JPH10152523A - Allyl group-modified norbornene-based polymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a norbornene-based polymer excellent in dielectric pharacteristics, heat resistance and chemical resistance, provide a method for producing the polymer and obtain a crosslinkable resin material. SOLUTION: This allyl group-modified norbornene-based polymer is obtained by introducing at least one allyl group into an aromatic ringcontaining a norbornene-based polymer and has 500-500,000 weight-average molecular weight(MW). The method for producing the polymer comprises a process for metallizing the aromatic ring-containing norbornene-based polymer with an organic metal and a process for subjecting the metallized polymer to substitution reaction with an allyl halide to introduce allyl group. This crosslinkable resin material comprises an ally group-modified norbornene-based polymer obtained by introducing at least one allyl group into an aromatic ring-containing weight- average molecular weight and having 500-500,000 weight-average molecular weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel modified norbornene-based polymer, a method for producing the same, and a crosslinkable resin material. More specifically, the present invention relates to an allyl group-modified norbornene-based polymer having excellent dielectric properties, heat resistance, and chemical resistance, a method for producing the same, and a crosslinkable resin material containing the modified polymer.

[0002]

2. Description of the Related Art In recent years, in the field of electronic equipment for communication, consumer use, industrial use, and the like, there has been a remarkable trend toward miniaturization and high density of mounting methods. However, better heat resistance, dimensional stability, and electrical properties are being demanded. For example, as a printed wiring board, a copper-clad laminate using a thermosetting resin such as a phenol resin or an epoxy resin as a base material has been used. Although these have various performances in a well-balanced manner, they have a drawback that electric characteristics, particularly dielectric characteristics in a high frequency range are poor.

As a new material for solving this problem, in recent years, norbornene-based polymers have attracted attention, and applications to copper-clad laminates have been attempted. For example, JP-A-6-248
No. 164 discloses a laminate in which a copper foil is adhered to a crosslinked substrate obtained by crosslinking a norbornene-based polymer with a crosslinking agent. However, in this method, a large amount of a crosslinking aid such as diallyl phthalate must be used, and the crosslinking aid causes a decrease in dielectric properties. On the other hand, when the blending ratio of the crosslinking assistant is small or not blended, the crosslinking reaction of the norbornene-based polymer does not proceed sufficiently, and only a laminate having insufficient heat resistance and chemical resistance can be obtained. Had a point.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a norbornene-based polymer having excellent dielectric properties, heat resistance and chemical resistance, and a method for producing the same. Another object of the present invention is to provide a crosslinkable resin material having excellent dielectric properties, heat resistance, and chemical resistance. The present inventors have conducted intensive studies to overcome the problems of the prior art, and as a result, among the norbornene-based polymers, the aromatic ring-containing norbornene-based polymer is easily formed of an organic metal such as n-butyllithium. Metallization (that is, introduction of a metal substituent), and when the metallized polymer is reacted with an allyl halide, demetallation halide occurs and an allyl group can be introduced into the polymer. Was found. And when this allyl group-modified norbornene-based polymer is used, no crosslinking aid is added,
Alternatively, it has been found that the crosslinking reaction proceeds sufficiently with a small amount of addition, and a crosslinked product having excellent heat resistance and chemical resistance and excellent dielectric properties can be obtained. The present invention has been completed based on these findings.

[0005]

Thus, according to the present invention, the aromatic ring-containing norbornene-based polymer having at least one allyl group introduced therein has a weight average molecular weight (Mw) of 500.
~ 500,000 allyl group-modified norbornene-based polymers are provided. Further, according to the present invention, an allyl group-modified norbornene characterized by comprising a step of metallating an aromatic ring-containing norbornene-based polymer with an organic metal, and then a step of introducing an allyl group by a substitution reaction with allyl halide. A method for producing a polymer is provided. Furthermore, according to the present invention, the aromatic ring-containing norbornene-based polymer having at least one allyl group introduced therein has a weight average molecular weight (Mw) of 50.
A crosslinkable resin material comprising 0 to 500,000 allyl group-modified norbornene-based polymer is provided.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Allyl group-modified norbornene polymer The allyl group-modified norbornene polymer of the present invention is obtained by introducing at least one allyl group into an aromatic ring-containing norbornene polymer by a modification reaction. Things.

<Aromatic Ring-Containing Norbornene-Based Polymer> (1) Polymer and Monomer The aromatic ring-containing norbornene-based polymer used in the present invention is a norbornene-based polymer and at least one aromatic compound in a molecule. There is no particular limitation as long as it has a ring, but a polymer containing an aromatic ring-containing monomer unit is preferably used. Examples of the aromatic ring-containing monomer include, for example, an aromatic ring-containing norbornene-based monomer and an aromatic vinyl compound. Among these, in order to increase the content of the aromatic ring and the content of the norbornene-based monomer unit, the aromatic ring-containing monomer is used. Norbornene monomers are preferred. Examples of the aromatic ring-containing norbornene-based polymer having an aromatic ring-containing monomer unit include a ring-opened polymer of an aromatic ring-containing norbornene-based monomer and a ring-opening of an aromatic ring-containing norbornene-based monomer and a norbornene-based monomer that does not contain an aromatic ring. Copolymers and hydrogenated products thereof are exemplified.

The aromatic ring-containing norbornene-based polymer includes (1) an addition polymer of an aromatic ring-containing norbornene-based monomer and an aromatic vinyl compound, and (2) an aromatic ring-containing norbornene-based monomer and a norbornene containing no aromatic ring. Addition polymer of a vinyl monomer and an aromatic vinyl compound,
(3) an addition copolymer of an aromatic ring-containing norbornene monomer and an aromatic vinyl compound; and (4) an addition copolymer of an aromatic ring-containing norbornene monomer and a vinyl compound other than the aromatic vinyl compound (eg, ethylene). Polymer, (5)
Addition polymers of an aromatic ring-containing norbornene-based monomer, and (6) an addition copolymer of an aromatic-containing norbornene-based monomer and a norbornene-based monomer containing no aromatic ring can be used.

In the above-mentioned hydrogenated product, the carbon-carbon double bond in the main chain may be hydrogenated to a hydrogenation rate of 99% or more, but not all of the aromatic rings are hydrogenated. . The hydrogenation rate of the aromatic ring is appropriately selected depending on the content of the aromatic ring-containing monomer, but is usually 90% or less, preferably 80% or less, and more preferably 70% or less. As the aromatic ring-containing norbornene-based monomer,
There is no particular limitation. For example, JP-A-5-97719, JP-A-7-41550, and JP-A-8-72
No. 210 can be used. That is, as the aromatic ring-containing monomer, typically, a compound represented by the following formula (I) can be used.

[0010]

Embedded image In the formula (I), the meaning of each symbol is as follows. m: 0, 1 or 2. h: 0, 1 or 2. j: 0, 1 or 2. k: 0, 1 or 2. R ^{1 to} R ¹¹ each independently represent a hydrogen atom, a hydrocarbon group,
And an atom or group selected from the group consisting of a polar group such as a halogen atom, an alkoxy group, a hydroxyl group, an ester group (eg, an alkyl ester group), a cyano group, an amide group, an imide group, and a silyl group; Represents a substituted hydrocarbon group. R ^{12 to} R ²⁰ each independently represent a hydrogen atom, a hydrocarbon group,
And an atom or group selected from the group consisting of a polar group such as a halogen atom, an alkoxy group, a hydroxyl group, an ester group (eg, an alkyl ester group), a cyano group, an amide group, an imide group, and a silyl group; Represents a substituted hydrocarbon group.

In the formula (I), the carbon atom to which R ¹⁰ and R ¹¹ are bonded and the carbon atom to which R ¹⁴ is bonded or the carbon atom to which R ¹² is bonded are directly or the number of carbon atoms. It may be bonded through 1-3 alkylene groups. When j = K = 0, R ¹⁶ and R ¹³ or R ¹⁶
And R ²⁰ may combine with each other to form a monocyclic or polycyclic aromatic ring.

The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the hydrocarbon group include, for example, those having 1 to 2 carbon atoms.
0, preferably 1-10, more preferably 1-6 alkyl groups, having 2-20 carbon atoms, preferably 2-10,
More preferably, it has 2 to 6 alkenyl groups and 2 carbon atoms.
-20, preferably 2-10, more preferably 2-6 alkynyl groups, having 2-20 carbon atoms, preferably 2-20
10, more preferably 2 to 6 alkylidene groups, 3 to 15 carbon atoms, preferably 3 to 8, more preferably 5 to 5
And a cycloalkyl group having 6 and an aromatic hydrocarbon group having 6 to 20, preferably 6 to 16, and more preferably 6 to 10 carbon atoms. Examples of the hydrocarbon group substituted with a polar group include a halogenated alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms.

Examples of such an aromatic ring-containing norbornene-based monomer include, for example, 5-phenyl-bicyclo [2.
2.1] Hept-2-ene (5-phenyl-2-norbornene), 5-methyl-5-phenyl-bicyclo [2.
2.1] Hept-2-ene, 5-benzyl-bicyclo [2.2.1] hept-2-ene, 5-tolyl-bicyclo [2.2.1] hept-2-ene [5- (4 -Methylphenyl) -2-norbornene], 5- (ethylphenyl) -bicyclo [2.2.1] hept-2-ene, 5-
(Isopropylphenyl) -bicyclo [2.2.1] hept-2-ene, 8-phenyl-tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-phenyl-tetracyclo [4.4.0.1 ^2,5 .
1 ^7,10] -3-dodecene, 8-benzyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-dodecene, 8-
Tolyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-dodecene, 8- (ethylphenyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8
-(Isopropylphenyl) -tetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-diphenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
3-dodecene, 8- (biphenyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-
(Β-naphthyl) -tetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -3-dodecene, 8- (α-naphthyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
3-dodecene, 8- (anthracenyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 11
-Phenyl-hexacyclo [6.6.1.1 ^3,6 .
0 ^2,7 . 0 ^9,14] -4-heptadecene, 6- (alpha-naphthyl) - bicyclo [2.2.1] - hept-2-ene, 5
-(Anthracenyl) -bicyclo [2.2.1] -hept-2-ene, 5- (biphenyl) -bicyclo [2.
2.1] -Hept-2-ene, 5- (β-naphthyl)-
Bicyclo [2.2.1] -hept-2-ene, 5,6-
Norbornene-based monomers having an aromatic substituent such as diphenyl-bicyclo [2.2.1] -hept-2-ene, 9- (2-norbornen-5-yl) -carbazole; 1,4-methano-1, 4,4a, 4b, 5,8,8
a, 9a-octahydrofluorenes; 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, 1,
4-methano-8-methyl-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-8-chloro-1,
1,4-methano-1,4,4a, 9a- such as 4,4a, 9a-tetrahydrofluorene and 1,4-methano-8-bromo-1,4,4a, 9a-tetrahydrofluorene
Tetrahydrofluorenes, 1,4-methano-1,4,
4a, 9a-tetrahydrodibenzofurans, 1,4-
Methano-1,4,4a, 9a-tetrahydrocarbazole, 1,4-methano-9-phenyl-1,4,4a, 9
1,4-methano- such as a-tetrahydrocarbazole
1,4,4a, 9a-tetrahydrocarbazoles,
1,4-methano-1, such as 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene,
4,4a, 5,10,10a-hexahydroanthracenes, 7,10-methano-6b, 7,10,10a-tetrahydrofluorancenes, (cyclopentadiene-
Acenaphthylene adduct) to which cyclopentadiene is further added, 11,12-benzo-pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene, 11,12-benzo-pentacyclo [6.6.
1.1 ^3,6 . 0 ^2,7 . 0 ^9,14 ] -4-hexadecene, 1
4,15-benzo-heptacyclo [8.7.0.
12 ⁹ . ^14,7 . 1 ^11,17 . 0 ^3,8 . 0 ^12,16 ] -5-eicosene, cyclopentadiene-acenaphthylene adduct and the like, and an aromatic ring-containing norbornene-based monomer having a norbornene ring structure and an aromatic ring structure in a polycyclic structure.

These aromatic ring-containing norbornene-based monomers include, in addition to the compounds of the above-mentioned specific examples, alkyl, alkylidene, alkenyl-substituted derivatives, and halogen, hydroxyl, ester groups (eg, alkyl) of these substituted or unsubstituted compounds. It may be a polar substituent such as an ester group), an alkoxy group, a cyano group, an amide group, an imide group, and a silyl group. As the aromatic vinyl compound, for example, styrene, α-methylstyrene, o-methylstyrene, p
-Methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene and the like.

These aromatic ring-containing monomers can be used alone or in combination of two or more. The content (bonding amount) of the aromatic ring-containing monomer unit in the aromatic ring-containing norbornene-based polymer is appropriately selected depending on the purpose of use, but is usually 10% by weight or more, preferably 20% by weight or more, more preferably. Is 30% by weight or more. By containing the aromatic ring-containing monomer unit, the dispersibility of various compounding agents is improved to a high degree. Examples of other norbornene monomers containing no aromatic ring include, for example, JP-A-2-227424 and JP-A-2-276842.
And known monomers disclosed in JP-A-8-72210 and the like. The norbornene-based monomer containing no aromatic ring is typically a compound represented by the following formula (II).

[0016]

Embedded image In the formula (II), the meaning of each symbol is as follows. n is 0 or 1. s: 0 or 1 p: 0 or an integer of 1 to 4; q is 0 or 1. r: 0 or 1. R _{1 to} R ₂₀ each independently represent a hydrogen atom, a hydrocarbon group,
And an atom or group selected from the group consisting of polar groups such as a halogen atom, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an amide group, an imide group, and a silyl group, and a hydrocarbon group substituted with these polar groups. . R _{a to} R _d each independently represent a hydrogen atom, a hydrocarbon group,
And an atom or group selected from the group consisting of polar groups such as a halogen atom, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an amide group, an imide group, and a silyl group, and a hydrocarbon group substituted with these polar groups. .

In the formula (II), R _{15 to} R ₁₈ may be bonded to each other to form an unsaturated bond, a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring is a double bond. May be provided. R ₁₅ and R ₁₆ or R ₁₇ and R ₁₈ may form an alkylidene group. q or r is 0
In the case of the above, each bond is bonded to form a 5-membered ring.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the hydrocarbon group include, for example, those having 1 to 2 carbon atoms.
0, preferably 1-10, more preferably 1-6 alkyl groups, having 2-20 carbon atoms, preferably 2-10,
More preferably, it has 2 to 6 alkenyl groups and 2 carbon atoms.
-20, preferably 2-10, more preferably 2-6 alkynyl groups, 3-15 carbon atoms, preferably 3-5 carbon atoms.
8, more preferably 5 to 6 cycloalkyl groups, and 6 to 20 carbon atoms, preferably 6 to 16 and more preferably 6 to 10 aromatic hydrocarbon groups. Examples of the alkylidene group include a methylidene group,
Examples thereof include lower alkylidene groups having 1 to 6 carbon atoms, such as an ethylidene group, a propylidene group and a butylidene group. Examples of the hydrocarbon group substituted with a polar group include a halogenated alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms.

Specific examples of the norbornene monomer having no aromatic ring include, for example, norbornene, its alkyl, alkylidene, and halogens, hydroxyl groups, ester groups, alkoxy groups, cyano groups, and amide groups of these substituted or unsubstituted norbornenes. And a substituent of a polar group such as an imide group and a silyl group. More specifically, for example, 2-norbornene [that is, bicyclo [2.2.
1] Hept-2-ene], 5-methyl-2-norbornene, 5,6-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-hexyl-2-norbornene, 5-octyl- 2-norbornene and 5-octadecyl-2-norbornene.

Further, other specific examples include a monomer obtained by adding one or more cyclopentadiene to norbornene, a derivative or a substitute thereof similar to the above, and more specifically, for example, 1,4: 5,8 -Dimethano-1,2,3,
4,4a, 5,8,8a-octahydro-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; polycyclic monomers which are multimers of cyclopentadiene, derivatives and substituents similar to the above, more specifically Is dicyclopentadiene,
2,3-dihydrodicyclopentadiene and the like; adducts of cyclopentadiene with tetrahydroindene and the like, derivatives and substituents similar to the above, more specifically 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 content (bonding amount) of the norbornene-based monomer (aromatic ring-containing and / or other norbornene-based monomer) unit in the aromatic ring-containing norbornene-based polymer is as follows:
It is appropriately selected according to the purpose of use, but is usually at least 30% by weight, preferably at least 50% by weight, more preferably at least 70% by weight. If the content of the norbornene-based monomer is excessively small, characteristics such as electric properties, heat resistance, solder resistance, chemical resistance, and mechanical strength may be insufficient, which is not preferable.

Examples of the vinyl compound other than the aromatic vinyl compound include ethylene, propylene, 1-butene,
1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4, 4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3
-Ethyl-1-hexene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene,
2 to 2 carbon atoms such as 1-octadecene and 1-eicosene
0 ethylene or α-olefin; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene,
3a, 5,6,7a-tetrahydro-4,7-methano-
Cycloolefins such as 1H-indene; non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene and 1,7-octadiene; These vinyl compounds can be used alone or in combination of two or more.

(2) Polymerization Method The ring-opened polymer or ring-opened copolymer of the norbornene-based monomer can be obtained by a known polymerization method. As the ring-opening polymerization catalyst, ruthenium, rhodium, palladium,
A catalyst comprising a metal halide, nitrate or acetylacetone compound selected from osmium, iridium, and platinum and a reducing agent; or a metal halide or acetylacetone compound selected from titanium, vanadium, zirconium, tungsten, and molybdenum And an organoaluminum compound.

By adding a third component to the above-mentioned catalyst system, polymerization activity and selectivity of ring-opening polymerization can be enhanced. Specific examples include molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound, sulfur-containing compound, halogen-containing compound, molecular iodine, and other Lewis. Acids and the like. As the nitrogen-containing compound, an aliphatic or aromatic tertiary amine is preferable, and specific examples include triethylamine, dimethylaniline, tri-n-butylamine, pyridine, α-picoline and the like.

The ring-opening (co) polymerization can be carried out without using a solvent, but can also be carried out in an inert organic solvent. As the solvent, for example, benzene, toluene, aromatic hydrocarbons such as xylene, n-pentane, hexane,
Examples thereof include aliphatic hydrocarbons such as heptane, alicyclic hydrocarbons such as cyclohexane, halogenated hydrocarbons such as styrene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, dichlorobenzene, and trichlorobenzene. The polymerization temperature is usually -50C to 100C, preferably -30C to 80C,
More preferably -20 ~ 60 ℃, the polymerization pressure,
Usually 0 to 50 kg / cm ² , preferably 0 to 20 kg
/ Cm ² .

In order to produce an addition copolymer of a norbornene monomer and an aromatic vinyl compound and / or a vinyl compound other than the aromatic vinyl compound, a known method can be employed. A method of copolymerizing in a hydrogen solvent or in the absence of a solvent in the presence of a catalyst comprising a vanadium compound and an organoaluminum compound, preferably a halogen-containing organoaluminum compound, soluble in a solvent or a norbornene-based monomer. be able to. Examples of the hydrocarbon catalyst include aliphatic hydrocarbons such as hexane, heptane, octane, and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene, and xylene. The polymerization temperature is usually
The polymerization temperature is usually 50 to 100 ° C, preferably -30 to 80 ° C, more preferably -20 to 60 ° C, and the polymerization pressure is usually 0 to 50 kg / cm ² , preferably 0 to 20 kg / cm ² .
cm ² .

(3) Hydrogenation Method A hydrogenated polymer (hydrogenated product) of an aromatic ring-containing norbornene-based polymer is prepared by subjecting a ring-opening polymer or a ring-opening copolymer to a hydrogenation catalyst in a conventional manner. , Hydrogenation with hydrogen. As a hydrogenation catalyst,
Catalyst comprising a combination of a transition metal compound and an alkyl metal compound, for example, cobalt acetate / triethyl aluminum, nickel acetylacetonate / triisobutyl aluminum, titanocene dichloride / n-butyl lithium, zirconocene dichloride / sec-butyl lithium, tetrabutoxy titanate / A combination of dimethylmagnesium and the like can be given.

The hydrogenation reaction is usually carried out in an inert organic solvent. As the organic solvent, a hydrocarbon-based solvent is preferable, and a cyclic hydrocarbon-based solvent is more preferable, because the resulting hydrogenated product is excellent in solubility. Examples of such hydrocarbon solvents include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as n-pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decalin; and tetrahydrofuran and ethylene glycol dimethyl ether. Ethers; and the like, and two or more of these can be used as a mixture. Usually, it may be the same as the polymerization reaction solvent, and the reaction may be carried out by adding a hydrogenation catalyst to the polymerization reaction solution as it is.

It is preferable that the aromatic ring-containing norbornene polymer used in the present invention has high weather resistance and high light degradation resistance. Therefore, the ring-opened (co) polymer is preferably a polymer having an unsaturated bond in the main chain structure. Usually, 95% or more, preferably 98% or more, more preferably 99% or more is preferably saturated. In order to achieve the object of the present invention, it is desirable that at least 20%, preferably 30% or more, preferably 40% or more of the aromatic ring structure remain. The unsaturated bond in the main chain structure and the unsaturated bond in the aromatic ring structure are ¹ H
-It can be distinguished and recognized by analysis by NMR. In order to mainly hydrogenate unsaturated bonds in the main chain structure, at a temperature of -20 ° C to 120 ° C, preferably 0 to 100 ° C, more preferably 20 to 80 ° C, 0.1 to 50 kg
/ Cm ² , preferably 0.5 to 30 kg / cm ² , more preferably 1 to 20 kg / cm ² .

<Method of Introducing Allyl Group> The allyl group-modified norbornene polymer of the present invention can be obtained by introducing an allyl group into the above aromatic ring-containing norbornene polymer. The method for introducing the allyl group is not particularly limited, and may be, for example, a method comprising a step of metallating an aromatic ring-containing norbornene-based polymer with an organic metal and a step of performing a substitution reaction with an allyl halide. Can be.
By this method, an allyl group can be easily introduced into a norbornene-based polymer having an aromatic ring (any of a ring-opened polymer, a hydrogenated product thereof, and an addition polymer).

Heretofore, it has been known that an allyl group is introduced into the α-position carbon atom of an aromatic ring in the main chain by metallizing polyphenylene ether with an organic metal and then subjecting it to a substitution reaction with allyl halide ( JP-A-64-696
No. 28). Further, in the present invention, in view of the fact that an allyl group cannot be introduced into a norbornene-based polymer having no aromatic ring by a similar method,
The allyl group is considered to be introduced at the carbon atom at the α-position of the aromatic ring or at the aromatic ring.

The production method of the present invention is particularly suitable for producing a hydrogenated product of a ring-opened polymer of a norbornene-based polymer having an allyl group. That is, as another method for producing an allyl group-containing norbornene-based polymer, there is a method of ring-opening polymerization of a norbornene-based monomer having an allyl group. However, in this method, in order to improve the heat resistance and chemical resistance of the obtained ring-opened polymer, when hydrogenating a carbon-carbon double bond formed in the main chain, an allyl group is selectively used. It is difficult to make it remain. On the other hand, according to the production method of the present invention, an allyl group can be introduced into the obtained hydrogenated product after hydrogenating the ring-opened polymer of the norbornene-based monomer.

The organic metal is not particularly limited as long as the aromatic ring norbornene-based polymer can be metallized, but an organic alkali metal is usually used. Examples of the organic alkali metal include organic lithium compounds such as methyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, and phenyllithium; organic sodium compounds such as alkyl sodium; Compound. These organic metals can be used alone or in combination of two or more. The amount of the organometallic compound can be appropriately selected depending on the target amount of the allyl group to be introduced, but is usually 0.01 to 1000 mmol, preferably 0.1 to 1000 parts by weight, per 100 parts by weight of the aromatic ring-containing norbornene-based polymer. It is in the range of 500 mmol, more preferably 1-250 mmol.

As the allyl halide, for example, allyl chloride, allyl bromide, allyl iodide and the like can be mentioned. These allyl halides
Each can be used alone or in combination of two or more. The amount of the allyl halide to be used is appropriately selected depending on the target amount of the allyl group to be introduced, but is usually at least an equivalent, preferably 1 to 5 equivalents, more preferably 1 to 2 equivalents to the organic metal. is there. The metalation reaction and the subsequent allylation reaction can be carried out by adding a solvent. Examples of the solvent include ethers such as 1,4-dioxane and dimethoxyethane; N, N, N ', N'-
Hydrocarbons such as cyclohexane, benzene, toluene, and xylene in the presence of tertiary amines such as tetramethylethylenediamine can be used.

The reaction temperature and the reaction time are not particularly limited, but in the metalation reaction, the reaction temperature is usually -7.
Between 8 ° C and (the boiling point of the system)
(Between (solidification point of system) to (boiling point of system)), preferably 5 ° C
To (the boiling point of the system), and the reaction time is usually in the range of 30 seconds to 24 hours, preferably 1 minute to 10 hours.
In the allylation reaction, the reaction temperature is usually between −78 ° C. and (the boiling point of the system).
~ (System boiling point)], preferably 5 ° C ~ (system boiling point)
And the reaction time is usually in the range of 30 seconds to 24 hours, preferably 1 minute to 10 hours. The metalation reaction and the allylation reaction are particularly preferably performed in an atmosphere of an inert gas such as nitrogen or argon.

<Allyl group-modified norbornene-based polymer> The allyl group-modified norbornene-based polymer of the present invention can sufficiently exhibit the effect of improvement if at least one allyl group is present in the polymer. (1) Allyl group modification rate = X / Y (1) X: Total number of moles of allyl group Y: Allyl group modification rate determined by the total number of monomer units of polymer (polymer weight / average molecular weight of monomer) is usually 0.1%. 1 to 100 mol%, preferably 1 to 50 mol%,
More preferably, the content is in the range of 5 to 30 mol%. When the allyl group modification ratio is in this range, the crosslinkability is good, and the dielectric properties, heat resistance and chemical resistance properties of the crosslinked product are highly balanced and suitable.

The content of the aromatic ring-containing norbornene monomer unit in the allyl group-modified norbornene polymer of the present invention is usually 10% by weight or more, preferably 20% by weight or more.
It is more preferably at least 30% by weight. By increasing the content of the aromatic ring-containing norbornene-based monomer unit in the allyl group-modified norbornene-based polymer, the compatibility with various resins, rubbery polymers, compounding agents, and solvents is improved, and the composition is obtained. Sometimes suitable.

The molecular weight of the allyl group-modified norbornene-based polymer of the present invention is determined by gel permeation chromatography (GPC) using toluene as a solvent in terms of polystyrene-equivalent weight average molecular weight (Mw) or allyl group-modified When the norbornene-based polymer is not dissolved in toluene, the weight average molecular weight (Mp in terms of polyisoprene) measured by GPC using cyclohexane as a solvent is used.
w), from 500 to 500,000, preferably from 1,000
0 to 200,000, more preferably 2,000 to 10
It is in the range of 0000. When the weight-average molecular weight (Mw) of the allyl group-modified norbornene-based polymer is in this range, the mechanical strength and the moldability are highly balanced, which is preferable.

The molecular weight distribution of the allyl group-modified norbornene polymer of the present invention is such that the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC under the above conditions is usually When the value is 4 or less, preferably 3 or less, more preferably 2 or less, the mechanical strength is high and suitable. The glass transition temperature (Tg) of the allyl group-modified norbornene polymer of the present invention may be appropriately selected according to the purpose of use, but is usually 50 to 300 ° C., preferably 10 to 300 ° C.
The range of 0 to 250 ° C, more preferably 120 to 200 ° C, is suitable because heat resistance and moldability are highly balanced.

The backbone polymer of the allyl group-modified norbornene-based polymer of the present invention is an aromatic ring-containing norbornene-based polymer, the structure of which varies depending on the type of polymerization such as ring-opening polymerization or addition polymerization and the presence or absence of copolymerization. I do. Typical trunk polymers include the following polymers. (1) A ring-opened polymer having a repeating unit represented by the formula (III) or a hydrogenated product thereof.

[0041]

Embedded image [Wherein the symbols have the same meanings as in the formula (I). However, ... represents a single bond or a double bond. In the formula (III), when the double bond in the main chain is hydrogenated, when there is a non-conjugated double bond in the side chain, the non-conjugated double bond is also hydrogenated, All or at least a part of the double bond of the aromatic ring remains. (2) The repeating unit represented by the formula (III) and the formula (I)
A ring-opening copolymer having a repeating unit represented by V) or a hydrogenated product thereof.

[0042]

Embedded image [Wherein the symbols have the same meanings as in the formula (II). However, ... represents a single bond or a double bond. In formula (IV), when the double bond in the main chain is hydrogenated, when there is a non-conjugated double bond in the side chain, the non-conjugated double bond is also hydrogenated. In the ring-opening copolymer, the proportion of the repeating unit represented by the formula (III) is as follows:
It is usually at least 10% by weight, preferably at least 30% by weight, more preferably at least 50% by weight. (3) An addition polymer having a repeating unit represented by the formula (V).

[0043]

Embedded image [Wherein the symbols have the same meanings as in the formula (I). (4) An addition copolymer having a repeating unit represented by the formula (V) and a repeating unit represented by the formula (VI).

[0044]

Embedded image [Wherein the symbols have the same meanings as in the formula (II). The proportion of the repeating unit represented by the formula (V) in the addition copolymer is usually at least 10% by weight, preferably at least 30% by weight, more preferably at least 50% by weight. (5) The repeating unit represented by the formula (V) and the formula (VII)
An addition copolymer having a repeating unit represented by the formula:

[0045]

Embedded image [Wherein, R ₂₁ and R ₂₂ each independently represent a hydrogen atom,
It is an alkyl group or an aryl group. ]

The repeating unit of the formula (VII) is a repeating unit derived from a vinyl compound such as ethylene. In the addition copolymer, the proportion of the repeating unit represented by the formula (V) is usually 10% by weight or more, preferably 30% by weight.
The content is more preferably 50% by weight or more. The allyl group-modified norbornene-based polymer of the present invention comprises a polymer having a repeating unit as described above as a trunk polymer, wherein the allyl group (—CH ₂ —CH ＝ CH ₂ ) has a carbon atom at the α-position of an aromatic ring,
It is introduced into an aromatic ring or the like. The modification ratio of the allyl group is 0.1 to 1 in terms of the number of moles of the allyl group / the total number of monomer units of the polymer (polymer weight / average molecular weight of monomer)
It is in the range of 00 mol%.

Crosslinkable Resin Material The crosslinkable resin material of the present invention comprises the above allyl group-modified norbornene-based polymer as an effective resin component. The method for crosslinking the crosslinkable resin material of the present invention is not particularly limited, and can be performed by heating or irradiation. Further, the crosslinkable resin material of the present invention,
A crosslinking reaction can be performed with a crosslinking agent. In particular, the crosslinkable resin material of the present invention does not deteriorate the electrical properties such as dielectric loss tangent since the crosslinkage proceeds with the crosslinking reaction with the crosslinking agent even if the amount of the crosslinking aid is sufficiently reduced.

(1) Crosslinking Agent The crosslinking agent is not particularly limited, but for example, an organic peroxide or a photocrosslinking agent is used. Examples of the organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide;
Peroxy ketals such as 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane and 2,2-bis (t-butylperoxy) butane; t-butyl hydroperoxide, Hydroperoxides such as 5-dimethylhexane-2,5-dihydroperoxide; dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3;
Dialkyl peroxides such as α, α'-bis (t-butylperoxy-m-isopropyl) benzene: diacyl peroxides such as octanoyl peroxide and isobutyryl peroxide; peroxyesters such as peroxydicarbonate And the like. Among these, dialkyl peroxide is preferred from the viewpoint of the performance of the resin after crosslinking, and the type of the alkyl group is preferably changed depending on the molding temperature.

Examples of the photocrosslinking agent include benzoin alkyl ether compounds such as benzoin ethyl ether and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl orthobenzoyl benzoate and 4,4'-dichlorobenzophenone; dibenzyl, benzyl methyl Benzylic compounds such as ketals;
2,2-diethoxyacetophenone, 2-hydroxy-
2-methylpropiophenone, 4-isopropyl-2-
Acetophenone-based compounds such as hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone, 2,2-diethoxyacetophenone, 4'-phenoxy-2,2-dichloroacetophenone; 2-chlorothioxanthone, 2-methylthioxanthone Thioxanthone compounds such as 2-isopropylthioxanthone; 2-ethylanthraquinone, 2-chloroanthraquinone and naphthoquinone; 2-hydroxy-
Propiophenone compounds such as 2-methylpropiophenone and 4'-dodecyl-2-hydroxy-2-methylpropiophenone; organic acid metals such as cobalt octenoate, cobalt naphthenate, manganese octenoate and manganese naphthenate And a photo-crosslinking agent such as a salt.

These crosslinking agents can be used alone or in combination of two or more. The amount of the crosslinking agent may be appropriately selected depending on the purpose of use, and is usually 0.001 to 30 parts by weight, preferably 0.001 to 30 parts by weight, based on 100 parts by weight of the allyl group-modified norbornene-based polymer. 15 parts by weight, more preferably 0.1 to 10
Parts by weight, most preferably 0.5 to 5 parts by weight. When the amount of the cross-linking agent is within this range, the properties such as cross-linking property and electric properties, chemical resistance and heat resistance of the cross-linked product are highly balanced and suitable.

(2) Crosslinking Aid In the present invention, a crosslinking aid can be appropriately used as long as the dielectric loss tangent is not significantly deteriorated. The crosslinking assistant is not particularly limited, but is disclosed in JP-A-62-34.
No. 924, etc., for example, oxime / nitroso type crosslinking assistants such as quinone dioxime, benzoquinone dioxime, p-nitrosophenol; N, Nm
Maleimide-based crosslinking aids such as phenylenebismaleimide; allyl-based crosslinking aids such as diallyl phthalate, triallyl cyanurate, and triallyl isocyanurate; methacrylate-based crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; Vinyl-based crosslinking aids such as vinyltoluene, ethylvinylbenzene and divinylbenzene; and the like. Among these, an allyl-based crosslinking assistant and a methacrylate-based crosslinking assistant are preferred because they can be uniformly dispersed.

These crosslinking aids can be used alone or in combination of two or more. The compounding amount is appropriately selected depending on the type of the crosslinking agent, but is usually 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight based on 1 part by weight of the crosslinking agent. The crosslinkable material of the present invention, other than a crosslinking agent and a crosslinking aid, if desired, a flame retardant,
Other compounding agents, solvents and the like can be compounded.

(3) Flame Retardant The flame retardant is not particularly limited, but is preferably one that does not decompose, modify, or degrade with a crosslinking agent. Usually, a halogen-based flame retardant is used. As the halogen-based flame retardant, various chlorine-based and bromine-based flame retardants can be used, but the flame retardant effect, heat resistance at the time of molding, dispersibility in the resin, influence on the physical properties of the resin, etc. are considered. From, for example, hexabromobenzene, pentabromoethylbenzene, hexabromobiphenyl, decabromodiphenyl, hexabromodiphenyloxide, octabromodiphenyloxide, decabromodiphenyloxide, pentabromocyclohexane, tetrabromobisphenol A, and derivatives thereof [for example, Tetrabromobisphenol A-bis (hydroxyethyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (bromoethyl ether), tetrabromobisphenol A-bis Allyl ether), tetrabromobisphenol S and derivatives thereof [eg, tetrabromobisphenol S-bis (hydroxyethyl ether), tetrabromobisphenol S-bis (2,3-dibromopropyl ether), etc.], tetrabromoanhydride phthalate Acids and derivatives thereof [eg, tetrabromophthalimide, ethylenebistetrabromophthalimide, etc.], ethylenebis (5,6-
Dibromonorbornene-2,3-dicarboximide), tris- (2,3-dibromopropyl-1) -isocyanurate, adduct of Diels-Alder reaction of hexachlorocyclopentadiene, tribromophenyl glycidyl ether, tribromophenyl acrylate , Ethylenebistribromophenylether, ethylenebispentabromophenylether, tetradecabromodiphenoxybenzene, brominated polystyrene, brominated polyphenylene oxide, brominated epoxy resin, brominated polycarbonate, polypentabromobenzyl acrylate, octabromonaphthalene, hexa Bromocyclododecane, bis (tribromophenyl) fumaramide,
It is preferable to use N-methylhexabromodiphenylamine, a halogenated bisphenol type epoxy compound, or the like.

These flame retardants can be used alone or in combination of two or more. The compounding amount of the flame retardant is 10% for allyl group-modified norbornene-based polymer.
The amount is usually 3 to 150 parts by weight, preferably 10 to 140 parts by weight, particularly preferably 15 to 120 parts by weight with respect to 0 parts by weight. As a flame retardant aid for more effectively exhibiting the flame retardant effect of the flame retardant, for example, an antimony-based flame retardant aid such as antimony trioxide, antimony pentoxide, sodium antimonate, and antimony trichloride may be used. it can. These flame retardant aids are used in a proportion of usually 1 to 30 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the flame retardant.

(4) Other Compounding Agents Other compounding agents include, for example, natural rubber, polyisoprene rubber and its hydrogenated product, polybutadiene rubber and its hydrogenated product, butadiene-isoprene copolymer rubber and its hydrogenated product Product, styrene-butadiene random copolymer rubber and hydrogenated product thereof, styrene-isoprene random copolymer and hydrogenated product thereof, acrylonitrile-butadiene copolymer rubber and hydrogenated product thereof, styrene-butadiene block copolymer rubber And its hydrogenated product, styrene-isoprene block copolymer and its hydrogenated product, ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber, ethylene-butene copolymer rubber, propylene-butene Elastomers such as copolymer rubbers; thermoplastic Norbornene-based resin, low-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, ultra-low-density polyethylene, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, polystyrene, polyphenylene sulfide, polyphenylene ether, Thermoplastic resins such as polyamide, polyester, polycarbonate and cellulose triacetate; tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2'-oxamidobis [ethyl-3
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], stabilizers such as trisnonylphenyl phosphite, tris (2,4-di-t-brylphenyl) phosphite, and tris (2,4-di-t-butylphenyl) phosphite; sodium alkyl sulfonate Antistatic agents such as alkyl sulfonate phosphonium salts and fatty acid ester hydroxyamine compounds such as glycerin ester of stearic acid; slip agents; anti-blocking agents; zinc stearate, calcium stearate, calcium 12-hydroxystearate and the like. Fatty acid metal salts such as glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate; Valence alcohol fatty acid ester;
Synthetic hydrotalcite; anti-fogging agent; lubricant; dye;
Natural oil; synthetic oil; wax; silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, basic magnesium carbonate, dowamite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, Clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite,
Organic or inorganic fillers such as aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, polyamide fiber; silane coupling agent, titanate coupling agent, aluminum coupling agent, zircoaluminum Various additives such as coupling agents such as nate coupling agents; plasticizers; coloring agents such as pigments and dyes; These other compounding agents can be used alone or in combination of two or more. The mixing ratio can be appropriately determined according to the respective functions and the intended use, but the smaller the ratio, the better.

(5) Solvent In the present invention, an allyl group-modified norbornene-based polymer is dissolved in a solvent to prepare an impregnation solution for prepreg, or a sheet (film) is produced by a solution casting method. Can be. Thus, when dissolving the allyl group-containing norbornene-based polymer using a solvent, for example, aromatic hydrocarbons such as toluene, xylene, ethylbenzene, n-pentane, hexane, aliphatic hydrocarbons such as heptane, Alicyclic hydrocarbons such as cyclohexane,
Examples thereof include halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene. These solvents can be used alone or in combination of two or more, and the amount of the solvent used is such that the aromatic ring-containing norbornene-based polymer and, if necessary, the components to be blended are uniformly dissolved or dispersed. It is a range with a sufficient quantity ratio.

In the present invention, such as a molded article, a prepreg, or a laminate , after the above-mentioned crosslinkable resin material is molded,
Crosslinking can be performed to obtain a crosslinkable molded article. The method of molding a crosslinkable resin material is to dissolve in a solvent and mold, or to melt at a temperature at which crosslinking is not performed, or at a sufficiently low crosslinking speed so that the moldability does not deteriorate due to crosslinking during molding. Molding. Specifically, a cross-linkable material dissolved in a solvent is cast to remove the solvent, and formed into a sheet (sheet or film) or impregnated into a base material.

(1) Prepreg A prepreg, which is a specific example of a crosslinkable molded article, is obtained by uniformly dissolving or dispersing an allyl group-modified norbornene-based polymer and various additives in a solvent such as toluene, cyclohexane, or xylene. Then, after impregnating the reinforcing substrate,
It is manufactured by drying to remove the solvent. Generally, it is preferable that the prepreg has a thickness of about 50 to 500 μm. As the solvent, those described above can be used. The amount of the solvent used is adjusted so that the solid content concentration is usually 1 to 90% by weight, preferably 5 to 85% by weight, more preferably 10 to 80% by weight, and most preferably 20 to 80% by weight.

As the reinforcing substrate, for example, a paper substrate (linter paper, kraft paper, etc.), a glass substrate (glass cloth, glass mat, glass paper quartz fiber, etc.) and a synthetic resin fiber substrate (polyester fiber, aramid, etc.) Fiber). These reinforcing base materials may be surface-treated with a treating agent such as a silane coupling agent. These reinforcing substrates can be used alone or in combination of two or more. The amount of the allyl group-containing norbornene-based polymer relative to the reinforcing substrate is appropriately selected depending on the purpose of use, but is in the range of 1 to 90% by weight, preferably 10 to 60% by weight based on the reinforcing substrate.

(2) Sheet A method for producing a sheet, which is one of the specific examples of the crosslinkable molded article, is not particularly limited, but generally, a solvent casting method is used. For example, the crosslinkable resin material of the present invention is dissolved and dispersed in a solvent such as toluene, xylene, or cyclohexane so as to have a solid concentration of about 5 to 50% by weight, cast or coated on a smooth surface, and dried. The solvent is removed by, for example, peeling off 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 to a certain extent at a low temperature, raise the temperature to sufficiently volatilize the solvent. do it.

As the smooth surface, a mirror-finished metal plate, a resin carrier film or the like can be used. When a resin carrier film is used, the solvent to be used and the drying conditions are 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. Further, it can be used for manufacturing a laminate described below.

(3) Laminate A laminate such as a laminate, which is a specific example of a cross-linked molded product, is formed by laminating the above-mentioned prepreg and / or uncross-linked sheet, and heat-press-molds to form a cross-linked / heat-fused sheet. By doing so, 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 is not only laminated on the outer surface of the finished laminate, but depending on the purpose of use,
It may be laminated inside the laminate. In order to prevent warpage at the time of secondary processing such as an etching process, it is preferable to stack the layers in a vertically symmetrical manner. For example, the surface of the laminated prepreg and / or sheet is heated at a heat fusion temperature or higher depending on the modified norbornene resin used, usually 150 to 3
The laminate is heated to about 00 ° C., pressurized to about 30 to 80 kgf / cm ² , and crosslinked and thermally fused between the layers to obtain a laminate. Other methods of applying metal to these insulating layers or substrates include deposition, electroplating, sputtering, ion mecca,
Spraying and layering. Commonly used metals are copper, nickel, tin, silver, gold, aluminum, platinum,
Titanium, zinc, chromium and the like. Copper is most frequently used in wiring boards.

(4) Crosslinking In the present invention, a crosslinkable molded article can be obtained by heating the 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 cross-linking agent and the cross-linking auxiliary, but is usually from 80 to 350 ° C, preferably from 120 to 30 ° C.
Crosslinking is performed by heating to a temperature of 0 ° C, more preferably 150 to 250 ° C. When an organic peroxide is used, the crosslinking time is preferably about four times the half-life of the organic peroxide, usually 5 to 120 minutes, preferably 10 to 9 minutes.
0 minutes, more preferably 20 to 60 minutes. When a photo-crosslinking agent is used as the cross-linking agent, crosslinking can be performed by light irradiation. 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.

[0064]

The present invention will be more specifically described below with reference to Synthesis Examples, Examples and Comparative Examples. The measuring methods of various physical properties are as follows. (1) Glass transition temperature The glass transition temperature was measured by a differential scanning calorimetry (DSC) method. (2) Molecular weight Unless otherwise specified, molecular weight is measured by gel permeation chromatography (GP) using toluene as a solvent.
It was measured as a polystyrene conversion value according to C). (3) Hydrogenation rate The hydrogenation rate of the main chain was measured by ¹ H-NMR. (4) Allyl group content The allyl group content was measured by ¹ H-NMR and calculated by the above formula (1). (5) Dielectric constant and dielectric loss tangent The dielectric constant and dielectric loss tangent at 1 MHz are based on JIS C6
481 was measured. (6) Toluene resistance Toluene resistance was determined by cutting a laminated film into 25 mm squares and boiling them in toluene for 5 minutes, then visually observing changes in appearance, and evaluating them according to the following criteria. ：: no change in appearance, ×: partially dissolved. (7) Solder resistance Solder resistance was measured by cutting a laminated film into 25 mm square.
After floating in a 260 ° C. solder bath for 120 seconds, changes in appearance were visually observed and evaluated according to the following criteria. ：: no change in appearance, ×: deformed.

[Examples 1 to 3] 1,4-methano-1,4,4a, 9a were placed in a 1-liter flask purged with nitrogen.
-5 g of tetrahydrofluorene (hereinafter abbreviated as MTF)
And 120 g of toluene, 0.287 mmol of triisobutylaluminum and 0.287 mmol of isobutyl alcohol as polymerization catalysts, and 1-molecule as a molecular weight regulator.
2.30 mmol of hexene was added. Here, 0.057 mmol of tungsten hexachloride is added,
Stirred for minutes. Thereafter, 45 g of MTF and 0.086 mmol of tungsten hexachloride were continuously dropped into the system in about 30 minutes, and after the dropping was completed, the mixture was stirred for another 30 minutes to terminate the polymerization. The polymerization reaction solution was transferred to a 1-liter autoclave, 160 g of toluene was added, and 0.5 g of nickel acetylacetonate and 3 g of triisobutylaluminum were added.
A mixture of 5.15 g of a 0% by weight toluene solution was added, the inside of the reactor was replaced with hydrogen, and the temperature was raised to 80 ° C. while stirring. 30 kg / c hydrogen pressure when temperature is stable
The reaction was carried out for 3 hours while the pressure was increased to m ² and the hydrogen consumed during the reaction was replenished. Then 4.2 g of water and activated alumina (surface area 320 cm ² / g, pore volume 0.8 cm ³ / g)
g, an average particle size of 15 μm, Neobead D powder manufactured by Mizusawa Chemical Co., Ltd.), and the mixture was stirred at 80 ° C. for 1 hour.
The hydrogenation reaction solution from which the solid content was removed by filtration was poured into 3 liters of isopropyl alcohol to precipitate out, and was collected by filtration. The recovered resin was dried at 100 ° C. and 1 Torr or less for 48 hours. 20 g of the obtained polymer is dissolved in 200 ml of tetrahydrofuran, and n-butyllithium (1.54 mol / l, hexane solution) 35
ml, 70 ml, and 150 ml were added, and the mixture was reacted under a nitrogen atmosphere under heating and reflux for 1 hour. After cooling to room temperature, 1.4 g, 2.7 g of allyl bromide, respectively,
g and 5.6 g were added, and the mixture was stirred at room temperature for 30 minutes. The reaction solution was coagulated and dried in the same manner as above to obtain three types of allyl group-modified polymers (A, B, and C) having different denaturation rates. Table 1 shows the respective physical properties.

[Examples 4 to 6] 50% by weight of MTF was 5-phenyl-2-norbornene (hereinafter abbreviated as PNB).
And three types of allyl group-modified polymers (D, E, F) having different denaturation rates in the same manner as in Examples 1 to 3, except that the mixed monomer was changed to 50% by weight of tetracyclododecene (hereinafter abbreviated as TCD). ) Was synthesized. Table 1 shows the respective physical properties.

[Examples 7 to 9] In a 1-liter polymerization reactor purged with nitrogen, a cyclohexane solution of MTF, a cyclohexane solution of VO (OC ₂ H ₅ ) Cl ₂ as a catalyst, and ethyl aluminum sesquichloride [Al (C ₂ H _5)
1.5 Cl _1.5 ] in a polymerization vessel having a concentration of 55 g / liter, 0.5 mmol / l, respectively.
The solution was supplied at 4.0 mmol / liter, ethylene was supplied at 14 liter / Hr, hydrogen was supplied at 0.5 liter / Hr, and the system was controlled at 10 ° C. On the other hand, the total amount of the polymerization liquid in the flask was continuously 1 liter from the upper portion of the polymerization vessel, and the polymerization liquid was withdrawn so as to have an average residence time of 0.5 hour. The polymerization was terminated by adding a small amount of isopropyl alcohol to the withdrawn polymerization solution, and then adding 1: 1 of an aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water.
Contact under strong stirring using a homogenizer at the ratio of
The catalyst residue was transferred to the aqueous phase. The mixture was allowed to stand, and after removing the aqueous phase, the mixture was further washed twice with distilled water, and the polymerization liquid was purified and separated. This polymerization solution was poured into 3 liters of acetone to precipitate, and was collected by filtration. 10 collected resin
It was dried at 0 ° C. and 1 Torr or less for 48 hours. The obtained polymer was modified with an allyl group in the same manner as in Examples 1 to 3, and three kinds of allyl group-modified polymers (G,
H, I). Table 1 shows the respective physical properties.

Comparative Example 1 A hydrogenated ring-opened polymer was synthesized in the same manner as in Example 3 except that MTF was changed to ethyl tetracyclododecene (hereinafter abbreviated as ETD), and allyl group modification was attempted. However, no allyl group was detected (polymer J). The synthesis results are shown in Table 1.

Comparative Example 2 An addition polymer was synthesized in the same manner as in Example 9 except that MTF was changed to TCD, and an allyl group modification was attempted, but no allyl group was detected (polymer K). . The synthesis results are shown in Table 1.

[0070]

[Table 1] (* 1) The copolymerization ratio is mol%.

Examples 10 to 18 Allyl group-modified norbornene-based polymers (AK) obtained in Examples 1 to 9
Were dissolved in toluene at the compounding ratios shown in Table 2 with various additives, and cast on a glass plate to a thickness of about 100 μm.
m, and fixed on a glass plate at 150 ° C
In an air oven for 1 hour. Twenty of these films are laminated and formed by sandwiching them in a vacuum press at 200 ° C.
Heat treatment was performed. Table 2 shows the characteristics of the obtained sheet having a thickness of 2 mm.

[Comparative Examples 3 to 6] The polymers (J, K) obtained in Comparative Examples 1 and 2 were mixed with various additives, respectively, as shown in Table 2.
Was dissolved in toluene at the compounding ratio shown in Table 1, and formed into a sheet in the same manner as in the Examples, and the physical properties were measured. Table 2 shows the measurement results.

[0073]

[Table 2]

Examples 19 to 21 Polymerization of 2-norbornene (NB) and 5-phenyl-2-norbornene (PNB) by a known method described in US Pat. No. 5,468,819. Addition copolymer (number average molecular weight (Mn) = 6 in terms of polystyrene)
6,400, weight average molecular weight (Mw) = 140,10
0, monomer composition ratio NB / PNB = 45/55 (molar ratio), Tg = 265 ° C.). [Allyl group modification] The obtained norbornene-based addition copolymer was modified with an allyl group in the same manner as in Examples 1 to 3 to obtain three types of allyl group-modified polymers having different modification rates. Table 3 shows the respective physical properties. In addition, the number of parts of the polymer in the table is 100 parts by weight.

[0075]

[Table 3]

[Examples 22 to 24] [Polymerization] An NB / styrene (St) copolymer (number-average molecular weight (Mn) = 14 in terms of polystyrene) was obtained by a known method described in JP-A-4-45113. 200, weight average molecular weight (Mw) = 38,600, copolymer composition ratio N
B / St = 54/46 (molar ratio), Tg = 264 ° C.). [Allyl group modification] The obtained norbornene-based addition copolymer was modified with an allyl group in the same manner as in Examples 1 to 3 to obtain three types of allyl group-modified polymers having different modification rates. Table 4 shows the respective physical properties. In addition, the number of parts of the polymer in the table is 100 parts by weight.

[0077]

[Table 4]

[0078]

According to the present invention, there is provided an allyl group-modified norbornene polymer having excellent dielectric properties, heat resistance and chemical resistance, and a method for producing the same. According to the production method of the present invention, an allyl group can be introduced after hydrogenation of a ring-opened polymer of a norbornene-based monomer. The crosslinkable resin material containing the allyl group-modified norbornene-based polymer of the present invention can provide a laminate excellent in solder heat resistance, dielectric properties, chemical resistance and the like.

Claims (4)

[Claims] A weight average molecular weight (M) obtained by introducing at least one allyl group into an aromatic ring-containing norbornene-based polymer.
w) is an allyl group-modified norbornene-based polymer of 500 to 500,000. 2. The method according to claim 1, wherein the modification ratio of the allyl group is in the range of 0.1 to 100 mol% in terms of the number of moles of the allyl group / the total number of monomer units of the polymer (polymer weight / average molecular weight of monomer). Allyl group-modified norbornene polymer. 3. An allyl group-modified norbornene polymer comprising a step of metallizing an aromatic ring-containing norbornene polymer with an organic metal, and a step of introducing an allyl group by a substitution reaction with allyl halide. Manufacturing method. 4. A weight average molecular weight (M) obtained by introducing at least one allyl group into an aromatic ring-containing norbornene-based polymer.
w) a crosslinkable resin material comprising an allyl group-modified norbornene-based polymer of 500 to 500,000.