JPH07268172A - Thermally crosslinkable cycloolefin resin composition and its crosslinked product - Google Patents

Abstract

PURPOSE:To provide a thermally crosslinkable cycloolefin resin composition containing respective specific cycloolefin resin and curing agent, resistant to solvent cracking even in stressed state, exhibiting low absorptivity and excellent solvent resistance, electrical insulation, adhesivity and heat-resistance and useful for high-frequency circuit board, etc. CONSTITUTION:This cycloolefin resin composition contains (A) a cycloolefin resin having cyclic reactive group and (B) a curing agent exhibiting its effect by heating. The cyclic reactive group of the component A is preferably selected from the groups of formula I and formula II (X is O, NR or CR2; R is H, an aliphatic group or an aromatic group; R1, to R4 are each aliphatic group, aromatic group or hydrogen group which may contain unsaturated C=C group, have functional group as substituent or together form a ring).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a heat-crosslinkable cyclic olefin resin composition excellent in heat resistance, solvent resistance, water resistance, electric insulation and adhesion, and a crosslinked product thereof. The present invention relates to a heat-crosslinkable cyclic olefin-based resin composition having excellent solvent resistance at a damaged portion, a crosslinkable molded article and a crosslinkable molded article comprising the same.

[0002]

2. Description of the Related Art Recently, a hydrogenated product of a ring-opening polymer of a cyclic olefin monomer, an addition polymer of a cyclic olefin monomer, or an addition copolymer of a cyclic olefin monomer and ethylene has been developed. Such a thermoplastic cyclic olefin resin,
Its transparency, heat resistance, low water absorption, chemical resistance, electrical properties, mechanical strength, moldability, and dimensional stability have attracted attention and are used in various fields. Has been done. However, depending on the application, heat resistance, solvent resistance, or mechanical strength may be required, and there is a tendency to modify the resin to enhance these properties and expand its field of application. As a technique along such a direction, a copolymer of a cyclic olefin-based monomer, which is a kind of a thermoplastic cyclic olefin-based resin, and ethylene is subjected to sulfur crosslinking, organic peroxide crosslinking, electron beam crosslinking, or radiation. A method for improving heat resistance, solvent resistance and the like by cross-linking has been proposed (JP-A-62-349).
No. 24). However, in general, thermoplastic cyclic olefin-based resins, like other amorphous resins, have a problem in solvent resistance in a stressed portion, and even if crosslinking is performed by the above method, cracking by a solvent is not always required. It turned out that it is not possible to prevent such problems.

[0003]

Therefore, as a result of intensive studies on a method for improving solvent resistance in a stressed portion, the present inventors have found that a thermoplastic cyclic olefin resin having a cyclic reactive group. Evenly disperse the curing agent into
It has been found that the crosslinking by heating can prevent cracks due to a solvent even in a stressed portion without impairing the properties of the cyclic olefin resin, and thus completed the present invention.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a thermoplastic cyclic olefin resin having a cyclic reactive group, which contains a curing agent capable of exerting its ability by heating and, if necessary, a curing auxiliary agent. The present invention relates to a crosslinkable cyclic olefin resin composition and a crosslinked product thereof.

The cyclic reactive group in the present invention has the following formula (1):

[Chemical 3] And equation (2)

[Chemical 4] (In the formula, X is a group independently selected from the group consisting of —O—, —NR—, and —CR ₂ —, and R is a group selected from hydrogen, an aliphatic group, or an aromatic group. The aliphatic group or aromatic group may contain a functional group as a substituent.R ¹ , R ² , R ³ and R ^{4 each} have an unsaturated carbon-carbon double bond. And an aliphatic group, an aromatic group which may have an unsaturated carbon / carbon double bond, and a hydrogen group, which are independently selected from the group consisting of these aliphatic groups and aromatic groups. May contain a functional group as a substituent, and R ¹ , R ² , R ³ and R ⁴ may combine with any of them to form a ring.). It is a base.

Regarding the cyclic olefin resin having a cyclic reactive group, the thermoplastic cyclic olefin resin having a cyclic reactive group used in the present invention has a cyclic reactive group in the molecular chain, at the side chain or at the terminal part. Resin, number average molecular weight 5,000 to 200,000 (G using cyclohexane as a solvent
Polystyrene-equivalent molecular weight measured by PC), preferably from 8000 to 100,000, and the content of the cyclic reactive group based on the total number of monomer units in the polymer is 0.5.
A thermoplastic cyclic olefin resin having a content of ˜50 mol%, preferably 1.0 to 30 mol%, can be preferably used. The thermoplastic cyclic olefin-based resin having a cyclic reactive group used in the method of the present invention can be produced by a known method. For example, a hydrogenated product of a ring-opening polymer of a cyclic olefin-based monomer, or an olefin group-containing cyclic compound in a random addition copolymer with a cyclic olefin-based monomer and optionally an olefin-based monomer such as ethylene. It can be carried out by a graft reaction of a reactive monomer, a random addition copolymerization of a cyclic olefin-based monomer with an olefin group-containing cyclic reactive monomer and, if necessary, an olefin-containing monomer. A part of the manufacturing method will be described below as an example.

(I) Method by Grafting Cyclic Reactive Monomer Containing Olefin Group Ring-opening obtained by polymerizing cyclic olefin monomer by a known ring-opening polymerization method using titanium or tungsten compound as a catalyst. Hydrogenated cyclic olefin-based resin produced by hydrogenating a polymer by a conventional hydrogenation method, a cyclic olefin monomer, and an unsaturated monomer such as ethylene are added to a transition metal compound / Addition of a polymer obtained by addition polymerization with an aluminum compound-based catalyst and / or a hydrogenated product thereof, or only a cyclic olefin monomer by a known method using a transition metal compound / aluminum compound-based catalyst or a palladium-based catalyst. At least one resin selected from the cyclic olefin-based resins obtained by polymerization, olefin group-containing cyclic reactive monomer It can be prepared by graft-modifying with.
This graft reaction can be carried out by a known method, and a cyclic olefin polymer having a cyclic reactive group can be obtained by a solution method or a melting method using a radical generator such as peroxide. (Ii) Method by Copolymerization of Olefin Group-Containing Cyclic Reactive Monomer When adding (co) polymerizing the cyclic olefin monomer and, if necessary, the unsaturated monomer such as ethylene by a known method By using the olefin group-containing reactive monomer as the copolymerization monomer, a cyclic olefin resin having a cyclic reactive group is obtained. As the olefin group-containing cyclic reactive monomer used at this time, a monomer (described later) used for graft modification can be similarly preferably used. This makes it possible to obtain a target cyclic olefin resin having a cyclic reactive group.

The cyclic olefin monomer used for producing the cyclic olefin resin having a cyclic reactive group is
For example: That is, JP-A-3-
14882, JP-A-3-122137, JP-A-2-
Known monomers such as 227424 and JP-A-2-276842, for example, norbornene, its alkyl, alkylidene, aromatic substituted derivatives and halogen, hydroxyl group, ester group, alkoxy of these substituted or unsubstituted olefins. Group, cyano group, amide group, imide group,
Substituted polar group such as 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, etc .; dicyclopentadiene, 2,3-dihydrodicyclopentadiene, 1,4: 5,8-dimethano-1,2,3,4,4a, 5,8,8a-2,3-cyclopentadiene Nonaphthalene, 6-ethyl-1,4:
5,8-Dimethano-1,4,4a, 5,6,7,8,8
a-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; adducts of cyclopentadiene and tetrahydroindene and the like, derivatives and substitution products similar to the 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 can be mentioned.

As the olefinic monomer which can be copolymerized at the time of addition polymerization, other than ethylene, for example, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl- 1-pentene, 4-methyl-1-
Pentene, 1-hexene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene,
Α-olefins such as 1-icosene; cyclopentene,
Cyclohexene, 3,4-dimethylcyclopentene, 3
-Methylcyclohexene, 2- (2-methylbutyl)-
1-cyclohexene, styrene, α-methylstyrene,
3a, 5,6,7a-tetrahydro-4,7-methano-
Cycloolefins and styrenes having no crosslinking such as 1H-indene; 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-
1,5-heptadiene, 7-methyl-1,6-octadiene, cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene,
5-ethylidene-2-norbornene, 5-methylene-2
Non-conjugated dienes such as -norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, divinylbenzene, 1,5-hexadiene, norbornadiene; 2,3-
Such as diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene, 1,3,5-octatriene, 1,4,9-decatriene. Examples thereof include trienes.

The olefin group-containing cyclic reactive monomer has the following formula (3):

[Chemical 5] And equation (4)

[Chemical 6] (In the formula, X is a group independently selected from the group consisting of —O—, —NR—, and —CR ₂ —, and R is a group selected from hydrogen, an aliphatic group, or an aromatic group. The aliphatic group or aromatic group may contain a functional group as a substituent.R ¹ , R ² , R ³ and R ^{4 each} have an unsaturated carbon-carbon double bond. And an aliphatic group, an aromatic group which may have an unsaturated carbon / carbon double bond, and a hydrogen group, which are independently selected from the group consisting of these aliphatic groups and aromatic groups. May contain a functional group as a substituent, and R ¹ , R ² , R ³ and R ⁴ may combine with any one of them to form a ring.). It is a monomer. The functional groups in R, R ¹ , R ² , R ³ and R ⁴ may be ester groups and / or ether groups. Specific examples of these olefin group-containing cyclic reactive monomers include 4-acryloxymethyl-1,3-dioxolan-2-one and 4-methacryloxymethyl-1,3-dioxolan-2-one. , 5-
Methacryloxymethyl-5-methyl-1,3-dioxan-2-one, 5-methacryloxymethyl-5-ethyl-1,3-dioxan-2-one, 4-allyloxymethyl-1,3- Dioxolan-2-one, 4- (2 '
-Methylallyloxy) methyl-1,3-dioxolane-
2-one, 5-allyloxymethyl-5-methyl-1,3
-Dioxan-2-one, 5- (2'-methylallyloxy) methyl-5-methyl-1,3-dioxolane-2-
On, 4- (5-norbornene-2-methyloxymethyl) -1,3-dioxolan-2-one, 4- (3-butenyl) -1,3-dioxolan-2-one, 1,2-
Carbonate-4-vinylcyclohexane, 4-vinyl-1,3-dioxolan-2-one, 4-vinyl-4-
Methyl-1,3-dioxolan-2-one, 4-allyl-1,3-dioxolan-2-one, 4- (2'-allylphenoxymethyl) -1,3-dioxolan-2-one, 5- ( 2'-allylphenoxymethyl) -5-methyl-1,3-dioxan-2-one, 4- (4'-isopropenylphenoxymethyl) -1,3-dioxolan-2-one, 5- (4'- Isopropenylphenoxymethyl) -5-methyl-1,3-dioxan-2-one,
4- (5'-norbornene-2'-carboxymethyl)
-1,3-dioxolan-2-one, 5- (5'-norbornene-2'-carboxymethyl) -5-methyl-
Cyclic carbonates such as 1,3-dioxan-2-one;

4-acryloxymethyl-1,3-oxazolidin-2-one, 4-acryloxymethyl-3-methyl-1,3-oxazolidin-2-one, 4-acryloxymethyl-3-phenyl-1 , 3-oxazolidin-2-one, 4-methacryloxymethyl-1,3-oxazolidin-2-one, 4-methacryloxymethyl-3-methyl-1,3-oxazolidin-2-one, 4
-Methacryloxymethyl-3-phenyl-1,3-oxazolidin-2-one, 4-allyloxymethyl-1,
3-oxazolidin-2-one, 4-allyloxymethyl-3-phenyl-1,3-oxazolidin-2-one,
4-allyloxymethyl-3-methyl-1,3-oxazolidin-2-one, 4- (2'-methylallyloxymethyl) -1,3-oxazolidin-2-one, 4- (2 '
-Methylallyloxymethyl) -3-phenyl-1,3-
Oxazolidin-2-one, 4-vinyl-1,3-oxazolidin-2-one, 4-vinyl-3-phenyl-
1,3-oxazolidin-2-one, 4-vinyl-4-
Methyl-1,3-oxazolidin-2-one, 4-vinyl-4-methyl-3-phenyl-1,3-oxazolidin-2-one, 4-allyl-1,3-oxazolidin-
2-one, 4-allyl-3-phenyl-1,3-oxazolidin-2-one, 4- (3'-butenyl) -1,3
-Oxazolidin-2-one, 4- (3'-butenyl)
-3-Methyl-1,3-oxazolidin-2-one, 4
-(2'-allylphenoxymethyl) -1,3-oxazolidin-2-one, 4- (2'-allylphenoxymethyl) -3-methyl-1,3-oxazolidin-2-one, 4- (2 ' -Allylphenoxymethyl) -3-phenyl-1,3-oxazolidin-2-one, 4- (4 '
-Isopropenylphenoxymethyl) -1,3-oxazolidin-2-one, 4- (4'-isopropenylphenoxymethyl) -3-methyl-1,3-oxazolidin-2-one, 4- (4'-iso Propenylphenoxymethyl) -3-phenyl-1,3-oxazolidine-2-
On, 4- (5'-norbornene-2'-carboxymethyl) -1,3-oxazolidin-2-one, 4-
(5'-norbornene-2'-carboxymethyl) -3
-Methyl-1,3-oxazolidin-2-one, 4-
(5'-norbornene-2'-carboxymethyl) -3
-Oxazolidinones such as phenyl-1,3-oxazolidin-2-one;

5-hexene-4-olide, 6-heptene-5-olide, 3-vinyl-4-butanolide, 3
-Vinyl-5-pentanolide, 5-allyloxy-4-
Lactones such as pentanolide and 9-deceno-5-olide are exemplified, and among these, 4-allyloxymethyl-1,3-dioxolan-2-one and 4-vinyl-1,3-dioxolane-2 are exemplified. -One, 1,2-carbonate-4-vinylcyclohexene, 4- (2'-allylphenoxymethyl) -1,3-dioxolan-2-one, 4-allyloxymethyl-3-phenyl-1,3-oxazolidine -2-one, 4- (2'-allylphenoxymethyl) -3-phenyl-1,3-oxazolidine-
2-one and the like are preferably used.

As the thermoplastic cyclic olefin resin having a cyclic reactive group of the present invention, the cyclic reactive group-containing cyclic olefin resin obtained by the above various methods can be used alone or in combination. Further, the thermoplastic cyclic olefin-based resin having a cyclic reactive group may be a mixture of a cyclic olefin-containing cyclic olefin resin and a cyclic olefin-free cyclic olefin resin. Further, the thermoplastic cyclic olefin-based resin having these cyclic reactive groups may contain a functional group such as a hydroxyl group, an ester group, an organic silicon group and a carboxylic acid group in addition to the cyclic reactive group, and if desired, Various additives such as a phenol-based or phosphorus-based antioxidant, a phenol-based heat deterioration inhibitor, a benzophenone-based ultraviolet stabilizer, an amine-based antistatic agent, and the like may be added. Further, other resins, rubbers, fillers and the like can be mixed and used as long as the object of the present invention is not impaired.

Curing agent The curing agent that can cross-link the thermoplastic cyclic olefin resin having a cyclic reactive group by heat is not particularly limited, but for example, hexamethylene diamine,
Fats such as diaminocyclohexane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.0 ^2,6 ] decane, triethylenetetraamine, 1,3- (diaminomethyl) cyclohexane Group polyamines;
4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, α, α′-bis (4-aminophenyl) -1,3-diisopropylbenzene, α,
Aromatic polyamines such as α'-bis (4-aminophenyl) -1,4-diisopropylbenzene, diaminodiphenylsulfone and phenylenediamine; 4,4'-
Diazidochalcone, 2,6-bis (4'-azidobenzal) cyclohexanone, 2,6-bis (4'-azidobenzal) 4-methylcyclohexanone, 4,4'-diazidodiphenylsulfone, 4,4'-diazide Bisazides such as diphenylmethane and 2,2′-diazidostilbene; dicarboxylic acids such as fumaric acid, phthalic acid, maleic acid, trimellitic acid and hymic acid; polyhydric phenols such as bisphenol A, phenol novolac resin, cresol novolac resin And the like. These may be used alone or as a mixture of two or more.
Among these, aliphatic polyamines, aromatic polyamines, and bisazide are preferable because they can be uniformly dispersed.
Further, if necessary, a curing aid may be added to enhance the efficiency of the crosslinking reaction.

The amount of the curing agent blended is not particularly limited, but 100% by weight of the cyclic olefin resin is used in order to efficiently carry out the crosslinking reaction, improve the physical properties of the resulting crosslinked product, and economically. It is used in the range of 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on parts.
If the amount of the curing agent is too small, crosslinking is difficult to occur and sufficient solvent resistance and heat resistance cannot be obtained, and if it is too large, the electrical properties, low water absorption, moisture resistance and other properties of the crosslinked resin deteriorate. It is not preferable because

Examples of the curing aid include tertiary amines such as pyridine, benzyldimethylamine, triethanolamine, triethylamine and the like. The purpose is to adjust the curing rate and to improve the efficiency of the crosslinking reaction. Is added in. The amount of the curing aid compounded is not particularly limited, but it is used in the range of 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the cyclic olefin resin.

As a method for uniformly dispersing the curing agent or, if necessary, the curing aid in the thermoplastic cyclic olefin resin having a cyclic reactive group, the resin is mixed in a resin solution and dissolved / dispersed to form a solvent. There are methods of removing the resin, mixing and dispersing the resin in a molten state, and the like. As a method of using these heat-crosslinkable cyclic olefin resin compositions, a resin solution is cast into a film or melted at a temperature at which crosslinking does not occur or at a temperature at which the crosslinking rate is sufficiently slow. The solvent of the resin solution is not particularly limited as long as it dissolves the resin, and for example, toluene, xylene, ethylbenzene, trimethylbenzene, chlorobenzene, decalin, tetralin and the like can be used. In addition, in the method of melting the resin and adding the curing agent, it is necessary to be able to melt, mix, and disperse at a temperature at which the crosslinking reaction does not occur, and this method cannot be used depending on the combination. Also in the method of adding to the resin solution, when heating for removing the solvent, it is necessary to set the temperature so that crosslinking does not occur.

The crosslinkable molded article of the present invention is obtained by molding the crosslinkable cyclic olefin resin composition at a temperature at which it does not crosslink. Molding is usually carried out by dissolving the resin composition in a solution at a temperature at which crosslinking does not occur and forming a resin solution.

The solvent is not particularly limited as long as it dissolves the resin, and examples thereof include toluene, xylene, ethylbenzene, trimethylbenzene, chlorobenzene, decalin and tetralin.

The resin solution may be molded by a dipping method in which the substrate is impregnated with the solution and dried to remove the solvent, a casting method in which the solution is cast on a smooth surface and dried to remove the solvent, and the solution is centrifuged. The spin coating method, the roll coating method, the curtain coating method and the like, in which the solvent is molded and dried to remove the solvent, are exemplified. The temperature for removing the solvent is a temperature at which crosslinking does not occur.

As the base material impregnated with the resin solution, cloth-like base materials such as glass cloth, aramid (trade name) cloth, polyester cloth, nylon cloth, etc .; mat-like base materials of these same materials; non-woven fabric, kraft paper, Examples include linter paper.

The crosslinkable molded article of the present invention can be used for prepregs, sheets and the like, and they can be used as materials for laminated plates, interlayer plates and interlayer insulating films. The prepreg is obtained by impregnating a base material with a resin solution by a casting method, and is usually molded to have a thickness of about 50 to 500 μm. The sheet is obtained by a casting method or a spin coating method. The thickness of the sheet formed by the casting method is usually about 10 μm to 1 mm.

The crosslinked molded article of the present invention is obtained by heating and crosslinking the crosslinkable cyclic olefin resin composition, or by crosslinking the crosslinkable molded article. The heating temperature is a temperature at which a crosslinking reaction occurs, and it varies depending on the types of the crosslinkable cyclic olefin resin composition and the curing agent, but is usually 30 to 400 ° C, preferably 50 to 350 ° C, more preferably 100 to 300. ℃. The heating time is several seconds to 24 hours, preferably about 5 minutes to 10 hours.
When the resin composition is used by dissolving it in a solution, the solvent is dried and removed, and then heated to carry out a crosslinking reaction. The solvent is not particularly limited as long as it dissolves the resin, and examples thereof include the same ones as described above.

The crosslinked molded article of the present invention has a water absorption of 0.1%.
It has low water absorption and insulation resistance of 10 ¹⁵ to 10 below.
The dielectric constant of ¹⁷ Ω, 1 MHz is 2.3 to 3.0, and the dielectric loss tangent of 1 MHz is 0.0001 to 0.01, which is excellent in electrical characteristics. It also has excellent heat resistance and crack resistance.

The cross-linked molded article of the present invention can be used as a laminate, an interlayer insulating film, or the like. The laminated plate is obtained by stacking the above-mentioned prepregs and sheets, compression-molding them under heating, and crosslinking and fusing each layer. 30 to compression molding
It is carried out under a pressure of about 80 kgf / cm ² . The laminated plate can be used alone, but can also be used as a circuit board by laminating a conductive layer for wiring. The interlayer insulating film is obtained by crosslinking the sheet under heating. The sheet may be a single layer or a multi-layer, but the thickness of the interlayer insulating film is usually set to 50 μm or less.

[0026]

EXAMPLES The present invention will be described more specifically with reference to the following Reference Examples, Examples and Comparative Examples. The insulation resistance, dielectric constant, dielectric loss tangent, and water absorption were measured according to JIS K6911. Regarding the solvent resistance, a xylene solution of the crosslinkable cyclic olefin resin composition is applied onto a silicon wafer by a spin coating method so as to have a film thickness of about 10 to 20 μm, and the applied product is heated to 250 ° C. Evaluation was carried out by immersing in a solvent what was crosslinked for 3 hours. The cyclic reactive group content was measured by ¹ H-NMR.

Reference Example-1 6-Methyl-1,4,5,8-dimethano-1,2,3,3
4,4a, 5,8,8a-octahydronaphthalene (M
TD) is subjected to ring-opening polymerization by a known method, and hydrogenated to obtain a cyclic olefin resin [glass transition temperature 152 ° C., hydrogenation rate approximately 100%: number average molecular weight approximately 28,000 (polystyrene conversion)] 50 weight Part and 4-allyloxymethyl-1,
3-dioxolan-2-one 10 parts by weight, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-
By mixing 32 parts by weight and melt-kneading at 260 ° C. using a twin-screw extruder having a diameter of 30 mm and a vent device,
51 parts of cyclic carbonate-modified cyclic olefin resin A was obtained [glass transition temperature 154 ° C., number average molecular weight about 26,
000 (polystyrene equivalent)]. The cyclic carbonate content of the obtained modified polymer was 3.5 mol% based on the total number of monomer units in the polymer.

Reference Example-2 An oxazolidinone-modified cyclic compound was prepared in the same manner as in Reference Example-1, except that 15 parts by weight of 4-allyloxymethyl-3-phenyl-1,3-oxazolidin-2-one was used as the modifying monomer. Olefin resin B was obtained [glass transition temperature 155 ° C., number average molecular weight 27,000 (polystyrene conversion)]. The oxazolidinone content of the obtained modified polymer was 3.8 mol% based on the total number of monomer units in the polymer.

Reference Example-3 50 parts by weight of the cyclic olefin resin used in Reference Example-1 and 4- (3-butenyl) -1,3-dioxolane-2-
14 parts by weight of ON and 3 parts by weight of dicumyl peroxide were dissolved in 120 parts by weight of cyclohexane, reacted at 150 ° C. for 3 hours in an autoclave, and then the reaction product solution was poured into 240 parts by weight of isopropyl alcohol. , Solidified. The solidified cyclic carbonate modified polymer is heated to 100 ° C.
After vacuum drying for 5 hours, 50 parts of cyclic carbonate-modified cyclic olefin resin C was obtained [glass transition temperature 154
C., number average molecular weight of about 27,000 (polystyrene conversion)]. The cyclic carbonate content of the obtained modified polymer was 6.0 mol% based on the total number of monomer units in the polymer.
Met.

Reference Example-4 A lactone-modified cyclic olefin system was used in the same manner as in Reference Example-3 except that 16 parts by weight of 5-hexene-4-olide was used as the modifying monomer and 4 parts by weight of dicumyl peroxide was used as the peroxide. Resin D was obtained [glass transition temperature 151 ° C., number average molecular weight 26,000 (in terms of polystyrene)]. The lactone group content of the obtained modified polymer is
It was 6.1 mol% based on the total number of monomer units in the polymer.

Reference Example-5 Random addition copolymer of ethylene and MTD produced according to a known method (ethylene composition 50%, glass transition temperature 141 ° C., number average molecular weight 30,000 (polystyrene conversion) is used as raw material resin. Except for doing
A cyclic carbonate-modified cyclic olefin resin E was obtained in the same manner as in 1 (glass transition temperature 140 ° C., number average molecular weight 28,000 (in terms of polystyrene)). The cyclic carbonate content of the obtained modified polymer was 4.0 mol% based on the total number of monomer units in the polymer.

Reference Example-6 50 parts by weight of the raw material resin used in Reference Example-5 and 4-allyloxymethyl-3-phenyl-1,3-as a modifying monomer
An oxazolidinone-modified cyclic olefin resin F was obtained in the same manner as in Reference Example 3 except that 23 parts by weight of oxazolidin-2-one was used [glass transition temperature 145 ° C.,
Number average molecular weight 26,500 (in terms of polystyrene)]. The oxazolidinone content of the obtained modified polymer was 4.5 mol% based on the total number of monomer units in the polymer.

Reference Example-7 Hydrogenated product of a copolymer obtained by ring-opening polymerization of a mixed monomer (MTD / DCP = 70/30 molar ratio) of MTD and dicyclopentadiene (DCP) [glass transition temperature 133 ℃,
A cyclic carbonate-modified cyclic olefin resin G was obtained in the same manner as in Reference Example 2 except that a hydrogenation rate of approximately 100% and a number average molecular weight of 27,000 (in terms of polystyrene) were used as the raw material resin. Temperature 135 ℃,
Number average molecular weight 26,000 (polystyrene conversion)]. The cyclic carbonate content of the obtained modified polymer was 7.0 mol% based on the total number of monomer units in the polymer.

Reference Example-8 MTD, ethylene and 4- (3-butenyl) -1,3
-Dioxolan-2-one (BDO) was used as a monomer component, and random addition copolymerization was performed by a known method using VO (Et) Cl ₂ and ethylaluminum sesquichloride as a catalyst, and the composition ratio of each monomer unit in the polymer was MTD / ethylene / BDO = 45/50/5 molar ratio of cyclic carbonate-containing cyclic olefin resin H was obtained [glass transition temperature 140 ° C., number average molecular weight 30,000].
(Polystyrene conversion)]. The cyclic carbonate content of the obtained modified polymer was 5.0 mol% based on the total number of monomer units in the polymer.

Example-1 30 parts by weight of the cyclic carbonate-modified cyclic olefin resin A obtained in Reference Example-1 and 1.8 parts by weight of α, α'-bis (4-aminophenyl) -1,3-diisopropylbenzene were used. When dispersed in 80 parts by weight of xylene, a uniform solution was obtained without causing precipitation or the like. This was applied onto a silicon wafer by spin coating so as to have a thickness of 10 μm, and heated in an oven under nitrogen at 250 ° C. for 3 hours to be cured. The stress on this sample is 25
It was MPa. Next, this sample was immersed in acetone, isopropanol, xylene, N, N-dimethylformamide, 50% NaOH aqueous solution, and concentrated hydrochloric acid for 1 minute, and the surface was observed. All the solvents showed no dissolution, cracks, swelling, etc. I couldn't do it.

Example-2 The heat-crosslinkable cyclic olefin resin composition solution obtained in Example-1 was applied on a Teflon plate to a thickness of 750 using a coating machine.
It was applied to have a thickness of μm. It was left to dry at 60 ° C. for 20 minutes and further at 110 ° C. for 10 minutes. After that, it was peeled off from the Teflon plate. The thickness of the obtained sheet is about 150μ.
It was m. 8 sheets of this sheet are laminated, and 3 on both sides.
A 5 μm copper foil was laminated, and pressed at a temperature of 200 ° C. and a pressure of 40 kgf / cm ² for 1 hour so as to have a thickness of 1 mm and thermally fused to obtain a crosslinked laminate. Even if the laminated plate was contacted with solder at 300 ° C. for 1 minute, no abnormality such as peeling of the copper foil or blistering was observed, and the water absorption rate was 0.06.
%, The insulation resistance was 4 × 10 ¹⁶ Ω, and the dielectric constant and dielectric loss tangent at 1 MHz were 2.6 and 0.005, respectively. This laminated plate was mixed with acetone, isopropanol, xylene,
When the surface was observed by immersing each in N, N-dimethylformamide for 1 minute, no dissolution, cracking, swelling or the like was observed in any solvent.

Example 3 A glass cloth substrate having a thickness of 0.1 mm was immersed in the crosslinkable cyclic olefin resin composition solution obtained in Example 1 and taken out. This is dried at 60 ° C. for 20 minutes, then 150
It was left at 10 ° C. for 10 minutes to obtain 8 prepregs. 40% by weight of this prepreg was the crosslinkable cyclic olefin resin of the present invention and had a thickness of about 110 μm. The eight prepregs were laminated, and 35 μm copper foil was further laminated on both sides, and the press temperature was 200 ° C. and the press pressure was 40 kgf /
In cm ^2, and heat sealed with 20 minutes pressed to a thickness of 1mm to give a laminate. With this laminated plate, no abnormality such as peeling of copper foil or blistering was observed even when soldering at 300 ° C. for 1 minute, water absorption was 0.10%, and dielectric constant at 1 MHz was 3.0. Met.

Examples-4 to 13 As shown in Tables 1 and 2, the same treatment as in Examples 1 and 2 was carried out by changing the combination and the compounding amount of the cyclic olefin resin having a cyclic reactive group and the curing agent. It was The results are shown in Table 1
The results are shown in Table 2.

[0039]

[Table 1] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example Resin Hardening agent Solvent ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 4 A 2,6-bis (4′-azidobenzal) xylene (30 ) -4-Methylcyclohexanone (1.5) (80) 5 A 3 (4), 8 (9) -bis (aminomethyl) 1,2,4-trimethyl (30) tricyclo [5.2.1.0 ^2.6 ] decane (0.8) Benzene (80) 6 B α, α′-bis (4-aminophenyl) 1,2,4-trimethyl (30) -1,3-diisopropylbenzene (1.5) Benzene (80) 7 C α, α′-bis (4-aminophenyl) 1,2,4-trimethyl (30) -1,3-diisopropylbenzene (1.7) benzene (80) 8 D 2,6-bis (4'-azidobenzal) 1,2,4-trimethyl (30) -4-Methylcyclohexanone (1.8) Benzene (80) 9 E 2,6-bis (4'-azidobenzal) 1,2,4-trimethyl (3 0) -4-methylcyclohexanone (1.1) benzene (80) 10 F 2,6-bis (4'-azidobenzal) 1,2,4-trimethyl (30) -4-methylcyclohexanone (1.2) benzene (80) 11 G 2,6-bis (4′-azidobenzal) 1,2,4-trimethyl (30) -4-methylcyclohexanone (1.3) benzene (80) 12 H 2,6-bis (4′-azidobenzal) 1,2 , 4-Trimethyl (30) -4-Methylcyclohexanone (2.6) Benzene (80) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━ ・ The figures in () for resin, curing agent and solvent represent parts by weight.

[0040]

[Table 2] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example Example Melt-resistant solder Dielectric constant Water absorption Insulation resistance Dielectric loss tangent property Heat resistance (%) (Ω / cm) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 4 〇 〇 2.6 0.07 3 × 10 ¹⁶ 0.0005 5 〇 〇 2.6 0.06 3 × 10 ¹⁶ 0.0005 6 〇 〇 2.6 0.07 3 × 10 ¹⁶ 0.0006 7 〇 ○ 2.7 0.09 2 × 10 ¹⁶ 0.001 8 ○ ○ 2.6 0.06 4 × 10 ¹⁶ 0.0007 9 ○ ○ 2.4 0.02 8 × 10 ¹⁶ 0.0001 10 ○ ○ 2 0.5 0.05 5 × 10 ¹⁶ 0.0003 11 〇 〇 2.7 0.098 8 × 10 ¹⁶ 0.0018 12 〇 〇 2.8 0.10 1 × 10 ¹⁶ 0.0031 ━━━━━━━ ━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ・ Check solvent resistance with acetone, isopropanol, xylene, N, N-dimethylformamide, 50%.
It was performed with an aqueous NaOH solution and concentrated hydrochloric acid, respectively. -Solvent resistance shows the result measured like Example-1. -Holder heat resistance, dielectric constant, water absorption, insulation resistance, and dielectric loss tangent are the measured values of the sample obtained in the same manner as in Example-2.

Comparative Example-1 In Example-1, a sample was similarly formed on a silicon wafer without compounding a curing agent, and a solvent resistance test was conducted. As a result, it was found that acetone and N, N-dimethylformamide caused cracking. Was generated and dissolved in xylene.

Comparative Example-2 Random addition copolymer of ethylene and MTD used as a raw material resin in Reference Example-5 [ethylene composition 50%, glass transition temperature 141 ° C, number average molecular weight 30,000 (polystyrene conversion)]. 20 parts by weight, 1 part by weight of α, α'-bis (t-butylperoxy-m-isopropyl) benzene,
1 part by weight of diallyl phthalate was dissolved in 60 parts by weight of xylene to obtain a heat-crosslinkable cyclic olefin resin composition solution.
This was applied onto a silicon wafer by a spin coating method so as to have a thickness of 10 μm, and was applied under nitrogen in an oven under nitrogen.
Curing was performed by heating at 0 ° C for 3 hours. Acetone, isopropanol, xylene, N, N-
When the surface was observed by immersing it in dimethylformamide, 50% NaOH aqueous solution, concentrated hydrochloric acid for 1 minute, acetone, N,
Cracks occurred in N-dimethylformamide, and swelling was slightly observed in xylene.

[0043]

[Effect] According to the present invention, cracks due to a solvent can be prevented even in a stressed portion without impairing the characteristics of the cyclic olefin resin. Further, the crosslinked molded article of the present invention has excellent solvent resistance, low water absorption, electrical insulation, and adhesion, and even if it is contacted with solder at 300 ° C for 1 minute, peeling or blistering of the laminated copper foil occurs. It has excellent heat resistance and is useful as a high-frequency circuit board.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/28 KEY C08L 23/08 LDC 31/00 LHQ 39/04 LJY (72) Inventor Yasuhiro Mitsuda 1-2-1 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Japan Zeon Corporation Research and Development Center

Claims (4)

[Claims] 1. A heat-crosslinkable cyclic olefin-based resin composition comprising a cyclic olefin-based resin having a cyclic reactive group and a curing agent that exerts its ability by heating. 2. The cyclic reactive group is represented by the following formula (1): And the formula (2) (In the formula, X is a group independently selected from the group consisting of —O—, —NR—, and —CR ₂ —, and R is a group selected from hydrogen, an aliphatic group, or an aromatic group. The aliphatic group or aromatic group may contain a functional group as a substituent.R ¹ , R ² , R ³ and R ^{4 each} have an unsaturated carbon-carbon double bond. And an aliphatic group, an aromatic group which may have an unsaturated carbon / carbon double bond, and a hydrogen group, which are independently selected from the group consisting of these aliphatic groups and aromatic groups. May contain a functional group as a substituent, and R ¹ , R ² , R ³ and R ⁴ may combine with any one of them to form a ring.). The thermally crosslinkable cyclic olefin resin composition according to claim 1, which is a group. 3. A crosslinkable molded article obtained by molding the heat-crosslinkable cyclic olefin resin composition according to claim 1. 4. A cross-linked molded article obtained by molding and cross-linking the heat-crosslinkable cyclic olefin resin composition according to claim 1.