organic peroxide is preferably added so as not to exceed 15 parts by weight, more preferably 10 parts by weight, particularly preferably 5 parts by weight.

The amount of the crosslinking aid is 0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 1 part by weight of the organic peroxide.
It is 2 to 5 parts by weight. If the amount of the crosslinking aid is too small, crosslinking is unlikely to occur, and the hydrogenated ring-opened norbornene-based resin is decomposed to reduce the molecular weight, so that heat resistance required for soldering cannot be obtained. If the amount of the crosslinking aid is too large, the electrical properties, water resistance, moisture resistance, etc. of the crosslinked resin are undesirably reduced.

Furthermore, in order to enhance the flame retardancy of the crosslinked molded article of the present invention, it is preferable that the flame retardant is uniformly dispersed in the norbornene-based resin composition of the present invention. The flame retardant used in the present invention can be uniformly dispersed as a resin composition, and is decomposed, denatured, or degraded by an organic peroxide in a state where the resin composition is blended or in a crosslinking reaction step. Those that do not are preferred.
Specifically, general formula 1

Embedded image (In the general formula 1, n, m ₁ , m ₂ , m ₃ , and m ₄ are integers,
n ≧ 0, 1 ≦ m ₁ ≦ 5, 1 ≦ m ₂ ≦ 4, 1 ≦ m ₃ ≦ 4, 1
≦ m ₄ ≦ 5, preferably 2 ≦ m ₁ ≦ 4, 2 ≦ m ₂ ≦ 3,2
≦ m ₃ ≦ 3, 2 ≦ m ₄ ≦ 4, particularly preferably m ₁ = 3, m ₂
= 2, m ₃ = 2, m ₄ = 3) or general formula 2

Embedded image(In the general formula 2, n, m₁, M_Two, M_Three, M_Four, M_Five, M₆Is in order
A number, n ≧ 0, 1 ≦ m₁≦ 5, 1 ≦ m_Two≦ 5, 1 ≦ m
_Three≦ 4, 1 ≦ m_Four≦ 4, 1 ≦ m_Five≦ 5, 1 ≦ m₆≦ 5, preferred
Or 2 ≦ m₁≦ 4, 2 ≦ m_Two≦ 4, 2 ≦ m_Three≦ 3, 2 ≦
m_Four≦ 3, 2 ≦ m_Five≦ 4, 2 ≦ m₆≦ 4, particularly preferably
m₁= 3, m_Two= 3, m_Three= 2, m_Four= 2, m_Five = 3, m₆=
3) can be uniformly dispersed, and
Not decomposed, denatured or deteriorated by organic peroxides. The amount of addition
5 to 100 parts by weight of hydrogenated ring-opened norbornene resin
To 150 parts by weight, preferably 20 to 140 parts by weight, especially
Preferably it is 40 to 120 parts by weight.

The method for uniformly dispersing the organic peroxide, the crosslinking aid, and, if necessary, the flame retardant in the hydrogenated ring-opened norbornene resin is not particularly limited. There are a method of dispersing and removing the solvent, and a method of mixing and dispersing the ring-opened resin in a molten state. The solvent for the ring-opening resin is not particularly limited as long as the solvent can dissolve the ring-opening resin, and for example, toluene, xylene, ethylbenzene, chlorobenzene and the like can be used. In the method in which the ring-opening resin is melted to mix and disperse the organic peroxide and the like, it must be able to melt, mix and disperse at a temperature that does not cause cross-linking. Depending on the combination of auxiliaries, this method cannot be used. Even in the method of mixing and dispersing in the ring-opening resin solution, when heating to remove the solvent, it is necessary to set the temperature so that crosslinking does not occur.

(Crosslinkable Molded Article) In the present invention, a crosslinkable norbornene-based resin composition is molded and then crosslinked to obtain a crosslinkable molded article.

The method for molding the crosslinkable norbornene-based resin composition may be carried out by dissolving in a solvent or by molding, or at a temperature at which crosslinking is not performed, or at a crosslinking rate sufficient to prevent deterioration in moldability due to crosslinking during molding. And melt at a slow temperature. As the solvent, a solvent that dissolves the above-mentioned hydrogenated ring-opened norbornene resin is used. Generally, it is dissolved in a solvent and molded.

Specifically, a crosslinkable norbornene-based resin composition dissolved in a solvent is cast to form a sheet or film by removing the solvent, or a glass cloth, aramid cloth, polyester cloth, nylon cloth, or the like. A cloth-like base material, a mat-like base material of the same material as these, a non-woven fabric, kraft paper, linter paper, etc. are impregnated and formed into a base material. As the crosslinkable molded article in which the base material is impregnated with the resin composition, a prepreg is exemplified.

(Crosslinking) In the present invention, a crosslinkable molded article is obtained by heating a crosslinkable molded article alone or by laminating it at a certain temperature or higher. The temperature at which the cross-linking reaction occurs is determined mainly by the combination of the organic peroxide and the cross-linking aid, but is generally 80 to 350 ° C, preferably 120 to 300 ° C, and more preferably 150 to 2 ° C.
Crosslinking is achieved by heating to a temperature of 50 ° C. The crosslinking time is preferably about 4 times the half-life of the organic peroxide, generally 5 to 120 minutes, preferably 10 to
90 minutes, more preferably 20 to 60 minutes. When cross-linking is performed by laminating cross-linkable molded articles, heat fusion and cross-linking occur between the respective layers, and an integrated cross-linked molded article is obtained.

(Crosslinked Molded Product) Examples of the crosslinked molded product of the present invention include crosslinked products such as laminated boards, circuit boards, interlayer insulating films, and films for forming moisture-proof layers.

The crosslinked molded article of the present invention usually has a water absorption of 0.03% or less and an insulation resistance of 10 ¹⁵ to 10 ¹⁷ Ω, 1 MH
the dielectric constant at z and the dielectric loss tangent are 2.0 to 2.5, respectively.
0.0001 to 0.0007, which is superior to conventional thermosetting resin molded products in water resistance and electrical properties.
On the other hand, the heat resistance is the same as that of a conventional thermosetting resin molded product. It is not allowed. For these reasons, the crosslinked molded product of the present invention is also preferred as a circuit board.

The crosslinked molded article of the present invention is excellent in flame retardancy, specifically, V-2 according to UL-94 standard.
Or those exhibiting superior flame retardancy are preferred,
Those exhibiting V-1 or V-0 flame retardancy are more preferred, and those exhibiting V-0 flame retardancy are particularly preferred. In order to obtain such a crosslinkable molded article, a crosslinkable norbornene-based resin composition containing the above-described flame retardant may be used.

(Prepreg) In the prepreg which is one of the specific examples of the crosslinkable molded article of the present invention, the base material is not particularly limited, and glass cloth, aramid cloth, polyester cloth, and the like generally used as a prepreg and a substrate are used. Cloth-like base materials such as nylon cloth, mat-like base materials of the same material, nonwoven fabric, kraft paper, linter paper and the like can be used.

The preparation of a prepreg using the crosslinkable norbornene resin composition of the present invention may be carried out in accordance with a conventional method. For example, a crosslinkable norbornene resin composition having a concentration of 5 in a solvent such as toluene, cyclohexane or xylene may be used. ~ 50% by weight
The solvent may be removed by dissolving the solution to a certain extent, impregnating the substrate with the solution, and then drying the solution. Generally, it is preferable that the prepreg has a thickness of about 50 to 500 μm.

(Sheet) The method for producing a sheet, which is one of the specific examples of the crosslinkable molded article of the present invention, is not particularly limited. Generally, a casting method is used. For example,
The crosslinkable norbornene-based resin composition of the present invention is dissolved and dispersed in a solvent such as toluene, xylene, or cyclohexane so as to have a concentration of about 5 to 50% by weight, cast or coated on a smooth surface, and dried. The solvent is removed, and the sheet is peeled off from the smooth surface to obtain a sheet. When removing the solvent by drying, it is preferable to select a method that does not foam by rapid drying, for example, after volatilizing the solvent at a low temperature to some extent, raise the temperature to sufficiently volatilize the solvent. do it. As the smooth surface, a mirror-finished metal plate or a resin carrier film may be used. When a resin carrier film is used, the solvent to be used and the drying conditions must be determined while paying attention to the solvent resistance and heat resistance of the material of the carrier film. The sheet obtained by the casting method generally has a thickness of about 10 μm to 1 mm. These sheets can be used as an interlayer insulating film, a film for forming a moisture-proof layer, etc. by crosslinking. Moreover, it can also be used for the production of a laminate described below.

(Laminated Plate) A laminated plate, which is one of the specific examples of the crosslinked molded product of the present invention, is formed by stacking the above-mentioned prepreg and / or uncrosslinked sheet, and heat-press-molding them to perform crosslinking and heat fusion. Thus, the required thickness is obtained.
When the laminate is used as a circuit board, for example, a circuit is formed by laminating a conductive layer for wiring made of metal foil or the like, or by etching the surface. The conductive layer for wiring may be laminated not only on the outer surface of the finished laminate, but also inside the laminate depending on the purpose or the like.
To prevent warpage during secondary processing such as etching,
It is preferable to laminate in combination with the upper and lower objects. For example, the surface of the laminated prepreg and / or sheet is heated to a temperature equal to or higher than the heat fusion temperature corresponding to the crosslinkable norbornene resin used, usually about 150 to 300 ° C., and 30 to 80 ° C.
A pressure is applied to about kgf / cm ² , and the layers are crosslinked and thermally fused between the layers to obtain a laminate.

[0032]

The present invention will be described more specifically with reference to the following examples and comparative examples. The insulation resistance, the dielectric constant, the dielectric loss tangent, and the water absorption were measured according to JIS C 6481, and the flame retardancy was evaluated by the following method according to the UL-94 standard.

Using a test piece having a thickness of 1/16 inch, fix the test piece vertically by clamping the upper end of the test piece with a clamp, and lay cotton under 12 inches below the test piece. The fire of the gas burner was applied to the lower end of the test piece for 10 seconds, and the first burning time of the test piece was measured. When the fire was extinguished, the fire of the gas burner was applied to the lower end again for 10 seconds, and the second burning time of the test piece was measured. Is measured. When the total of ten data of the first burning time and the second burning time for five test pieces is T, and the maximum data is M, V-0,
V-1 and V-2 were determined to be unacceptable. V-0: T is 50 seconds or less, M is 10 seconds or less, the fire does not burn up to the clamp, and the flamed melt falls and the cotton does not ignite. V-1: T is 250 seconds or less, M is 30 seconds or less, the flame does not burn up, the flamed melt falls, and the cotton does not ignite. V-2: T was not longer than 250 seconds, M was not longer than 30 seconds, and the fire did not burn up to the clamp, but the flamed melt dropped and the cotton was ignited. Fail: Does not satisfy the above requirements of V-0, V-1, and V-2.

Example 1 Hydrogenated ring-opened norbornene resin (ZEONEX 28)
0, manufactured by Zeon Corporation, glass transition temperature 140 ° C,
20 parts by weight of a number average molecular weight of about 28,000 and a hydrogenation rate of 99.7% or more), 1 part by weight of α, α'-bis (t-butylperoxy-m-isopropyl) benzene and 1 part by weight of diallyl phthalate When dispersed in 80 parts by weight, no precipitation or the like occurred, and a uniform solution was obtained.

Example 2 The crosslinkable norbornene resin composition solution obtained in Example 1 was coated on a mirror finished SUS plate with a thickness of 75 using a coating machine.
It was applied so as to have a thickness of 0 μm. It was left to dry at 60 ° C. for 20 minutes and further at 120 ° C. for 10 minutes. Thereafter, the formed sheet was peeled off from the SUS plate. The thickness of the obtained sheet was about 150 μm.

The eight sheets are laminated, and 3
A 5 μm copper foil was laminated, pressed at a pressing temperature of 180 ° C. and a pressing pressure of 40 kgf / cm ² for 20 minutes to a thickness of 1 mm, and heat-fused to obtain a laminated plate.

Even when the laminate was brought into contact with solder at 260 ° C. for 30 seconds, no peeling or blistering of the copper foil was observed, the water absorption was 0.01% or less, and the insulation resistance was 4 × 10 4
The dielectric constant and dielectric loss tangent at ¹⁶ Ω and 1 MHz, respectively, are 2.
4, 0.0005.

When this laminate was immersed in toluene and allowed to stand for 24 hours, swelling was observed, but no dissolution was observed.

Thirteen sheets were laminated, and the thickness was reduced to 1/1 at a pressing temperature of 180 ° C. and a pressing pressure of 40 kgf / cm ^2.
The resultant was pressed for 20 minutes so as to have a thickness of 6 inches and thermally fused to obtain a test piece for flame retardancy test. When the flame retardancy was evaluated using this test piece, it failed in the UL-94 standard.

Example 3 A 0.1 mm-thick glass chlor base material was immersed in the solution of the crosslinkable norbornene-based resin composition obtained in Example 1, and was taken out. After drying the glass cloth substrate impregnated with the crosslinkable norbornene-based resin composition at 60 ° C. for 20 minutes,
The mixture was left at 10 ° C. for 10 minutes to obtain eight prepregs. 40% by weight of this prepreg is a crosslinkable molded article of the present invention,
The thickness was about 110 μm.

Eight prepregs were laminated, and a copper foil of 35 μm was further laminated on both sides, and pressed at a temperature of 180 ° C. and a pressure of 40 kgf / cm ² to a thickness of 1 mm.
It was pressed for 0 minutes and heat-sealed to obtain a laminate.

Even when the laminate was brought into contact with solder at 260 ° C. for 30 seconds, no peeling of copper foil or blistering was observed, the water absorption was 0.01%, the insulation resistance was 1 × 10 ¹⁷ Ω, 1
The dielectric constant and the dielectric loss tangent at MHz are 2.7 and 0, respectively.
0009.

When this laminate was immersed in toluene and allowed to stand for 24 hours, swelling was observed, but no dissolution was observed. In addition, when the flame retardancy was evaluated in the same manner as in Example 2, it was rejected in the UL-94 standard.

Example 4 Hydrogenated ring-opened norbornene resin (ZEONEX 28)
0) When 20 parts by weight, 1 part by weight of dicumyl peroxide and 1 part by weight of trimethylolpropane trimethacrylate were dispersed in 80 parts by weight of toluene, a uniform solution was obtained without precipitation.

Example 5 The crosslinkable norbornene resin composition solution obtained in Example 4 was coated on a mirror finished SUS plate with a thickness of 75 using a coating machine.
It was applied so as to have a thickness of 0 μm. It was left to dry at 60 ° C. for 20 minutes and further at 120 ° C. for 10 minutes. Thereafter, the formed sheet was peeled off from the SUS plate. The thickness of the obtained sheet was about 150 μm.

The eight sheets are laminated, and three sheets are
A 5 μm copper foil was laminated, pressed at a pressing temperature of 180 ° C. and a pressing pressure of 40 kgf / cm ² for 20 minutes to a thickness of 1 mm, and heat-fused to obtain a laminated plate.

Even when the laminate was brought into contact with solder at 260 ° C. for 30 seconds, no peeling of copper foil or blistering was observed, the water absorption was 0.02%, the insulation resistance was 2 × 10 ¹⁶ Ω, 1
The dielectric constant and the dielectric loss tangent at MHz are 2.6 and 0.8, respectively.
0007.

When this laminate was immersed in toluene and allowed to stand for 24 hours, swelling was observed but no dissolution was observed. In addition, when the flame retardancy was evaluated in the same manner as in Example 2, it was rejected in the UL-94 standard.

Example 6 A glass chlorinated substrate having a thickness of 0.1 mm was immersed in the solution of the crosslinkable norbornene-based resin composition obtained in Example 5, and was taken out. After drying the glass cloth substrate impregnated with the crosslinkable norbornene-based resin composition at 60 ° C. for 20 minutes,
The mixture was left at 10 ° C. for 10 minutes to obtain eight prepregs. 40% by weight of this prepreg is a crosslinkable molded article of the present invention,
The thickness was about 110 μm.

Eight prepregs were laminated, and copper foil of 35 μm was further laminated on both sides. The prepreg was pressed at 180 ° C. under a pressure of 40 kgf / cm ² to a thickness of 1 mm.
It was pressed for 0 minutes and heat-sealed to obtain a laminate.

Even when the laminate was brought into contact with solder at 260 ° C. for 30 seconds, no peeling or blistering of the copper foil was observed, the water absorption was 0.03%, the insulation resistance was 1 × 10 ¹⁷ Ω, 1
The dielectric constant and dielectric loss tangent at 2.8 MHz are 2.8 and 0.8, respectively.
0011.

When this laminate was immersed in toluene and allowed to stand for 24 hours, swelling was observed but no dissolution was observed. In addition, when the flame retardancy was evaluated in the same manner as in Example 2, it was rejected in the UL-94 standard.

Example 7 A brominated bisphenol-based flame retardant (Praceft EB-242, manufactured by Manac Co., Ltd., structural formula: 80 parts by weight of toluene)

Embedded image ) Was dissolved in 20 parts by weight. When 100 parts by weight of this solution was mixed with 100 parts by weight of the resin solution obtained in Example 1, precipitation and separation did not occur, and a uniform solution was obtained.

Example 8 Using the crosslinkable norbornene-based resin composition solution obtained in Example 7, a laminate was obtained in the same manner as in Example 3. Even when the laminate was brought into contact with a solder at 260 ° C. for 30 seconds, no peeling or blistering of the copper foil was observed, and the water absorption was 0.1%.
The insulation resistance was 5 × 10 ¹⁶ Ω, the dielectric constant at 1 MHz, and the dielectric loss tangent were 3.0 and 0.001, respectively. No dissolution was observed when the laminate was immersed in toluene and left for 24 hours. When the flame retardancy was evaluated, it was V-0 in the UL-94 standard.

Example 9 A brominated aromatic triazine-based flame retardant (Pirogard SR245, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used in 80 parts by weight of toluene.
Structural formula

Embedded image ) Was dissolved in 20 parts by weight. When 100 parts by weight of this solution was mixed with 100 parts by weight of the resin solution obtained in Example 1, precipitation and separation did not occur, and a uniform solution was obtained.

Example 10 Using the crosslinkable norbornene-based resin composition solution obtained in Example 9, a laminate was obtained in the same manner as in Example 3. Even when the laminate was brought into contact with a solder at 260 ° C. for 30 seconds, no peeling or blistering of the copper foil was observed, and the water absorption was 0.1%.
The insulation resistance was 3 × 10 ¹⁶ Ω, the dielectric constant at 1 MHz, and the dielectric loss tangent were 3.0 and 0.001, respectively. No dissolution was observed when the laminate was immersed in toluene and left for 24 hours. When the flame retardancy was evaluated, it was V-0 in the UL-94 standard.

Example 11 A bisphenol-based flame retardant (Fireguard 3100, manufactured by Teijin Chemicals Ltd., structural formula: 80 parts by weight in toluene)

Embedded image ) Was dissolved in 20 parts by weight. When 100 parts by weight of this solution was mixed with 100 parts by weight of the resin solution obtained in Example 1, precipitation and separation did not occur, and a uniform solution was obtained.

Example 12 Using the crosslinkable norbornene-based resin composition solution obtained in Example 11, a laminate was obtained in the same manner as in Example 3. Even when the laminate was contacted with a solder at 260 ° C. for 30 seconds, no peeling or blistering of the copper foil was observed, the water absorption was 0.02%, the insulation resistance was 3 × 10 ¹⁶ Ω, and 1 MHz. Have a dielectric constant and a dielectric loss tangent of 3.0 and 0.001, respectively. No dissolution was observed when the laminate was immersed in toluene and left for 24 hours. When the flame retardancy was evaluated, it was V-2 in the UL-94 standard.

Comparative Example 1 A high-viscosity liquid epoxy thermosetting composition (Epicoat 504 manufactured by Yuka Shell Co., Ltd. as a curable epoxy compound)
6 100 parts by weight of dicyandiamide 4 as a curing agent
70 parts by weight), which were obtained by adding 14 parts by weight of dimethylformamide and 0.2 part by weight of benzyldimethylamine as a curing aid), were dispersed and dissolved in 100 parts by weight of methyl ethyl ketone.

A glass cloth substrate having a thickness of 0.1 mm was immersed in this solution. The glass cloth substrate impregnated with the epoxy-based thermosetting composition was dried at 60 ° C. for 10 minutes, and then left at 150 ° C. for 10 minutes to obtain eight prepregs. About 50% by weight of this prepreg was a crosslinkable norbornene-based resin composition, and the thickness was about 130 μm.

The eight prepregs were laminated, and copper foil of 35 μm was further laminated on both sides.
The laminate was pressed at a pressing pressure of 40 kgf / cm ² to a thickness of 1 mm for about 90 minutes and heat-sealed to obtain a laminate.

This laminate had no abnormalities such as peeling of copper foil and blisters even after contact with solder at 260 ° C. for 30 seconds, but had a water absorption of 0.15% and an insulation resistance of 1 × 10 5.
The dielectric constant and dielectric loss tangent at ¹⁵ Ω and 1 MHz are respectively 4.
8, 0.022, and water absorption, dielectric constant, and dielectric loss tangent were not preferable as an electrical insulating material.

Comparative Example 2 Hydrogenated ring-opened norbornene resin (ZEONEX 28)
0) When 20 parts by weight of dicumyl peroxide and 1 part by weight of dicumyl peroxide were dispersed in 80 parts by weight of toluene, a uniform solution was obtained without precipitation or the like.

The crosslinkable norbornene-based resin composition solution was applied to a mirror finished SUS plate to a thickness of 750 μm using a coating machine. Leave to dry at 60 ° C for 20 minutes and at 120 ° C for 10 minutes, then SUS
Peeled off the board. The thickness of the obtained sheet was about 150 μm.

The eight sheets are laminated, and 3
A 5 μm copper foil was laminated, pressed at a pressing temperature of 180 ° C. and a pressing pressure of 40 kgf / cm ² for 20 minutes to a thickness of 1 mm, and heat-fused to obtain a laminated plate.

When this laminate was brought into contact with solder at 260 ° C. for 30 seconds, peeling of copper foil and generation of blisters were observed.
Further deformation was observed.

When this laminate was immersed in toluene and left for 24 hours, most of the laminate dissolved.

Comparative Example 3 Toluene (80 parts by weight) was mixed with a cyclic chloroparaffin-based flame retardant (Dechlorane Plus, manufactured by Odental Chemical Co., Ltd., structural formula:

Embedded image ) 20 parts by weight were dissolved. When 100 parts by weight of this solution was mixed with 100 parts by weight of the resin solution obtained in Example 1, the solution did not dissolve, and when left for one week, a precipitate was formed.

[0069]

The molded article obtained by crosslinking the crosslinkable norbornene resin composition of the present invention is excellent in heat resistance, chemical resistance, moisture resistance, water resistance and electric properties.
Even when contacted for seconds, the copper foil does not peel off, blisters do not occur, and it does not easily dissolve in toluene. For example, it has excellent heat resistance and chemical resistance, has no unevenness, and is useful as a high-frequency circuit board or the like.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-63-39936 (JP, A) JP-A-50-61452 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08J 5/18 C08J 5/24 C08L 65/00

Claims (8)

(57) [Claims] An organic peroxide is used in an amount of 0.001 to 30 parts by weight based on 100 parts by weight of a thermoplastic hydrogenated ring-opened norbornene resin and a crosslinking aid is used in an amount of 0.1 part by weight of an organic peroxide.
A uniform crosslinkable norbornene-based resin composition comprising 10 to 10 parts by weight dispersed therein. 2. The crosslinkable norbornene-based resin composition according to claim 1, wherein the hydrogenation rate of the hydrogenated ring-opened norbornene-based resin is 90% or more. 3. The crosslinkable norbornene resin composition according to claim 1, wherein the crosslinker is an allylic crosslinker or a methacrylate crosslinker. 4. A thermoplastic hydrogenated ring-opened norbornene-based resin in an amount of 100 parts by weight represented by the general formula 1 (In the general formula 1, n, m ₁ , m ₂ , m ₃ , and m ₄ are integers,
n ≧ 0, 1 ≦ m ₁ ≦ 5, 1 ≦ m ₂ ≦ 4, 1 ≦ m ₃ ≦ 4, 1
≦ m ₄ ≦ 5) or the general formula 2 (In the general formula 2, n, m ₁ , m ₂ , m ₃ , m ₄ , m ₅ , and m ₆ are integers, and n ≧ 0, 1 ≦ m ₁ ≦ 5, 1 ≦ m ₂ ≦ 5, 1 ≦ m
₃ ≦ 4, 1 ≦ m ₄ ≦ 4, 1 ≦ m ₅ ≦ 5, 1 ≦ m ₆ ≦ 5), wherein 5 to 150 parts by weight of a flame retardant is added. 4. The crosslinkable norbornene-based resin composition according to 3. 5. A crosslinkable molded article comprising the crosslinkable norbornene-based resin composition according to claim 1, 2, 3 or 4. 6. A film or a sheet.
The crosslinkable molded article according to the above. 7. The crosslinkable molded article according to claim 5, which is a prepreg. 8. A crosslinked molded article obtained by heating and crosslinking the crosslinkable molded article according to claim 5, 6, or 7.