Hardening components and their hardened bodies, molded bodies, electrical insulating materials, laminates

Abstract

The present invention provides a composition of a hardened body that exhibits high mechanical strength (elastic modulus, etc.) at both room temperature and high temperature. The hardened composition contains an olefin-aromatic vinyl compound-aromatic polyene copolymer that satisfies the conditions described in (1) to (4) below, and an additive resin; wherein the additive resin is selected from one or more of the group consisting of hydrocarbon elastomers, polyphenylene ethers, olefin-aromatic vinyl compound-aromatic polyene copolymer oligomers, and aromatic polyene resins. (1) The average molecular weight of the copolymer is between 5,000 and 100,000. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound with 8 or more carbon atoms and less than 20 carbon atoms, and the content of the aromatic vinyl compound monomer unit is more than 0% by mass and less than 70% by mass. (3) The aromatic polyene is selected from polyenes with a number of vinyl and / or elongated vinyl groups having a number of carbons of 5 to 20, and the content of vinyl and / or elongated vinyl groups derived from the aromatic polyene unit is 1.5 to less than 20 based on the number average molecular weight. (4) The olefins are selected from olefins with 2 or more carbon atoms to less than 20, and the total number of monomer units of olefins, aromatic vinyl compounds and aromatic polyenes is 100 by mass.

Description

[Technical field]

[0001] The present invention is a composition. The so-called sheet in this specification also contains the concept of the film. Further, even if the film is described in this specification, the concept of the sheet is also included. [Previous technology]

[0002] Due to the communication frequency transition to the Gigahertz band and a higher high frequency band, the demand for insulating materials with low dielectric characteristics is rising. Since the aromatic vinyl compound polymers such as polyethylene or polystyrene or the like are not polar groups in the molecular structure, it is used as a material that shows excellent low dielectric constant and low dielectric loss tangent. I know it. However, since these polymerization resistance is dependent on the crystallization melting point or the glass transfer temperature, there is a problem as the heat resistance of the electrical insulator, and therefore, due to the thermoplastic resin, there is also a problem in the formation of the film formulation (Patent Document 1). .

[0003] Although fluorine-like resin such as fluoride is excellent in low dielectric constants, low dielectric losses, and excellent heat resistance, but is formed, and the film formation is difficult and the components are low. In addition, there is also a problem with respect to the focus of the copper foil of the wiring. On the other hand, the substrate, the insulating material, the insulating material, the dielectric constant, the dielectric constant, the dielectric constant, the dielectric constant, the dielectric constant, the dielectric constant, the dielectric constant, the dielectric constant The electric loss is relatively high, and it is desirable to improve as a high-frequency insulating material (Patent Document 2).

[0004] The electrical insulating material constituted by the graft or block copolymer constituted by the polymer segment of the olefin and a styrene system (Patent Document 3) has been proposed. This material is at the essential low dielectric constant, low dielectric loss in the essential low dielectric constant of the olefin or a styrene hydrocarbon polymer. The method of manufacturing the material is, in the presence of a styrene monomer, a dilycene monomer, and a radical polymerization initiator, a general grafting polymerization of the commercially available polyethylene, polypropylene, this method is present The branch efficiency cannot be increased and the uniformity of the polymer is inadequate. Further, the resulting polymer contains a gel, workability, and a problem of poor filling. The material is a thermoplastic resin and is insufficient heat resistance, and a heat-resistant resin such as a 4-methyl-1-pentene system is required. This material is difficult to apply or fill the forming method of hardening or filled in a predetermined place.

[0005] Patent Document 4 describes an insulating layer constructed from a crosslinked structure, and the crosslinked structure contains a hydrocarbon compound having a plurality of aromatic ethylene as a crosslinking component. In the embodiment, the crosslinking component of the crosslinking component is just straight, and it is considered to be difficult to fill a large amount of filler.

[0006] Patent Document 5 discloses having a particular polymerization catalyst resulting from a specific composition, a vinyl-olefin (aromatic vinyl compound)-polylene copolymer, non-polar compound copolymer Hardware. Although the hardening body described in Patent Document 5 has a low dielectric constant, the low dielectric loss is characterized, but is extremely soft, it is necessary to increase the mechanical strength of the elastic modulus of normal temperature and high temperature. In the case of an insulating material such as FPC (Flexible Printed Circuit; flexible printed circuit) or FCCL (flexible Copper Clad Laminate; flexible Copper Clad Laminate; Coverlay) Size stability such as thickness in the configuration step or after the construct. In addition, the hardening body of the composed of the composition is improved in the mid-metal foil (especially copper foil) in the embodiment. Patent Document 6 discloses having a different polymerization catalyst resulting from a particular polymeric catalyst, a ethylene-olefin (aromatic vinyl compound)-polylene copolymer, non-polar vinyl compound copolymer. The hardening body, but in the examples, the hardening body of the composed of the composed of the composition relative to the metacular or low temperature characteristics of the metal foil (especially the copper foil) is also improved. Patent Document 7 has also been described in the hardening body comprising the same copolymer, but the hardening body of the composition in the examples is improved relative to the metaglativity of the metal foil (especially copper foil).

[0007] Patent Document 5, Patent Document 6, Patent Document 7, discloses the ethylene-olefin (aromatic vinyl compound)-polylene copolymer obtained by specific polymerization catalysts and by specific composition Hardcore body constituted by a polar vinyl compound. These hardened compositions contain relatively large amounts of monomer components (aromatic vinyl compounds or aromatic polynenes) for varnish. It is therefore not only a smell, but it is also possible to easily manufacture the topic of B-class material (semi-financing sheet). These hardened compositions have a complex problem that makes manufacturing equipment. [Previous Technical Document] [Patent Document]

[0008] [Patent Document 1] Japan Special Joho 52-31272. [Patent Document 2] Japan Kaixa No. 6-192392. [Patent Document 3] Japan Kaixa No. 11-60645. [Patent Document 4] Japanese Laid-Open Patent Publication No. 2004-087639. [Patent Document 5] Japanese Laid-Open No. 2010-280771. Patent Document 6] Japanese Laid-Open Patent Publication No. 2009-161743. [Patent Document 7] Japanese Laid-Open No. 2010-280860. [Summary]

[0009] [Subject to Solving Projects]

[0010] In the previous technique described above, it is impossible to obtain a thermoplastic composition of forming processing, and highly low dielectric properties and mechanical strength (elastic modulus, etc.) at room temperature and high temperature. The body is desired to provide this composition and hardening body. [To solve the means of the project]

[0011] The present invention can be provided in the present invention.

[0012] A hardere composition comprising an olefin-aromatic vinyl compound-aromatic polylene copolymer that satisfies the conditions (1) to (4), and adding a resin; the aforementioned addition resin is selected from the group consisting of free hydrocarbon-based elasticity. Body, polyphenylene ether, olefin-aromatic vinyl compound - aromatic polylene copolymerization and aromatic polyene resin constitutes more or more. (1) The number of copolymers has an average molecular weight of 5,000 or more to 100,000 or less. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having a carbon number of 8 or more to 20 or less, and the content of the aromatic vinyl compound monomer unit is from 0% by mass or more to 70% by mass or less. (3) Aromatic polyethylene is selected from the group consisting of a polyene having a plurality of carbon numbers 5 or more and 20 or less in the molecule, and is derived from an aromatic polyene unit The content of the base and / or dethylvinyl group is 1.5 or more than 20 or more in the amount average molecular weight. (4) The olefin is one or more types selected from the group consisting of an olefin having a carbon number 2 or more, an olefin monomer unit, an aromatic vinyl compound monomer unit, and an aromatic polyely monomer unit a total of 100% by mass. .

[0013] An electrically insulating material is formed by a hardening body obtained by an olefin-aromatic vinyl compound-aromatic polyalkylene copolymer that satisfies the following (1) to (4), and the hardened body obtained by adding a resin. The addition of the resin is one of the groups selected from the group consisting of a hydrocarbon elastomer, a polyphenylene ether, an olefin-aromatic vinyl compound-aromatic polylene copolymer, and the aromatic polynene resin; the electrical insulation The material is from 300 ° C, the modulus of 5 × 105Pa is 5 × 105Pa, preferably 1 × 106Pa or more, and 23 ° C, 10 GHz dielectric constant is 2.0 or more to 2.5 or more, and dielectric loss is 0.0005 or more to 0.003 or less. . (1) The number of copolymers has an average molecular weight of 5,000 or more to 100,000 or less. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having a carbon number of 8 or more to 20 or less, and the content of the aromatic vinyl compound monomer unit is from 0% by mass or more to 70% by mass or less. (3) Aromatic polyethylene is selected from the group consisting of a polyene having a plurality of carbon numbers 5 or more and 20 or less in the molecule, and is derived from an aromatic polyene unit The content of the base and / or dethylvinyl group is 1.5 or more than 20 or more in the amount average molecular weight. (4) The olefin is one or more types selected from the group consisting of an olefin having a carbon number 2 or more, an olefin monomer unit, an aromatic vinyl compound monomer unit, and an aromatic polyely monomer unit a total of 100% by mass. . [Inventive efficacy] The hardening composition of the present invention has the properties of the thermoplastic resin. Further, the hardening body has excellent dielectric characteristics by hardening the hardening composition to be hardened, and the mechanical strength (elastic modulus, etc.) of room temperature and high temperature. [Embodiment]

[0015] More detailed description. In this specification, the olefin-aromatic vinyl compound-aromatic polyene copolymer may be simply described as a copolymer. The numerical range in this specification is as long as there is no particular instruction, and the upper limit and the lower limit value of the numerical range are included. The so-called sheet in this specification also includes the concept of the film. Further, even in this specification, it is described as a film, which is also indicative of the same content as the sheet. Further, in this specification, the hardening body is the same as the hardening. In this specification, the content is also referred to as content.

[0016] [Compose] In this specification, the composition (hardened composition) is sometimes described as a resin composition or a hardened resin composition. The composition of the present invention comprises a foregoing olefin-aromatic vinyl compound-aromatic polylene copolymer having a molecular weight range of the aforementioned sources. Further, the present composition includes one of the predetermined amounts of "adding a resin". Further, the composition may also include "monomers" and "hardeners" described later.

[0017] [Olefin-Aromatic Vinyl Compound-Aromatic Polythylene Copolymer] The method for producing an olefin-aromatic vinyl compound-aromatic polylene copolymer according to the present invention is described, for example, is described in Japan. 2009-161743 Bulletin, Japanese Laid-Open No. 2010-280771, International Publication WO00 / 37517. The olefin-aromatic vinyl compound-aromatic polylene copolymer (below the present specification is sometimes simply described as "copolymer") to satisfy all of the following (1) to (4). (1) The number of copolymers is 5,000 or more to 100,000 or less, preferably 20,000 or more to 100,000 or less, more preferably 30,000 or more to 100,000. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound having a carbon number of 8 or more to 20 or less, and the content of the aromatic vinyl compound monomer unit is from 0% by mass or more to 70% by mass or less. (3) Aromatic polyethylene is selected from the group consisting of a polyene having a plurality of carbon numbers 5 or more and 20 or less in the molecule, and is derived from an aromatic polyene unit The content of the base and / or dethylvinyl group is 1.5 or more to 50 or more, preferably 1.5 or more to without 7, more preferably 2 or more. (4) The olefin is one or more types selected from the group consisting of an olefin having a carbon number 2 or more, an olefin monomer unit, an aromatic vinyl compound monomer unit, and an aromatic polyely monomer unit a total of 100% by mass. .

[0018] The olefin-aromatic vinyl compound-Aromatic polylene copolymer is obtained by copolymerizing each of the olefins, aromatic vinyl compounds, aromatic polynenes.

[0019] The so-called olefin monomer is selected from the group consisting of an alpha olefin and an alpha olefin and a carbon number of 5 or more to 20 or less, which are substantially free of oxygen, nitrogen or halogen. Compounds made of carbon and hydrogen. The carbon number 2 is 2 or more alpha olefins, for example, can be exemplified: ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodene, 4-methyl -1-pentene, 3,5,5-trimethyl-1-hexene. As the carbon number of 5 or more to 20 or less, a norbornene, cyclopentene can be exemplified. Examples of the olefin, a combination of alpha olefins or cyclic olefins other than ethylene and ethylene or alone is ethylene. When the mass ratio of alpha olefin / ethylene α olefin / ethylene other than the ethylene contained is 1 / 7 or less, it is better to be 1 / 10 or less, and the resulting hardening body can be improved on the stripping of the copper foil or copper wire. The strength is better. More preferably, the content of the alpha olefin monomer unit other than the ethylene contained in the copolymer is 6% by mass or less, preferably 4% by mass or less, or the olefin is alone ethylene. In this case, it is further improved to better peel strength for the copper foil or the copper distribution line. Further, in the combination of better ethylene and ethylene, the ethylene-allefin-aromatic vinyl compound-aromatic polyene chain of the finally obtained hardening body can be obtained by the type of alpha olefins. The content, and the range freely adjusted from substantially -60 ° C to -5 ° C, preferably from -50 ° C to -10 ° C.

[0020] The aromatic vinyl compound monomer is an aromatic vinyl compound having a carbon number of 8 or more to 20 or less, and for example, styrene, methylstyrene, isobutylstyrene, various vinyl naphthalene, various Vinyl anthracene.

[0021] As an aromatic polyelycene monomer, a polyene having a plurality of carbon number 5 or more to 20 or less in the molecule, preferably 8 or more to 20 or more Polyethylene. As the aromatic polyely, it is preferred to have a polyethylene having a plurality of vinyl carbon having a plurality of vinyl groups in the molecules, more preferably adjacent, interconnected, aligned with various disylene zends. Mixtures, Diathylene, Diethylene, -2-propenyl styrene, with an aromatic ethylene structure of -3-butene styrene or the like and substantially free of oxygen, nitrogen or halogen, composed of carbon and hydrogen Compound. Further, it is also possible to use Japanese Laid-Open Patent Publication No. 2004-087639, such as 1,2-bis (vinylphenyl) ethane (referred to as BVPE). Among them, it is preferred to use neighbor, interstitial, aligned, or these mixtures, most preferably used between diethylenebenzene and a mixture of diodebenzene. In this specification, these diethylene benzenes are used as denernalbenzene. When using divinite as an aromatic polyene, the hardening efficiency is high and easy to harden, so it is preferred.

[0022] As each of the alkylene hydrocarbons, aromatic vinyl compounds, aromatic polynenes, or additionally, containing polarity, oxygen atoms, nitrogen atoms, etc., containing an aroma of oxygen atom or nitrogen atoms. Ethylene compound, or an aromatic polyene, or the like of oxygen atom or nitrogen atom, but the total mass of these monomers containing the polarity is preferably 10% by mass or less of the total mass of the composition, more preferably 3 quality. % Or less, optimal is a monomer containing polar-containing base. By setting to 10% by mass or less, the low dielectric characteristics (low dielectric constant / low dielectric loss) of the hardening body obtained by hardened the composition can be improved.

[0023] The amount of the present copolymer is 5,000 or more to 100,000 or less, preferably 20,000 or more to 100,000 or less, more than 30,000 or more to 100,000. By setting to this range, even if the addition of the resin is added to the unheated state, it is not easy to stick, and the effect of improving the thermoplastic can be obtained, which in turn can easily impart a high fracture point strength, high. Good physical properties such as fracture point elongation. If the number average molecular weight does not reach 5000, since the composition of the composition in the unheated stage is low, the additional adhesion is high, and the present composition is sometimes difficult to perform the formation of the thermoplastic resin. If the number average molecular weight is higher than 100,000, the forming processability is reduced. The content of the aromatic vinyl compound monomer unit contained in this copolymer is from 0% by mass or more to 70% by mass or less, preferably 10% by mass or more to 60% by mass or less, more preferably 10% by mass or more to 55 quality. %the following. When the content of the aromatic vinyl compound monomer unit is greater than 70% by mass, the glass transfer temperature of the hardenating body of the final obtained composition is near room temperature, resulting in a low temperature toughness or elongation. If the content of the aromatic vinyl compound monomer unit is 10% by mass or more, the aromatic character of the present copolymer is improved, and the affinity of the filling agent or the filling is good, and the filling agent does not exudes, and the filler can be filled. . Further, if the content of the aromatic vinyl compound monomer unit is 10% by mass or more, a hardening body having a high peel strength having a stripping strength of a copper foil or a copper distribution can be obtained.

[0024] In the present copolymer, the content of the vinyl and / or detexyl group from the aromatic polyethylene unit is 1.5 or more than that of the number average molecular weight, preferably 2 or more More than 20, more than 3 or more until 10. The content of the vinyl and / or tereting vinyl group is also generally referred to as "vinyl content". If there is no 1.5, the crosslinking efficiency is low, and it is difficult to obtain a hardening body that sufficient crosslink density. If the vinyl content is increased, it is easy to improve the final obtained hardening body and the mechanical properties of high temperature at normal temperature. The vinyl content of the source from the number average molecular weight meter from the present copolymer can be used to use the usual knowledge known in the field of knowledge, which is known in the field, known in the field. The number of standard polystyrene conversations in the method is average molecular weight (Mn), and the vinyl content or teretin content derived from the aromatic polyethylene unit derived from the aromatic polyethylene unit was determined by 1H-NMR (Nuclear Magnetic Resonance; NMR). Compare. As an example, the source from the aromatic polyelycene unit is 0.095% by mass, and the standard polystyrene obtained by GPC was determined by GPC, based on the intensity of each wave area obtained by 1H-NMR. When the amount of the converted number is 68000, the molecular weight of the vinyl source derived from the aromatic polyelycene unit in the average molecular weight of this amount is 64.8, which is divided by the amount of the vinyl formula 27, thereby 2.4. That is, the source of the source from the number average molecular weight meter from the source of the present copolymer is 2.4. The copolymer is known from the peak of peaks obtained by 1H-NMR. Further, the method of obtaining the composition of the copolymer is also known based on the comparison of the peak area obtained by 1H-NMR. Further, in the present specification, the content of the dihetobenzene unit in the copolymer is determined according to the peak intensity of the vinyl source derived from the vinyl-benzene unit (determined by 1H-NMR). That is, according to the vinyl content derived from the divinyl unit, one diethylene benzene unit derived from the copolymer is provided, and the content of the divinobenzene unit is determined.

[0025] In this copolymer, the optimum olefin monomer unit content is 30% by mass or more, especially 45% by mass or more. The aforementioned olefin monomer unit, the aromatic vinyl compound monomer unit and the aromatic polyely monomer unit are 100% by mass. If the olefin monomer unit content is 30% by mass, the toughness (elongation) of the hardening body finally obtained is increased, and the cracking or impact resistance of the hardening body does not occur, the hardening body is in the thermal cycle test. Cracked. In the present copolymer, the optimum olefin monomer unit content is 90% by mass or less. In this copolymer, a suitable olefin-aromatic polylene copolymer as an aromatic vinyl compound monomer unit can be exemplified: ethylene-divinylphenyl copolymer, ethylene-propylene-Diethylene Benzophenyl copolymer, ethylene-1-butene - divinobenzene copolymer, ethylene-1-hexene-divinyanobenzene copolymer, ethylene-1-octene-divinobenzene copolymer. In this copolymer, as an olefin-aromatic vinyl compound-aromatic polylene copolymer containing an aromatic vinyl compound monomer unit, an ethylene-styrene-divinylbenzene copolymer, ethylene- Propylene - Styrene - Diethylene Benzene Copolymers, Ethylene-1-Hexene - Styrene - Diethylene Benzene Copolymers, Ethylene-1-octene - Styrene - Diethylene Benzene Copolymers.

[0028] [Add Resin] The composition of the present invention can comprise preferably 1 part by mass to 500 parts by mass, more preferably 1 parts by mass to 300 parts by mass, relative to the copolymer contained. Hydrocarbon elastomer, polyphenylene ether, olefin-aromatic vinyl compound - aromatic polylene copolymer, one or a plurality of resins in aromatic polynene resin (in this specification, simply as "Add" Resin "). As the addition of a resin, a polyphenylene ether and / or a hydrocarbon elastomer can also be used. In the hydrocarbon-based elastomer, the conjugated diene polymer is preferred. The conjugated diene polymer is preferably 1,2-polybutadiene. By using polyphenylene ether and / or 1,2-polybutadiene, the amount of monomer can be reduced, for example, even without using a monomer, the preferred hardening body of the present invention can also be obtained.

[0029] [hydrocarbon elastomer] 100 parts by mass of the copolymer, the amount of hydrocarbon-based elastomer for the composition of the present invention is preferably from 1% by weight to 500 parts by mass, more preferably 1 parts by weight to 200. Quality. The hydrocarbon-based elastomer which can be used in the composition of the present invention is an ethylene or propylene-based elastomer, a conjugated diene polymer or an aromatic vinyl compound-conjugated diene system. Copolymers or random copolymers, and one of these hydride (hydrogenates) or a plurality of elastomers. The number of hydrocarbon elastomers is 1000 or more, better than 2000 or more, preferably more than 20,000, preferably more than 30,000. The number of hydrocarbon elastomers is preferably 80,000 or less, more preferably 60,000. Examples of the ethylene-based elastomer include ethylene-octene copolymers or ethylene-1-hexen copolymers such as ethylene-α olefin copolymers, Ethylene-Propylene Rubber; Ethylene-propylene-propylene- Diene monomer; three-dimensional ethylene ethylene rubber), as a propylene-based elastomer, can be mentioned: ATACTIC polypropylene, low stereo regular polypropylene, propylene-1-butene copolymer, etc. propylene-α olefin copolymer .

[0030] As the conjugated diene polymer, polybutadiene or 1,2-polybutadiene may be mentioned. As a block copolymer or random copolymer of an aromatic vinyl compound - conjugate diene, and these hydrides (hydrogenates), can be exemplified: SBS (Styrene-Butadiene-Styrene; Styrene - Di) Allene - Styrene), SIS (Styrene-Isoprene-Styrene; Styrene-Ethylene-Butylene-Styrene; Styrene-Ethylene-Butylene-Styrene; Styrene-Ethylene-Butene-Styrene), Seps STYRENE-ETHYLENE-PROPYLENE-STYRENE; Styrene-Ethylene-Ethylene-propylene-Styrene; Styrene-ethylene-propylene-styrene), SeeBs (Styrene-Ethylene- Ethylene-butylene-Styrene; Styrene-ethylene-ethylene-butene-styrene), etc. It is preferable to use 1,2-polybutadiene, for example, in addition to the products from JSR Co., Ltd., it can also be obtained from the Liquid polybutadiene (product name B-1000 of Cao Dai Co., Ltd.). B-2000, B-3000). In addition, as a copolymer having a 1,2-polybutadiene structure which is preferably used, TOTAL CRICON 100 "can be exemplified. Any or complex resin selected from these hydrocarbon-based elastomers is especially similar to the case where the present invention is in the case of the unklarged state in the case of a liquid (25 ° C) as a liquid (substantially 300,000 mPa · s or less). Or in the viewpoint of forming processability (as the operability of the thermoplastic resin), with respect to 100 parts by mass of the copolymer, the resin is preferably 1 parts by mass to 30 parts by mass, especially 1 parts by mass to 20 quality. The range of copies.

[0031] [Polyphenylene ether] as polyphenylene ether, can be used for polyphenylene ethers of commercially available. The number of polyphenylene ethers is arbitrary. If the formation processability of the composition is considered, the number average molecular weight is preferably 10,000 or less, optimal is 5000 or less. The number average molecular weight is preferably 500 or more, and the best is 1000 or more. Further, it is an object to make the composition of the composition of the present invention to be added, and it is preferred to be modified, and / or preferred to have a plurality of functional groups in one molecule. As a functional group, an allyl group, a vinyl group, an epoxy group or the like, an optimum is a functional group, a vinyl group, especially (meth) acrylic or aromatic ethylene. That is, in the composition of the present invention, it is especially a two-function polyphenylene ether that is substantially modified by the radical polymerizable functional base. As such polyphenylene ether, the NORYL (trademark) SA9000, etc. of SABIC is mentioned, especially for the use of Mitsubishi Gas Chemical Company, which is available to Mitsubishi Gascco, and OPE-2ST). With respect to 100 parts by mass of the copolymer, the amount of polyphenylene ether used in the composition of the present invention is preferably from 1% by weight to 200 parts by mass, more preferably 10 parts by mass to 100 parts by mass.

[0032] [Olefin-Aromatic Vinyl Compound-Aromatic Polythylene Coopolymer] Further, when the hardened of the present invention, an olefin-aromatic vinyl compound-aromatic polylene copolymer can be added. A olefin-aromatic vinyl compound-aromatic polylene copolymer-aromatic polylene copolymer having a condition satisfying the conditions (1a) to (4a) can also be added. The olefin-aromatic vinyl compound-aromatic polylene copolymer, which is described above, except for the above-described olefin-aromatic vinyl compound-aromatic polylene copolymer that satisfies the conditions (1) to (4). . (1A) The number of copolymerizations is 500 or more to 50,000. (2A) Aromatic vinyl compound monomer is an aromatic vinyl compound having a carbon number of 8 or more to 20 or less, and the content of the aromatic vinyl compound monomer unit is from 0% by mass or more to 70% by mass or less. (3A) Aromatic polyethylene is selected from the group consisting of a polyethylene having a plurality of vinyl and / or extension of the vinyl group in the molecule, and is derived from an aromatic polyene unit ethylene The base contains 1.5 or more in the amount of average molecular weight. (4a) olefin is one or more types selected from the selected olefin of carbon number 2 or more, and the olefin monomer unit content is 30% by mass, and the olefin monomer unit, aromatic vinyl compound monomer unit and aroma The total of the polylene monomer unit is 100% by mass. With respect to 100 parts by mass of the copolymer, the amount of olefin-aromatic vinyl compound for the present invention is preferably from 1% by weight to 49 parts by mass. Further, in the viewpoint of the composition of the present invention, 100 parts by mass to 30 parts by mass, preferably from 1 mass to 30 parts by mass, especially 1 parts by mass, relative to the copolymer. The range of 20 parts by mass.

[0033] Olefin, aromatic vinyl compound, aromatic polyethylene, number average molecular weight, and vinyl content are defined, and the method of obtaining the same case as the consensus of the copolymer. The evaluation method of the number average molecular weight of the present copolymerization is as follows. The molecular weight system uses GPC (gel penetration chromatography) to obtain a standard polystyrene conversion number average molecular weight (MN). The measurement can be carried out under the following conditions.

[0034] [Number Average molecular weight is more than 1000 or more] Piece: Two series of TSK-Gel MultiPorehxL-M φ7.8 × 300mm (manufactured by TOSOH)). Cylindrical temperature: 40 ° C Media: THF (Tetrahydrofuran; Tetrahydrofuran) in liquid flow: 1.0ml / min. Detector: RI detector (Direction refractive index detector)

[0035] [Number Average molecular weight does not reach 1000] Pipe: TSKGELG3000HXL φ7.8 × 300mm, TSKGELG2000HXL φ7.8 × 300mm, TSKgelG1000HXL φ7.8 × 300mm (manufactured by Dongcao) four series use. Tube temperature: 40 ° C Media: THF in liquid flow: 0.5ml / min. Detector: RI detector

[0036] [Aromatic polyene-based resin] The so-called aromatic polyene resin comprises a dihetin-based reactive multi-branch copolymer (PDV) manufactured by Nippon Steel Chemical & Material. Such PDVs are described, for example, in the literature "Synthesis of multi-functional aromatic ethylene copolymers and the development of novel IPN low dielectric loss materials using this multi-functional aromatic ethylene copolymer" (Sichuan-riped is equal, electronic confession " Magazine, P125, Vol. 12 No.2 (2009)). Further, as an aromatic polyene resin, an aromatic polyelycene monomer according to the above may be mentioned as the aromatic polylene polymer resin of the main constituent unit. [Masterin] As a hardening agent which can be used in the hardened composition of the present invention, a known hardener that is previously used for the polymerization or hardened of aromatic polyethylene, aromatic vinyl compounds can be used. In such a hardener, a radical polymerization initiator, a cationic polymerization starter, anion polymerization starter, preferably a free radical polymerizer can be used. Preferably, the organic peroxide (peroxide), azo-based polymerization starter, or the like, can be freely selected depending on the use, condition. The catalog of organic peroxide can be downloaded from the homepage of the company, such as https: / / www.nof.co.jp / business / chemic / product01a.html, https: / / www.nof.co. JP / Business / Chemical / Product01b.html, https: / / www.nof.co.jp / business / chemic / product01c.html. In addition, the examples of organic peroxides are also described in the directory of the intensive drug company or Tokyo into industrial companies. The hardening agent used in the present invention can be obtained from these companies. Further, a well known use of light, ultraviolet rays, and a radiation initiator can be used as a hardener. As the hardening agent using photopolymerizable starting agent, it is possible to include a radical polymerization starter, a photorepolymerization initiator or a photoreal polymerization starter. Such photopolymerization initiators can be obtained, for example, from Tokyo into Industrial Co., Ltd. Further, it is also possible to harden by radiation or electron beam itself. Further, it is also possible to contain a hardening agent, and crosslinking, hardening is performed by the thermal polymerization of the raw material.

[0038] The amount of hardener is not particularly limited, and is generally 100 parts by mass of the composition, preferably 0.01 parts by mass to 10 parts by mass. When a hardening agent such as an organic peroxide (peroxide), azo-based polymerization starter is considered, the half-life of the hardener is considered to be hardened at an appropriate temperature and time. The condition of this situation is arbitrarily based on the hardener, and is generally the temperature range of about 50 ° C to 180 ° C.

[0039] [Monomer] The amount of monomer which may contain the composition of the present invention is arbitrary, preferably 100 parts by mass with respect to the copolymer, and below 10 parts by mass. Further, the composition can also be substantially free of monomers. If the monomer is 10 parts by mass, the unheated composition does not have a viscous property, and it is easy to form a thermoplastic resin. In addition, if the amount of monomers that are easy to volatilize is equal to or less, the odor in the unheated stage is not a problem. When the solvent is added to the composition, the form is set to a varnish case, and the monomer disappears in use with the evaporation of the solvent (solvent), and the substantial content of the monomer is easily reduced. In addition, when the form of the product is the unknown sheet, if a monomer is contained below, the content of the monomer is not easily changed at the time of storage. The monomer which can be used in the composition of the present invention is preferably a molecular weight of less than 1000, and it is better to reach 500. The monomers which can be used in the compositions of the present invention are aromatic vinyl compound monomers, aromatic polyely monomers, and / or polar monomers. As the monomer, it is preferred to be a monomer that can be polymerized by a radical polymerization initiator, more preferably the aramid vinyl compound or aromatic polyene. In addition, BVPE (1,2-bis (vinylphenyl) ethane) (1,2-bis (vinylphenyl) ethane) according to Japanese Laid-Open No. 2003-212941 is also preferred. In view of the viewpoint of improving the hardenpects of high temperature (elastic modulus), 100 parts by mass of the aromatic polyene is preferably 1 parts by mass or more to 30 parts by mass. Further, a relatively small amount of polar monomer can also be used in order to impart a relative to other materials necessary to be the insulating material or to increase crosslink density. Examples of the polarity monomer include various Malay imine, double malaiimine, maleic anhydride, (meth) acrylate, isocyanate, trioxyl isocyanrate, three (methyl) ) Acrylic uric acid, trimethylolpropane tri (meth) acrylate, or the like. It can be used in the maleimide of the present invention, and the double-Malaysimide is described in international disclosure WO2016 / 114287 or Japanese Laid-Open, 2008-291227, such as the large and chemical industrial shares or Designer. Molecules Inc purchases. These male-containing-containing-containing compounds are preferably two-malaimide in terms of high-frequency characteristics, high frequency characteristics, and high-frequency characteristics, and prefilmous formability of the conductor. kind.

[0040] Double Malay imine is preferred to be a double maleimide in the following formula (B-1).

[0041] Formula (B-1) [化 1]

[0042] In the formula (B-1), R represents the number of carbon atoms having a carbon atom, and L represents a single bond or a divalent connection. R and L can also have a substituent independently. Further, the maleimide denoted by the formula (B-1) is preferably represented by the following formula (B-2).

[0043] Formula (B-2) [化 2] In the formula (B-2), R 'separately indicated that the number of carbon atoms having a substituent is 5 or more, and A is independently indicated, respectively, can also have a substituent carbon atom number of 5 The above is alkyl, or may have a second price of the substituent having an aromatic ring. n represents an integer of 1 to 10.

[0045] As the maleimide represented by the formula (B-2), a compound represented by the following formula (B-3) can be mentioned. In the formula, n represents an integer of 1 to 10. As the compound represented by the formula (B-3), the BMI-1500 (N mean = 1.3) manufactured by Designer Molecules Inc.

[0046] Formula (B-3) [化 3]

[0047] Double Malay imine can also be used as a polyamine bisemicimide compound. The polyamine-based double malaiimide compound is, for example, by a compound having two maleimide metyl groups in the end and an aromatic diamine compound having two primary amine groups in the molecule to perform wheat. The reaction is obtained by Michael Addition Reaction. When a high cross-linking efficiency is obtained by a small amount of addition, it is preferred to use a polar monomer having a polyfunctional basal base above a difunctional basis, which can be exemplified by a double malaiimide, isocyanic acid triohne. Propyl ester (TAIC), trimethylolpropane three (meth) acrylate. Compared to 100 parts by mass of the copolymer, the composition can contain a polar monomer of 0.1 parts by mass to 10 parts by mass, preferably from 0.1 parts by mass to 5 parts by mass. The dielectric constant or dielectric loss obtained by using 10 parts by mass or less, the dielectric constant of the obtained hardening body is testee. For example, the dielectric constant becomes less than 3.0, and the dielectric loss is orthogonally lower than 0.005.

[0048] [Solvent (Media)] For the composition of the present invention, an appropriate solvent can also be added as needed. The solvent is used to regulate the viscosity and fluidity of the composition. Except for solvent, it is preferably volatile, for example, cyclohexanone, toluene, ethylbenzene, acetone, isopropanol, and the like can be used. Further, regarding the amount of use of the solvent, it is preferably 10 parts by mass or less than 100 parts by mass of the copolymer of the present invention as the composition of the thermoplastic resin. In addition, in the scaling, the solvent removed after hardened is better, and the solvent is not used substantially. The so-called substance is not used, preferably 5 parts by mass, more preferably 1 parts by mass, preferably 0 parts by mass. Further, in the case of a varnish, it is preferred to add a suitable solvent to the composition of the present invention. The solvent is used to regulate the viscosity and fluidity of the composition as a varnish. Examples of the solvent, if the boiling point of atmospheric pressure is high, if the volatility is low, the thickness of the coated film is uniform, so it is preferably a solvent having a boiling point to a certain degree. Preferably, the boiling point is approximately 100 ° C or more, preferably 130 ° C or higher to 300 ° C or less. As a solvent suitable for varnish, toluene, xylene, average trimethyl benzene, ethylbenzene, citarne, ether ether acetate, ethylene glycol monthyl ether acetate, ethylene glycol monobutyl ether, etc. . Further, with respect to 100 parts by mass of the composition of the present invention, the amount of solvent is preferably 10 parts by mass to 2000 parts by mass.

[0049] [Compose] The composition of the present invention further contains one or plural species selected from the group consisting of filler, refractory, surface modifiers relative to the above composition. In order to make the composition of the present invention can be a matrix of a hardening body, and the filling property of other materials is excellent in hardening, one or a plurality of fillers selected from these fillers, refunds, surface modifiers, that is, After hardened, the hardening body is also easy to display impact resistance or toughness.

[0050] [Filler] Additionally, a known inorganic filler or organic filler can also be added as needed. These filler systems are added to control thermal conductivity, and the use of low price is added, and the amount of the filler is arbitrary depending on the purpose. The compositions of the present invention include, in particular, a large amount of inorganic filler, 100 parts by mass relative to the copolymer, the amount of use of the inorganic filler can reach 2000 parts by mass. In particular, when the inorganic filler is added, it is preferred to use a known surface modifier, such as a silicone coupling agent. In particular, as the composition of the low dielectric constant of one of the purposes of the present invention, the low dielectric loss is excellent, as an inorganic filler, preferably boron nitride (BN) and / or dioxide It is preferred for dioxide. Dioxide, preferably molten dioxide. For the viewpoint of low dielectric characteristics, if a large amount of addition of additions, there is especially possible to increase the dielectric constant, so it is better to use 100 parts by mass of the copolymer, and it is not more than 500 parts by mass. 400 parts by mass of the filler. Further, it is also possible to improve the low dielectric characteristics (low dielectric constant, low dielectric loss orthose) to add a filling agent of the hollow filler or a void.

[0051] Additionally, an organic filler such as high molecular weight or ultra-high molecular weight polyethylene can be used instead of inorganic filler. The organic filler is preferably crosslinked to the organic fill itself on the viewpoint of heat resistance, preferably used in a state of particles or powder. These organic fillers can inhibit dielectric constants and dielectric losses are rising. With respect to 100 parts by mass of the copolymer, the amount of the filler is preferably 1 parts by mass or more until 400 parts by mass.

[0052] On the other hand, it can be dispersed by a high dielectric constant insulator filler of 1 GHz (preferably 3 to 10,000, more preferably 5 to 10000) in the composition of the present invention. Inhibition of dielectric losses, the dielectric loss is increased, and the insulating hardening body having a high dielectric constant insulating layer having a dielectric constant of 3.1 to 20 is fabricated. The miniaturization of the circuit can be achieved by increasing the dielectric constant of the film constituted by the insulating hardening body, and high capacitance of the capacitor can contribute to the miniaturization of high frequency electrical parts. High dielectric constant, low dielectric loss is suitable for capacitors, resonance circuit inductors, filters, antenna, etc.. As a high dielectric constant insulator filler for the present invention, an inorganic filler or a metal particles for insulating treatment may be carried out. The specific example is a known high dielectric constant inorganic filler with barium titanate, barium titanate, etc., for example, for example, is specifically described in Japanese Laid-Open Patent Publication No. 2004-087639.

[0053] [Filler] A known refractory combustion can be used in the composition of the present invention. In terms of low dielectric constants, low dielectric losses, preferred hard combustments are phosphate esters or these condensates or the like or known bromine-based flammable or red phosphorus. In particular phosphate ester, it is preferred to have a compound having a plurality of dimethylenyl groups in the molecule in the molecule in terms of difficult combustion and low dielectric losses.

[0054] Further, in addition to the difficult burning agent, antimony compound or melamine such as trioxide, tetraoxide, antimony trim, antimonium oxide, sodium oxide, and triazine-1,3,5-triazine-triazine is added. 2, 3, 4- (1H, 3H, 5H) - triaclone, 2,4,6-trianey propoxy 1,3,5-triazine and the like are used as a refueling agent. These difficult burning agents are generally preferably 1 parts by mass to 100 parts by mass relative to 100 parts by mass of the composition. Further, a resin having a low dielectric constant of 30 parts by mass to 200 parts by mass and a resin of a low dielectric constant of the polyphenylene ether (PPE) is also prepared relative to the difficult burner.

[0055] [Surface Model] In the composition of the present invention, various surface modifiers can be contained in order to increase the contact of the filler or copper plate and wiring. With respect to 100 parts by mass of the composition of the present invention, the amount of surface modifier is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 5 parts by mass. Examples of the surface modifier include a variety of silicate coupling agents, thlycomide-based coupling agents. One or a plural species can also be used in various silicate coupling agents or phthalate coupling agents.

[0056] In the present invention, a copolymer, monomer, a monomer, addition resin, which can be changed within the above range, and the formation ratio of solvents as needed, or by altering a refilling agent or filler, surface modification The mixture ratio of the agent is adjusted according to the target, and the forming method is adjusted in accordance with the target and forming method. Specifically, the composition of the present invention can take "thermoplastic composition", "semi-hardening state (B-class material, etc.)," ​​varnish "product form.

[0057] The composition of the present invention is as previously described, one of the copolymers and hardeners, and one of the selected forms of monomers, solvents, adding resins, fillers, refunds, and surface modifiers as needed or Complex, dissolved or melted, mixed, dissolved, and the method of melting can be used.

[0058] [thermoplastic composition, shaped body] Since the composition of the present invention has a coner having a molecular weight of the present invention, the priority of the thermoplastic resin is displayed in the predetermined addition of the resin. Therefore, it can be formed into a sheet, tube, short strip, particles, etc., which is formed into a sheet, tube, short strip, particles, etc., by means of a known forming method of the thermoplastic resin, and substantially in the shape of the unheated state, and then Union (hardening). The so-called sheet in this specification also includes the concept of the film. Further, even if the film is described in this specification, the concept of the sheet is also included.

[0059] Further, the preferred embodiment of this form is as follows. The selected from the group consisting of a certain ratio or more of the polyfelt-based elastomer, polyphenylene ether, olefin-aromatic vinyl compound-aromatic polylene copolymer, or a plurality of resins in the aromatic polynene resin When the resin (except for the resin of the room temperature is liquid, it is easy to perform forming processing as a thermoplastic resin in the state of unharitage. Specifically, it is preferred to add 100 parts by mass of the copolymer, and the aforementioned hydrocarbon elastomer (except for liquid resin) and / or polyphenylene ether can be added in the range of 30 parts by mass to 200 parts by mass. Further, when the addition of the resin is liquid as the liquid shape, 100 parts by mass of the copolymer can be added to the range of 1 parts by mass to 30 parts by mass, especially 1 parts by mass to 20 parts by mass. The amount of monomer that can be used in the composition of the thermoplastic is preferably 10 parts by mass or less than 100 parts by mass of the copolymer. The number of copolymers used is 5,000 or more to 100,000 or less, preferably 20,000 or more to 100,000 or less, more than 30,000 or more to 100,000. The above thermoplastic composition can be preformed into various shapes such as sheets, and the semiconductor elements or wiring, or with the substrate product, or with the substrate product layer, or in combination with the substrate latency, or in combination with the substrate product layer, or in combination with the substrate product. then. The compositions of the present invention may also be provided in the form of a sheet, which is formed by using a known method of the hardening agent or a temperature below the temperature below the decomposition temperature. The mold is formed into a sheet, which can be extruded with a T-shaped mold, and a two roller can also be used, and the extruded layer is pressed against the substrate film. In this case, in the case where the temperature or decomposition temperature of the hardening agent is melted, the composition of the composition, the mass ratio of copolymer / monomer or solvent is added, and the resin is added, and the mass ratio or solvent is added. Choice, adjustment of the agent. The case of this situation is substantially unknown. Then, after various processes, assembly steps, it is finally hardenated by the temperature of the hardening agent, or the temperature above the temperature, or the temperature above temperature, and the time is completely hardened. This method is a general technique of cross-linking sealant sheets for ethylene-acetate resin systems of solar cells (solar light emission devices).

[0061] [Semi-hardening state (B-order, etc.) is further, the composition of the present invention can also be formed into a local cross-linking state, such as reacting one of the hardeners contained in the composition. Semi-hardness (so-called B-order state), for example, a sheet, tube, or the like. For example, by using a complex number of hardening and / or hardening conditions having different hardening temperatures, semi-hardening, melt viscosity or fluidity is set to a B-order state. That is, the hardening resin or composition can be formed into an easy-to-operate B-order material by hardening (topically hardening), and the B-order material is laminated and crimped. After the second phase of hardening (complete hardening) is performed, it is formed into a final shape. In this case, the composition can be made (the composition of the composition, that is, the mass ratio of the copolymer / monomer, adding a solvent, adding a resin, a refueling, and further comprising a hardener such as a peroxide. Topical hardening is adjusted to a sheet shape (B-order state), forming, assembled components, heat-hardened under pressure under pressure. As a method of topically hardening the composition, a known method can be employed, for example, the following method: the peroxide having different decomposition temperatures, for a predetermined time of only a temperature of only one kind of peroxide substantially actually functioning for a half The hardening sheet is finally the temperature of all the hardening agents to perform a sufficient time to completely hardened.

[0062] Further, the molded body can also be a sheet. The sheet can also maintain the degree of sheet shape and untick (semi-hardening), or a complete hardened latter. The degree of hardness of the composition can be quantified by a known DMA (Dynamic Mechanical Analysis; dynamic viscous determination).

[0063] [The composition of the invention and its molded body] The composition of the present invention can also be made into a viscous liquid-shaped lacquer. For example, a varnish can be made by using a solvent having a sufficient amount and / or by appropriately using a liquid monomer. In particular, when used as a varnish, it is preferred to add a suitable solvent to the composition of the present invention. The solvent is used to regulate the viscosity and fluidity of the composition as a varnish. Examples of the solvent, if the boiling point of atmospheric pressure is high, if the volatility is small, the thickness of the coated film becomes uniform, so it is preferably a solvent having a boiling point to a certain degree. Preferably, the boiling point is approximately 100 ° C or more, preferably 130 ° C or higher to 300 ° C or less. As a solvent suitable for such varnishes, xylene, average trimethylene, ethylbenzene, citarne, ethylene glycol methyl ether acetate, ethylene glycol monthyl ether, ethylene glycol monobutyl ether, and the like can be used. Further, with respect to 100 parts by mass of the composition of the present invention, the amount of solvent is preferably 10 parts by mass to 2000 parts by mass. The composition of the present invention can also be produced by a polymerization of a copolymer obtained by polymerizing the present invention. For example, the treatment of concentrating or removing the residual monomer can also be carried out as needed, and various additives, etc., various additives, or the like can be produced, and the component concentration or solution viscosity or the like can be added.

[0064] This cleaner can be applied to the substrate or so that the substrate is immersed, and the solvent or the like is removed by drying or the like, and is made into an unknown or semi-hardening molded body. In general, the forming body has a sheet, a film, a strip shape. []] With regard to the hardening of the composition, refer to the hardening conditions (temperature, time, pressure) of the hardening agent contained, by hardening. When the hardening agent used is the case of the peroxide, the hardening conditions can be determined in reference to the half-life temperature or the like disclosed for each peroxide.

[0066] [Harded body obtained by the composition] The dielectric constant of the hardening body obtained by the composition of the present invention is 2.0 or more to 3.0 or less, preferably 2.0 or more to 2.8 or less, especially 2.0 or more to 2.5. the following. Dielectric losses are tescent to 0.0003 or more to 0.005 or less, preferably 0.0005 or more to 0.003 or less. These dielectric constants or dielectric losses are specifically determined by any method known in the field of the present invention, for example, by resonance method (cavity resonator alharging method or equilibrium circular panel resonator method) Approving. In addition, the volume resistivity of the obtained hardening body is preferably 1 × 1015 Ω · cm or more. These values ​​are, for example, the value of high frequency electrical insulating materials above 3GHz. The copolymerization system used in the composition of the present invention is relatively soft and has a tensile length, so that the hardening body obtained by the composition of the copolymer can have the following characteristics: show sufficient strength, and is relatively more Soft quality and high impact resistance can follow the thermal expansion of substrates. That is, the hardening body of the present invention is not up to 3 GPa at room temperature (23 ° C), and is 3 MPa or more, preferably 5 MPa or more. Further, in particular, when the relatively larger filler is allocated, the stretchable elastic modulus sometimes takes the value of 3 GPa or more to 20 GPa. Further, the strength of the stretch-breaking point is preferably 50 MPa and is 3 MPa, more preferably 5 MPa, and the elongation of the pull-off point is preferably 30% or more until 300%, more preferably 50% or more Not 250%. In addition, especially when the relatively larger filler is blended, the elongation of the retraction of the retraction is also at a value of 30%. The hardening body of the composition of the present invention may have practical adequate heat resistance. Specifically, if in the practicality, the hardening body of the composition of the present invention can be said to be 5 × 105 Pa or more, preferably a value of 1 × 106Pa or more. In the field of technical field, it is possible to refer to the information described in this specification and well-known data, determine the composition of the composition having the above physical properties, and easy to produce a hardening body. For the hardening body obtained by the composition of the present invention, it is possible to display a practical heat resistant to the condition of the composition as a monomer or the composition of the composition as a monomer or monomer. Sex or mechanical properties at high temperatures. As described above, in order to ensure the forming processability as a thermoplastic resin is ensured even if it is an unknown state, it is also important to suppress an aromatic polyylene having a composition of the monomer or monomer to be below a certain ratio.

[0067] [Oriented to the composition] The composition of the present invention can be used as a wiring, preferably a variety of insulating materials for the high-frequency signal, such as a cover layer, a solder resist, a buildup material, a layer External insulating agent, bonding sheet, layer indirect agent, bump sheet for coating engagement machine. Further, it is also possible to be used as a single layer or multi-layer printed substrate, a flexible printed substrate, a CCL (copper plate), an electrical insulating layer or a substrate, or the substrate, or the substrate.

[0068] As the use of undated sheets or local hardening sheets] The unkdaminated sheet or topical hardening sheet of the composition of the present invention can preferably be used as a high frequency electrical insulating material. For example, it is preferable to be used as a laminate, bonding sheet, covering sheet, and an insulating layer or a substrate for a bump sheet or a substrate. It can also be used to replace the sheet previously used epoxy resin or poly silicon resin, hardening treatment, forming a low dielectric constant, a hardening insulating layer or a hardening matrix layer of a low dielectric loss. The thickness of the sheet is generally 1 micron to 300 microns. The sheet may contain a woven fabric, a nonwoven fabric, or a woven fabric, no woven fabric or such as a glass or ceramic fiber or the like, or may also be formed into a multilayer. In addition, it can be used as an antenna cable such as a mobile phone, and a portion of the previous coaxial cable can be used or all of the soft-bendable wiring of the sheet insulated. For example, LCP (Liquid Crystal Polymer; Liquid Crystal Polymer) or PPE (polyphenylene ether; polyphenylene ether) sheet, fluorine-based resin or polyviltyimine resin can also be used as a substrate, a sheet or a B step of the present invention. The sheet (covering sheet) is covered with a wiring and hardening and the substrate is then used as an insulating material.

[0069] The multi-layer wiring substrate for the hardening body obtained by using the composition of the present invention is a multi-layer wiring substrate of the insulating layer, which is a wiring substrate which is excellent in high frequency characteristics of the dielectric loss. In this case, in addition to the low dielectric loss, tolerate the heat resistance of welding, and the degree of impact resistance and elongation of the stress that can be resistant to the heat cycle or thermal expansion. . For example, a general resin sheet such as a cloth, a nonwoven fabric, a diaphragm, a ceramic substrate, a glass substrate, an epoxide, or the like, and a generalized laminated plate such as a glass or quartz, a germplating plate, and a generalized layer of the generic laminate. The conductor foil is laminated, pressed, thereby making a wiring substrate. Further, it is also possible to apply a slurry or solution containing the present composition and dry, hardening to form an insulating layer in the core material. The thickness of the insulating layer is generally 1 micron to 300 microns. Such multilayer wiring substrates can also be used in multiple layers and integralization.

[0070] The hardening body of the present invention, in particular the varnish composition, can be used as previously used as previously used as an electrical insulating material, especially as a bonding material, a surface, a cover layer, and a resistance. Flux, laminating material, bottom filler material, filling insulator, interlayer insulator, layer indirect agent, or as a hardening body, a printed substrate, a flexible printed substrate, FcCl (flexible coating plate) substrate, Alternatively, as a regenerative body of a laminate, a bond sheet, a cladding sheet, a bump sheet for a crystal engagement machine (especially high frequency electrical insulating material).

[0071] Another view of the present invention is an electrically insulating material comprising an olefin-aromatic vinyl compound-aromatic polylene copolymer, a storage elastic modulus of 300 ° C is 5 × 105Pa, and 23 ° C, 10GHz The dielectric constant is 2.0 or more to 2.5 or less, and the dielectric losses are titled to 0.0005 or more to 0.003 or less.

[0072] The composition of the immature or semi-hardening of the present invention can also be subjected to a metal foil (especially copper foil) for wiring, by heating pressurization, even if the adhesive coating or then treatment is not particularly performed. . The so-called copper foil here is a concept comprising copper wiring, and the shape of the copper foil is arbitrary. In particular, in the case where the anlefin-aromatic vinyl compound-aromatic polylene copolymer is preferably used to use an aromatic vinyl compound content of 10% by mass or more, and / or olefin is ethylene alone, or Olyne hydrocarbon monomer components other than ethylene contained with respect to the ethylene monomer component are 1 / 7 or less, whereby 1N can be given in accordance with JIS (Japanese Industrial Standards; Japanese Industry Standard) C6481: 1996 / MM or more peel strength. Further, it is better to give a peel strength to 1.3 N / mm or more. More preferably, if in the above copolymer, the olefin is alone ethylene alone, or an olefin monomer component other than ethylene contained in the olefin is 1 / 10 or less, and the ethylene contained in the copolymer. The content of the alpha olefin monomer unit is less than 4% by mass or less, or the olefin is alone is ethylene, and the peel strength can be further improved. Generally, it is known that the adhering or continuous treatment will result in deterioration of the dielectric characteristics of the laminated body of the copper-shaped layer sheet, preferably without such treatment, and is also based on the Japanese Industrial Standard (JIS) C6481: 1996. In the measurement, the peel strength of 1 N / mm or more is given. As such, the composition of the imminent-free thermoplasticity of the present invention is not particularly carried out, and the copper foil for the wiring can be followed by a heat-pressing process such as heat pressurization. In the present invention, however, regarding the adherity to the copper foil or other member, the slight does not impede other impartial countermeasures (subsequent coating or then disposal, etc.).

[0073] In another embodiment of the present invention, the sclerosis composition can also be provided, and a olefin-aromatic vinyl compound containing the conditions (1) to (4) satisfies the olefin-aromatic vinyl compound - aromatic polyene The copolymer, and a single body of more than 0 parts by mass to 10 parts by mass below the present copolymer; the aforementioned monomer is selected from the group consisting of aromatic vinyl compound monomers, aromatic polyely monomers and polarity One of the groups of groups constituted. (1) The number of copolymers has an average molecular weight of 5,000 or more to 100,000 or less. (2) The aromatic vinyl compound monomer in the copolymer is an aromatic vinyl compound having a carbon number of 8 or more to 20 or less, and the content of the aromatic vinyl compound monomer unit is from 0% by mass or more to 70% by mass or less. (3) Aromatic polyethylene is selected from the group consisting of a plurality of polymenes having a plurality of carbon numbers 5 or more and 20 or less, and derived from an aromatic polyelycene unit The content of the base and / or dethylvinyl group is 1.5 or more than 20 or more in the amount average molecular weight. (4) The olefin is one or more types selected from the group consisting of an olefin having a carbon number 2 or more, an olefin monomer unit, an aromatic vinyl compound monomer unit, and an aromatic polyely monomer unit a total of 100% by mass. .

[0074] It is preferred to be a polar monomer.

[0075] Alternatively, an electrically insulating material may also be provided which is a hardening body having a hardening composition of the aqueous sclerosis, and the storage elastic modulus of 300 ° C is 5 × 105Pa, preferably 1 × 106Pa or more, And the dielectric constant of 23 ° C, 10 GHz is 2.0 or more to 2.5 or less, and the dielectric losses are testee to 0.0005 or more to 0.003 or less.

[0076] The hardening composition can be equipped with the same manner as the hardening composition comprising the aforementioned olefin-aromatic vinyl compound-aromatic polyene copolymer and resin (hereinafter simply described as the composition of the resin). Any or complex species in the group consisting of solvents, hardeners, fillers, filling agents, and surface modifiers. The hardening composition can exert thermoplastic and form a variety of shapes comprising sheets such as the composition of the aforementioned resin. The hardening composition can be used as a varnish as a solvent according to the composition of the resin. The present invention is a hardening body obtained by hardening the hardening composition, and various material properties as the hardening body of the composition of the resin may be displayed. The hardening composition can also be formed in the same manner as the composition of the aforementioned resin, and a laminate comprising a core having a hardened composition is also formed by hardening the moisture of the substantially laminate.

[0077] Further, the composition of the present invention, or other embodiments of the present invention, or other embodiments can be hardened with the LCP (liquid crystal polymer) layer to be hardened relatively moderately hardening conditions, and imparted high joint strength. The so-called LCP layer here is, in particular, the LCP sheet or film. Therefore, for example, various lampposts comprising an LCP sheet, a metal foil (preferably a copper foil), the composition of the present invention can be made. The layers of the cultivation or the lay layer sequence are arbitrary. Such a present invention, the composition of the present invention is useful as a layer of metal foil (copper foil) to the LCP sheet. The composition of the present invention can display high adhesion to both the metal foil and the LCP sheet. The first LCP sheet and the copper foil must be heated to the melting point of the LCP (substantially from 280 ° C to 330 ° C or the temperature close to this temperature). However, by using the composition of the present invention as a back layer, the LCP is then followed by a crimping temperature in the vicinity of the hardening temperature of the composition of the present invention. At this time, the low dielectric constant of the hardening body of the composition of the present invention, the low dielectric loss positive cutting value is given useful as a wiring of the local laminate, in particular high frequency signal transmission. Examples of the convalent laminate include a structure in which a metal wiring (preferably a copper distribution) disposed on the LCP layer is provided from the opposite side of the LCP layer. This is the use of the cover layer as the LCP substrate wiring.

[0078] Here, as the LCP (Liquid Crystal Polymer), a thermoplastic polymer having a liquid crystal state or in the nature of optical birefringence is referred to in melting. As the LCP, a liquid crystal polymer having a liquid crystalline property in a solution state is shown, or the thermocytropic liquid crystal polymer is shown when melting. The liquid crystal polymer is classified as type I, II, and III type according to the temperature of the thermal deformation, can be any type. Examples of the liquid crystal polymer include a thermoplastic aromatic liquid crystal polyester, or an aromatic liquid crystal polyester ocantine such as a thermoplastic-introducing an amine bond to the thermoplastic aromatic liquid crystal polyester. The LCP can also be further introduced to the aromatic polyester or aromatic polyester amine into the 醯 amine bond, a carbonate bond, a carbon diimine bond or isocyanate bond or the like, or the like. polymer. Examples of the LCP can also be used, a molten liquid crystal forming polyester made of 2-hydroxy-6-naphthoic acid, such as the manufactured by Upper Pharmaceutical Corporation (product number A-5000, melting point 280 ° C).

[0079] About the melting point of the LCP, in DSC (Differential Scanning CalorimeiMetry; 40 ° C to 400 ° C, more preferably 260 ° C to 380 ° C). If the melting point is within the foregoing range, the film having excellent extrusion formability and excellent heat resistance can be obtained. Such LCP can be obtained, for example, from Uenan Pharmaceutical Co., Ltd., Sumitom Chemical Co., Ltd., and Polyplastics. Here, the so-called LCP sheet is a known LCP sheet, which is also arbitrary. The LCP sheet can be obtained by a known method such as a T-shaped extrusion method or a blow molding method, a ring belt (dual-band press) method. [Example]

[0080] Hereinafter, the present invention will be described with reference to the embodiments, but the present invention is not limited to the following examples.

[0081] The analysis of the copolymer obtained in the comparative example is carried out by the following method.

[0082] The determination of the content from ethylene, hexene, styrene, and divinite units from the copolymer is performed by 1H-NMR, according to the intensity of the peak area of ​​each vinyl unit. The sample was dissolved in deuterated 1,1,2,2-tetrachlorborne, and the measurement was carried out at 80 ° C to 130 ° C.

[0083] The number average molecular weight (Mn) of standard polystyrene conversion was obtained with GPC (gel permeation chromatography). The measurement was performed under the following conditions. [Situation of the number of average molecular weights is more than 1000] Pipe: Two series of TSK-Gel MultiporehxL-M φ7.8 × 300mm (manufactured by Dongcao). Tube temperature: 40 ° C Media: THF in liquid flow: 1.0ml / min. Detector: Ri detector (refractive index detector)

[0084] When the copolymer is not easily dissolved in the THF inventory, for example, the styrene content is less than 40% by mass in the case of the ethylene-styrene-divinylbenzene copolymer, the standard is obtained by the following high temperature GPC method. The molecular weight of polystyrene conversion. The measurement was performed under the following conditions. Device: HLC-8121GPC / HT Pipe: TSKgelgmhhr-h (20) HT, φ7.8 × 300mm Triple Piece: RI Media: Ri Media: Neighborne Benzene Influential flow: 1.0ml / min. Sample concentration: 0.1 wt / vol%, sample injection amount: 100μL

[0085] [Tensile Test] According to JIS K-6251: 2017, the diaphragm of about 1 mm is cut into the shape of the No. 2 dumbbell 1 / 2 test piece, using the Tensilon UCT-1T type manufacturing manufactured by Orient, with 23 The measurement was measured at ° C, tensile speed of 500 mm / min, and the tensile elastic modulus, tensile breaking point strength, tensile breaking point elongation.

[0086] [DSC Determination] DSC Determination is carried out by DSC6200 manufactured by Seiko Electronics. That is, the resin is 10 mg, and the alpha-alumina 10 mg is used as the reference substance, and the heating speed is 10 ° C / divided by the temperature of 10 ° C / divided by the temperature of 10 ° C to 240 ° C. of 20 ° C / min. -120 ° C. Then, the glass transfer temperature was obtained as the temperature of the temperature of 10 ° C / pellette temperature to 240 ° C. The glass transfer temperature of JIS K7121: 2012 is the start temperature of the glass transfer. In order to extend the straight line of the low temperature side to the high temperature side, the gradient of the curve of the step-shaped change portion of the glass transfer reaches the maximum point The temperature of the tangent of the tangent. [Normal Survey Elastic Modulus and Crosslinking Density] The measurement was measured using a dynamic viscous elastic assay device (RSA-III of Rheometric Co., Ltd.), the frequency of 1 Hz, the temperature region -60 ° C to +300 ° C. The measuring sample (3 mm × 40 mm) was measured by a film cutout measurement sample (3 mm × 40 mm), and the storage elastic modulus was determined. The main measurement parameters associated with the assay are as follows. Measurement frequency: 1 Hz temperature rise speed: 3 ° C / division Sample length: 13mm test type: Dynamic Temperature Ramp, DTEMPRAMP) Initial Static Force: 5.0g Auto Tension Sensitivity : 1.0G maximum automatic stretch (Max Applied Strain): 1.5% Minimal License Power M (Min Allowed Force): 1.0g Strain: 0.1%

[0088] [water absorption rate] is determined according to ASTM D570-98.

[0089] [dielectric constant and dielectric loss (tangential dielectric loss)] With regard to dielectric constant, dielectric losses, use cavity resonator Drash (Agilent Technology (Agilent Technology) 8722ES-type network analysis The cavity resonator for the development and manufacturing of Nangdong Electronics Application, using a sample of 1 mm × 1.5 mm × 80 mm from the sheet, measured at a value of 23 ° C, 10 GHz.

[0090] [Volumerate resistivity] The film having a thickness of about 0.5 mm was used, according to JIS K6911: 2006, the measurement was carried out at room temperature. [Olefin-Aromatic Vinyl Compound-Aromatic Dultiene Copolymers] Refer to Japanese Laid-Open Patent Publication No. 2009-161743, Japanese Laid-Open No. 2010-280771, International Public WO00 / 37517 manufacturing method, appropriate change The amount of monomers, ratios, polymerization, polymerization temperature, and copolymers of P-1 to P-4 are obtained. The olefin monomer unit, the aromatic vinyl compound monomer unit and the aromatic polyely monomer unit are set to 100% by mass. The composition of the copolymer, the number average molecular weight, and the glass transfer temperature are shown in Table 1.

[0092] The raw material is as follows. Diethylene benzene is used to produce disylene benzene (metallic bodies, the pttal mixture, and divinity pure). Regarding the second functional polyphenylene ether oligomer (OPE-2ST, the number average molecular weight is 1200), the toluene solution of Mitsubishi Gascco is further diluted with toluene, and thereby adding a large amount of methanol for methanol precipitation. Dry, thereby obtaining a powdery polyphenylene oligomer. As SEBS, Tuftec H-1041 manufactured by Asahi Kasei is 58000). 1,2-Polypineene system uses Liquid polybutadiene manufactured by Cao Dao Co., Ltd., Cao Ding Co., Ltd .: Product Name B-3000 (number average molecular weight of 3200). Differential peroxide (trade name "Percunyl D"), or 2,5-dimethyl-2,5-double (third D) Base peroxide) hexene-3 (trade name "Perhexyne 25b).

[0093] [Table 1] Ethylene content 1-hexene content Styrene content Diethylene benzene Vinyl Number average molecular weight Glass transfer temperature Copolymer quality% quality% quality% (Single / quantity average molecular weight) Mn ° C P-1 46 0 53 2.4 68000 -8 P-2 59 0 40 3.5 47000 -15 P-3 47 3.8 48 3.5 37000 -18 P-4 67 0 30 10.6 48000 -15

[0094] [Table 2] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 P-1 100 - - - - - - - 100 - - - P-2 - 100 100 - - - - 100 - - - - P-3 - - - 100 - - - - - - - - P-4 - - - - 100 100 100 - - - - - Monomer 1 Styrene 5 - - - - - - - - - - - Monomer 2 Ethylene - - - - - - - - - - - - Monomer 3 Diethylene benzene 4 - - - 5 - - - - - - - Differential polyphenylene ether oligomers (OPE-2ST) 70 70 50 - 70 90 50 70 - 100 70 - 1,2-polybutadiene - - 20 20 - - 30 - - - 30 100 Tuftec H1041 (SEBS) - - - 20 - - 10 - - - - - Solvent - - - - - - 200 (Average toluene) 200 (Average toluene) - 200 (Average toluene) 200 (Average toluene) 200 (Average toluene) hardener 1 parts by mass * 1 parts by mass * 1 parts by mass * 1 parts by mass * 1 parts by mass * 1 parts by mass * 1 parts by mass * 1 parts by mass * 1 parts by mass * 1 parts by mass * 1 parts by mass * 1 parts by mass * Character of composition (room temperature) Half-hard resin Soft resin Soft resin Soft resin Half-hard resin Soft resin Varnish Varnish Soft resin Varnish Varnish Varnish Storage elastic modulus (300 ° C) / PA 2.0 × 10 6 2.1 × 10 6 1.9 × 10 6 1.5 × 10 6 2.6 × 10 6 2.3 × 10 6 1.8 × 10 6 2.0 × 10 6 Fracture and cannot determine ★ The hardenat produces most cracks and cannot be determined Unmeated Unmeated Tension elastic modulus / MPA 160 180 85 P 370 210 54 160 Unmeated Unmeated Unmeated Volume resistivity / Ω · cm 8 × 10 15 5 × 10 15 4 × 10 15 5 × 10 15 8 × 10 15 2 × 10 15 3 × 10 15 6 × 10 15 Unmeated Unmeated Unmeated Dielectric constant 2.3 2.4 2.2 2.3 2.3 2.4 2.3 2.3 Unmeated 2.5 2.6 Dielectric loss 0.0018 0.0011 0.0014 0.0020 0.0010 0.0011 0.0012 0.0012 Unmeated 0.0033 0.005 Water absorption rate / quality% <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Unmeated Unmeated Unmeated The formation of the table represents the mass. ★ In the assay, in 250 ° C, the stored elastic modulus 3 × 105Pa is half-melted. * Add 1 part by mass of 100 parts by mass of the raw material other than the hardener. [Example 1] PL2000 manufactured by Brabender Plasti-Corder (Brabender) is used to invest in a pre-substantial resin P-1 (ethylene-styrene-dilyne copolymer) The monomers and resins shown in Table 2 (formulated in the table), at 120 ° C for 10 minutes in rotation speed 30 rpm, and then add 1 quality to 100 parts by mass of the resin and monomer. The hardening agent (dual isophenyl isryl peroxide, and yield.) Produced by mixing for 5 minutes under the above conditions. The resulting composition is clamped in the mold frame and 2 ferrofillon (TEFLON, registered trademark) sheet and secretly, and is suppressed by heating the pressing method (120 ° C, time 5 minutes, pressure 5 MPa) to obtain various kinds. The thickness (thickness of 1.0 mm, 0.5 mm, etc.) (unchemical sheet). The resulting sheet was sandwiched by the glass plate, and the heating was applied, and the heating treatment was applied for 30 minutes at 120 ° C for 30 minutes, and then heated at 180 ° C. 200 minutes of hardening. After hardened, remove the glass plate, Teflon (registered trademark) sheet and modules to obtain a film-shaped hardening body of the composition of the present invention.

[0096] [Example 2 to Example 6, Comparative Example 1] The composition was prepared in the same order as in Example 1 (formulated in the table). It is molded and hardening it in the same manner as in Example 1. Among the examples, the 5-minute mixture is added to 100 ° C for 10 minutes by the raw material of the hardener at 100 ° C for 10 minutes. . Among them, Example 4 is used as a hardener using PerhexYne 25b. Further, in Example 3, Example 4, in Example 7 described later, 1,2-polybutadene was added prior to the addition of the hardener. Examples 1 to Example 6, the traits (room temperature) of the comparative example 1 were the character (room temperature) of the formula (room temperature) of the soft resin, semi-rigid resin shape, as the method of the sheet, even after the suppression Dragon (registered trademark) sheet peeling, the self-suction property of the sheet itself is low, which can be operated as a separate sheet. Examples of the preferred conditions of the present invention are not well-hardened. It is easy to perform forming processing as a thermoplastic resin.

[0097] [Examples 7 to Example 8, Comparative Example 2 to Comparative Example 4] A raw material other than the hardener is added to 60 ° C in Table 2, which is added to 60 ° C in the container including heating cooling jacket and the stirring wing. The composition of the varnish (viscous liquid shape) is obtained and stirred. Then the hardener is added and stirred to dissolve. The hardener is used for bisphenyl peroxide. The resulting cleaned composition is injected into Teflon (registered trademark) mold frame on Teflon (registered trademark) sheet, and the solvent is sufficiently blown by the air dryer of about 100 ° C and then further in reduced pressure. , Then carefully remove Teflon (registered trademark) module, resulting in a sheet of soft resin. The resulting sheet is further clamped in the sheet frame and 2 ferrofillon (registered trademark) sheet and secretly, and is compressed by heating the pressing method (120 ° C, time 5 minutes, pressure 1.5 MPa) to obtain various kinds. The thickness (thickness of 1.0 mm, 0.5 mm, etc.) (unchemical sheet). This sheet is easy to operate, even from Teflon (registered trademark) sheet peeling, the self-adherity of the sheet is also low, and can be operated as a single sheet. That is, it is easy to perform the forming processing of the thermoplastic resin in the state of unheated. The resulting sheet was sandwiched along with Telelon (registered trademark) sheet with a glass plate, and the load was applied, and the heating treatment was carried out at 120 ° C for 30 minutes to heat treatment, and then at 200 ° C 120 minutes of heating treatment and hardened. After hardened, remove the peeling plate, Teflon (registered trademark) sheet and frame, and obtain a hardening sheet of the composition of the present invention.

[0098] The hardening body of the sheet obtained by Example 1 to Example 8 was measured in a viscoelastic spectrometer, and the elastic modulus of the elastic modulus of 300 ° C (573K) can be determined in 300 ° C. It is 5 × 105Pa or more. Further, the crosslinking density obtained from the storage elastic modulus of 300 ° C (573K) is higher than 3 × 10-5 mol / cm3, indicating sufficient crosslinking. In addition, both 3 MPa or more to the tensile elastic modulus of 3 GPa are displayed. Further, the tensile breaking point strength is 5 MPa or more until 50 MPa, and the elongation of the tensile breakage is 50% or more to 250%. Dielectric constant, dielectric loss is also satisfied with the scope of the invention. The water absorption rate of the hardening sheet obtained by Example 1 to Example 8 was not up to 0.1% by mass, and the volume resistivity was 1 × 1015 Ω · cm or more. The hardening sheet obtained by the first embodiment to Example 8 was determined by 10 GHz to 2.0 or more to 2.5 or more and the dielectric losses were precipitated to 0.0005 or more to 0.003 or less, showing good low dielectric properties. The storage elastic modulus of 300 ° C from the sheet obtained by Comparative Example 1 is also not satisfied with the conditions of the present invention. Most of the cracks produced by the sheet obtained by Comparative Example 2 are not suitable for use as an insulating material without performing various physical properties. The sheets obtained by Comparative Example 3, Comparative Example 4 did not satisfy the preferred dielectric constant of the present invention, the range of dielectric loss, and other evaluations were not implemented.

[0099] [For the stripping strength of the coarse surface of the copper foil] Copper foil is manufactured using three well metal mining Co., Ltd. (VSP series, TQ-M7-VSP, thickness 12 μm). The eliminated sheet having a thickness of 0.3 mm obtained by pressing a thickness of 0.3 mm in a thickness of 0.3 mm in 2 minutes in 120 ° C for 2 minutes in 120 ° C, so that the coarse surface of the copper foil contacts the aforementioned unknown sheet. It was heated by the pressure 5 MPa at 120 ° C for 30 minutes by pressure 5 MPa at 120 ° C, and then heated at 150 ° C for 30 minutes, then heated at 200 ° C for 120 minutes, thereby making the sheet and The copper foil is then hardened. The release strength determination of the copper foil is based on the Japanese Industrial Standard (JIS) C6481: 1996 by 90 ° peeling. As a result, the peel strength was 2.3 N / mm. The composition of Example 4 also determines the peel strength of the copper foil, resulting in 1.5 N / mm.

[0100] Synthesis of [Ethylene-Styrene-Diethylene Benzopolymerization] Refesction method of Japanese Special Top 9-40709, a high endor with a capacity of 10L and a mixer and a heating cooling jacket, Use dichloromethyl methacyclopentadienyl zirconium as a catalyst using methyl aluminoxane (Tosoh Fine Chem), MMAO-3A toluene solution) as a help of contact, use ring Hexanone is used as a solvent, using styrene, divinyl, ethylene as a raw material, and appropriately change the amount of monomer, ratio, polymerization pressure, and polymerization temperature. 1-isopropyl alcohol was administered in the resulting polymerization, and then a large amount of methanol in the presence of a polymerization inhibitor and recovered copolymer. The copolymer o-1 was vacuum dry for two days and two days at 50 ° C. [Olefin-Aromatic Vinyl Compound - Aromatic Dultiene Copolymers] Refer to Japanese Laid-Open Patent Publication No. 2009-161743, Japan's special production method, the method, ratio, and polymerization of the monomer, ratio, polymerization Pressure, polymerization temperature, copolymer of P-5. The olefin monomer unit, the aforementioned aromatic vinyl compound monomer unit and the aromatic polyely monomer unit are set to 100% by mass. The composition of the obtained O-1, P-5, the number average molecular weight, the glass transfer temperature is shown in Table 3.

[0102] Double Malay Imaphylation BMI-1500 manufactured using Designer Molecules Inc.

[0103] Dioxaroxysite system uses the molten dioxide SFP-130MC (D50 = 0.6 μm, a specific surface area of ​​6.2 m2 / g, true specific gravity of 2.26 g / cm3) without pre-treatment .

[0104] [Table 3] Ethylene content Styrene content Diethylene benzene Vinyl Number average molecular weight Glass transfer temperature Copolymer / Oligomer quality% quality% (indivual / Number average molecular weight) Mn ° C P-5 48 51 4.3 46000 -9 O-1 54 35 3.1 3800 -10 [Example 9, Example 10] In a container including heating cooling jacket and a stirring wing, a raw material other than the hardener is added to 60 ° C and stirred according to Table 4, and a varnish is obtained (viscous) Finds of liquid shapes. Then add a hardener for stirring to dissolve. The hardener is used using Perhexyne 25b. Inject the resulting cleaning composition into Teflon (registered trademark) mold frame on Teflon (registered trademark) sheet, using a dryer dryer to 60 ° C, then adequately blow up the solvent under reduced pressure . The resulting sheet is sandwiched along with the Mirror metal plate, and the load is applied, and the load is applied, and the heat treatment is heated at 120 ° C for 30 minutes, and the treatment is 30 minutes at 150 ° C, and then heated at 200 ° C. 120 minutes and hardening. After hardened, remove the metal plate, Teflon (registered trademark) sheet and frame, and obtain a hardening sheet of the composition of the present invention. [Example 11] The dioxide fillement (50% by volume of 50% by volume of the resin) was obtained in the same manner as in Example 9, Example 10. Further agbject, the obtained slurry varnish is further stirred by the bubble mixing Talang (New Group) to stir, injected into Teflon (registered trademark) on Teflon (registered trademark) sheet (registered trademark) The mold frame is utilized by a dryer of about 60 ° C, and then the solvent is sufficiently blown under reduced pressure. The resulting sheet is sandwiched along with the Mirror metal plate, and the load is applied, and the load is applied, and the heat treatment is heated at 120 ° C for 30 minutes, and the treatment is 30 minutes at 150 ° C, and then heated at 200 ° C. 200 minutes of hardening. After hardened, remove the metal plate, Teflon (registered trademark) sheet and frame, and obtain a hardening sheet of the composition of the present invention.

[0107] [Table 4] Example 9 Example 10 Example 11 Copolymer P-5 100 100 100 Common oligomer O-1 40 - - Differential polyphenylene ether oligomers (OPE-2ST) - - 100 Double Malay 醯 Immine (Designer Molecules Inc. BMI-1500) - 8 - Solvent (toluene) 250 200 400 Dioxide filler (SFP-130MC) - - 452 (50 vol%) Harder PerhexYne 25b 1 parts by mass * 1 parts by mass * 1 parts by mass * Numerous resin composition character (room temperature) Soft resin Soft resin Hard resin Storage elastic modulus (300 ° C) / PA 1.6 × 10 6 1.5 × 10 6 2.3 × 10 8 Tension elastic modulus / MPA 15 20 2400 Volume resistivity / Ω · cm > 10 15 > 10 15 > 10 15 Dielectric constant 2.3 2.4 2.9 Dielectric loss 0.0012 0.0018 0.0022 Water absorption rate / quality% <0.1 <0.1 <0.1 The formation of the table represents the mass. * Add 1 part by mass of 100 parts by mass of the raw material other than the hardener. The hardening body obtained by Example 9, Example 10 and the hardening body added by the addition of the filler obtained by Example 11 met the conditions of the hardening body of the present invention. [Example 12, Example 13] [Evaluation as the Copper Foil and LCP (Liquid Crystal Polymer) sheet] The varnish obtained by Example 9 and Example 10, as shown in the following manner Copper foil relative to the LCP sheet. As the copper foil is used, the copper foil is used as the LCP sheet system, and the LCP resin (product number A-5000, melting point 280 ° C) manufactured by U.S. Paste (using the method described by the International Publication WO JO TET N). The sheet). The lacquer was applied to the LCP sheet, first removing the solvent at 60 ° C, then at 60 ° C, at normal pressure to vacuum, in a non-foaming, was carefully removed. The varnish layer has a thickness of about 30 μm after the solvent removal. The coarse surface of the copper foil is mounted on the dark side of the sheet to remove the sheet of the solvent, while pressurizing by pressurizing machine by pressing a press machine, heating at 120 ° C for 30 minutes, 30 minutes at 150 ° C, then Heating was heated at 180 ° C for 120 minutes and hardened. The sheet was cut into a width of 10 mm, length 100 mM, and the LCP sheet was evaluated by the Japanese Industrial Standard (JIS) C6481: 1996 by the Japanese Industrial Standard (JIS) C6481: 1996. The peel strength was 1.4 N / mm in the case of the varnish obtained by Example 9. The peel strength was 1.3 N / mm in the case of the varnish obtained by Example 10. The peeling surface was observed, and the result was peeled off from the laminated hardening body and the LCP sheet. Therefore, the LCP sheet was 1.4 N / mm and 1.3 N / mm for the peel strength derived from the varnish hardening body. Further, in the same test piece, the peel strength of the copper foil for the hardening body derived from the varnish is higher than the value of the above value.

[0110] [Comparative Example 5] The copper foil and LCP sheet were used, and the same condition was heated with the same conditions as the examples, but the substantially both were not followed.

[0111] [Sample Example] According to the following raw materials, the second state copolymer P-1a to the copolymer P-4A is prepared by the formulation according to the formulation.

[0112] Diethylene benzene is used to produce disylene benzene (metallic bodies, and the pure body mixture, and divinite pure). BVPE (1,2-bis (vinylphenyl) ethane) is synthesized by the synthesis method of Japanese Laid-Open No. 2003-212941. For the interstitial - interconnected body, interlayer - to the bodies, the mixture of the opposite position. 1, 2-PBD is manufactured using Japanese Cao Da. Regarding the second functional polyphenylene ether oligomer (OPE-2ST, the number average molecular weight is 1200), the toluene solution of Mitsubishi Gascco is further diluted with toluene, and thereby adding a large amount of methanol for methanol precipitation. Dry, thereby obtaining a powdery polyphenylene oligomer. The SEBS is H-1041 manufactured using Asahi Chemical Company. The hardener is used to use the bisphenyl peroxide (Percumyl D) manufactured by Ricin Company.

[0113] [Table 5] Ethylene content 1-hexene content Styrene content Diethylene benzene Vinyl Number average molecular weight Glass transfer temperature Copolymer quality% quality% quality% (indivual / Number average molecular weight) Mn ° C P-1A 46 0 53 2.4 68000 -8 P-2A 59 0 40 3.5 47000 -15 P-3A 62 20 15 3.5 15000 -47 P-4A 64 10 25 2.4 24000 -47

[0114] Table 6 is shown in Table 6, etc.

[0115] [Table 6] Example 1A Example 2A Example 3A Example 4A Comparative Example 1A Comparative example 2A P-1A 100 - - - - - P-2A - 100 100 100 - - P-3A - - - - 100 - P-4A - - - - - 100 Monomer 1 Styrene 4 - - - - 20 Monomer 2 Ethylene - 5 - - 20 - Monomer 3 Diethylene benzene 3 3 - - - - Monomer 4 BVPE (1,2-double (vinylphenyl) ethane) - - 10 - - - Monomer 5 Isocanic acid triolel esters (TAIC) - - - 3 - - Harder dual isophenyl benesyl peroxide 1 parts by mass * 1 parts by mass * 1 parts by mass * 1 parts by mass * 1 parts by mass * 1 parts by mass * Numerous resin composition character (room temperature) Soft resin Soft resin Soft resin Soft resin Visible resin Visible resin Storage elastic modulus (300 ° C) / PA 1.1 × 10 6 1.4 × 10 6 2.3 × 10 6 1.3 × 10 6 ★ 1.5 × 10 5 Bridge density (300 ° C) / mol / cm 3 7.7 × 10 -5 9.8 × 10 -5 1.6 × 10 -4 9.1 × 10 -5 2.1 × 10 -5 the following 1.1 × 10 -5 Tensile elastic modulus / MPA 5 6 20 Mean 1 1 Volume resistivity / Ω · cm 5 × 10 15 3 × 10 15 5 × 10 15 2 × 10 15 6 × 10 15 3 × 10 15 Dielectric constant 2.2 2.3 2.3 2.5 2.3 2.1 Dielectric loss 0.0011 0.0011 0.0013 0.0016 0.0012 0.0013 Water absorption rate / quality% <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 * Add 1 part by mass of 100 parts by mass of the raw material other than the hardener. ★ In the assay, in 250 ° C, the storage elastic modulus 3 × 105Pa is half-melted. [Example 1A] Use Brabender Plasti-Corder (PL2000 type manufactured by Branette) to invest in a pre-substantial copolymer P-1A (ethylene-styrene-divinylbenzene copolymer) and monomer 5 minutes in 100 ° C for 5 minutes, and then add 1 parts by mass of the hardening agent (dual-isophenyl peroxide, and yarn company manufacturing with respect to the total 100 parts by mass of the copolymer and the monomer. ), The composition is produced by mixing at 100 ° C, rotational speed 50 rpm, 5 minutes. The resulting composition is clamped in the mold frame and 2 iron fluoron (registered trademark) sheets and secretly, and compressed by heating the pressing method (120 ° C, time 5 min, pressure 5 MPa) to obtain various thicknesses ( A sheet (unchemical sheet) of 1.0 mm, 0.5 mm, etc.). The resulting sheet is sandwiched along with the fiberglass (registered trademark) sheet, and the load is applied, and the heating is applied for 30 minutes at 120 ° C, and the heat treatment is 30 minutes at 150 ° C, and then heated at 180 ° C. 120 Minutes were hardened. After hardened, remove the glass plate, Teflon (registered trademark) sheet and modules to obtain a film-shaped hardening body of the composition of the present invention.

[0117] [Example 2A to Example 4A, Comparative Examples 1A to Comparative Example 2A] The composition is prepared in the same order as in Example 1A, and the composition is prepared according to Table 6 (in the table. The molding is formed in the same manner as in Example 1A and is hardening. Examples 1A to Example 4A The character (room temperature) of the hardening of the hardening (room temperature) is a soft resin shape, a sheet of semi-hard resin shape, as a sheet of operation, even from Teflon (registered trademark) The sheet peeling, the self-adherity of the sheet itself is low, and can be operated as a separate sheet. Examples of the preferred conditions of the present invention are not well-hardened. It is easy to perform forming processing as a thermoplastic resin.

[0118] On the other hand, with respect to Comparative Example 1A, Comparative Example 2A, a glass container having a mixer and a warm jacket is used, and the raw material is mixed by stirring, and the hardener is added to the above conditions. Carry out for 10 minutes. The molding is formed in the same manner as in Example 1A and is hardening. Comparative Example 1A, the character (room temperature) of the comparative example 2a is a hardening of the hardening (room temperature) of the semi-solids. When these compositions are peeled off from the stripping sheet (Teflon (registered trademark) sheet), the adhesion is displayed, and the self-receiving property is difficult to operate as a separate sheet, which can only be taken from the stripping sheet. The state of clamping is operated.

[0119] The hardening body of the composition sheet obtained by Example 1A to Example 4A is in the viscoelastic spectroscopy, and the elastic modulus can be determined at 300 ° C, and the elastic modulus can be determined at 300 ° C (573K). The modulus is 5 × 105Pa or more. Further, the crosslinking density obtained from the storage elastic modulus of 300 ° C (573K) is higher than 3 × 10-5 mol / cm3, indicating sufficient crosslinking. In addition, both 3 MPa or more to the tensile elastic modulus of 3 GPa are displayed. Further, the tensile breaking point strength is 5 MPa or more until 50 MPa, and the elongation of the tensile breakage is 50% or more to 250%. Dielectric constant, dielectric loss is also satisfied with the scope of the invention. The water absorption rate of the hardening film obtained by Example 1A to Example 4A did not reach 0.1% by mass, and the volume resistivity was 1 × 10 15 Ω · cm or more. On the other hand, the tensile elastic modulus of the end of the sheet temperature of the sheet obtained by Comparative Example 1a, Comparative Example 2a, and the storage elastic modulus of the additional 300 ° C or crosslinking density is also not satisfied with the conditions of the present invention.

[0120] [Stripping strength for the coarse surface of the copper foil] Copper foil is made of three well metal mining Co., Ltd. (VSP series, TQ-M7-VSP, thickness 12 μm). The composition of Example 1A was 0.3 mm of an unknown sheet having a thickness of 0.3 mm obtained by 5 MPa by 5 MPa, such that the coarse surface of the copper foil was contacted, and the thickness of 0.3 mm is used. The heat pressing machine of the frame was heated at a pressure of 5 MPa at 120 ° C for 30 minutes, and then heated at 150 ° C for 30 minutes, then heated at 180 ° C for 120 minutes, thereby so that the sheet and the copper foil were further hardened. The release strength determination of the copper foil is based on the Japanese Industrial Standard (JIS) C6481: 1996 by 90 ° peeling. The resulting peel strength was 1.7 N / mm.

[0121] According to the above results, the hardening body of the composition of the present invention is hardened to have excellent low dielectric properties and electrical insulation, showing a specific range of elastic modulus, heat resistance, water resistance, and The intensity (elastic modulus) of the high temperature and high temperature domain is sufficiently hardening body. In addition, the peel strength of the copper foil is also a practical strength. Further, a high peel strength can also be displayed under relatively moderate conditions with the LCP (liquid crystal polymer) sheet. The composition of the hardening property showed the following thermoplastic: may be shown as a state in which a film-shaped solid is shown, and can be melted by heating below the hardened condition, and is formed into a variety of shapes and hardened. Therefore, it is easy to form a variety of shapes comprising the sheet, which can then be heated and hardened. The hardening body can be used in particular for high-frequency electrical insulation materials. The hard chemical body can be suitably used as an electrical insulating material of the film, a high frequency electrical insulation material. In particular, the present invention is small in the composition of the monomer (single body) component, or may also be substantially free of monomers. The composition of the present invention can be used as a cover film, a solder resist film, a lamination film, a bond sheet, a layer insulator, and an inter-layer interlayer, and interlayer. Etume. The present invention can be used as a printed substrate, a flexible printed substrate, a CCL (coat copper) substrate, FcCl (flexible coat copper) substrate. Further, the insulating layer for the substrate is used.

Claims

1. A curable composition comprising an olefin-aromatic vinyl compound-aromatic polyene copolymer satisfying the conditions (1) to (5) below, and an additive resin; wherein the additive resin is selected from one or more of the group consisting of hydrocarbon elastomers, polyphenylene ethers, olefin-aromatic vinyl compound-aromatic polyene co-oligomers, and aromatic polyene resins; wherein the hydrocarbon elastomer is selected from one or more of the group consisting of ethylene elastomers, propylene elastomers, and 1,2-polybutadiene which is liquid at 25°C; (1) the number average molecular weight of the olefin-aromatic vinyl compound-aromatic polyene copolymer is 5,000 or more to 100,000 or less; (2) the aromatic vinyl compound monomer is an aromatic vinyl compound with 8 or more to 20 or less carbon atoms, and the content of the aromatic vinyl compound monomer unit in the olefin-aromatic vinyl compound-aromatic polyene copolymer is 10% by mass or more to 55% by mass or less; (3) The aromatic polyene is selected from one or more polyenes having a plurality of vinyl and / or extended vinyl groups having 5 to 20 carbon atoms, and the content of vinyl and / or extended vinyl groups derived from the aromatic polyene unit is 3 to less than 20 based on the number average molecular weight; (4) The olefin is selected from one or more olefins having 2 to 20 carbon atoms, and the total of the olefin monomer unit, the aforementioned aromatic vinyl compound monomer unit, and the aromatic polyene monomer unit is 100% by mass; (5) In the aforementioned olefin-aromatic vinyl compound-aromatic polyene copolymer, the content of the aforementioned olefin monomer unit is 45% to 90% by mass.

2. The curable composition as described in claim 1, wherein, relative to 100 parts by mass of the aforementioned olefin-aromatic vinyl compound-aromatic polyene copolymer, it contains 1 to 500 parts by mass of the aforementioned additive resin.

3. The curable composition as described in claim 1 or 2, wherein the aforementioned added resin is selected from one or more of the group consisting of polyphenylene ether and 1,2-polybutadiene which is liquid at 25°C.

4. The curing composition as described in claim 1 or 2 further contains one or more monomers selected from the group consisting of aromatic vinyl compound monomers, aromatic polyene monomers, and polar monomers.

5. The curable composition as described in claim 4, wherein, relative to 100 parts by mass of the aforementioned olefin-aromatic vinyl compound-aromatic polyene copolymer, it contains more than 0 parts by mass but less than 10 parts by mass of one or more of the aforementioned monomers selected from the group consisting of aromatic vinyl compound monomers, aromatic polyene monomers, and polar monomers.

6. A curable composition comprising a curable composition as described in any one of claims 1 to 5, and a solvent, wherein the curable composition is in the form of a varnish.

7. The hardening composition as described in claim 1 or 2 further contains a hardening agent.

8. The hardening composition described in claim 1 or 2 further comprises one or more of the group consisting of fillers, flame retardants, and surface modifiers.

9. A molded body comprising a hardening composition as described in any one of claims 1 to 8.

10. The molded body as described in claim 9, wherein the molded body is a sheet.

11. A hardening body formed by hardening a hardening composition as described in any one of claims 1 to 8.

12. The hardened body as described in claim 11, wherein the storage elastic modulus of the hardened body at 300°C is 5 × 10⁵ Pa or more.

13. The hardened body as described in claim 11 or 12, wherein the aforementioned hardened body is an electrical insulating material.

14. An electrical insulating material, which is a hardened body obtained from a composition comprising an olefin-aromatic vinyl compound-aromatic polyene copolymer and an added resin satisfying the conditions of (1) to (5) below; wherein the added resin is selected from one or more of the group consisting of hydrocarbon elastomers, polyphenylene ethers, olefin-aromatic vinyl compound-aromatic polyene co-oligomers, and aromatic polyene resins; wherein the hydrocarbon elastomer is selected from one or more of the group consisting of ethylene elastomers, propylene elastomers, and 1,2-polybutadiene which is liquid at 25°C; wherein the electrical insulating material has a storage modulus of elasticity of 5×10⁵ Pa or more at 300°C, and a dielectric constant of 2.0 or more to 2.5 or less at 23°C and 10 GHz, and a dielectric loss tangent of 0.0005 or more to 0.003 or less; (1) wherein the number average molecular weight of the olefin-aromatic vinyl compound-aromatic polyene copolymer is 5,000 or more to 100,000 or less. (2) The aromatic vinyl compound monomer is an aromatic vinyl compound with 8 to 20 carbon atoms, and the content of the aromatic vinyl compound monomer unit in the aforementioned olefin-aromatic vinyl compound-aromatic polyene copolymer is 10% to 55% by mass; (3) The aromatic polyene is selected from one or more polyenes with 5 to 20 carbon atoms having a plurality of vinyl and / or extended vinyl groups in the molecule, and the content of vinyl and / or extended vinyl groups derived from the aromatic polyene unit is 3 to less than 20 based on the number average molecular weight; (4) The olefin is selected from one or more olefins with 2 to 20 carbon atoms, and the total of the olefin monomer unit, the aforementioned aromatic vinyl compound monomer unit, and the aromatic polyene monomer unit is 100% by mass; (5) The content of the aforementioned olefin monomer unit in the aforementioned olefin-aromatic vinyl compound-aromatic polyene copolymer is 45% to 90% by mass.

15. The electrical insulating material as described in claim 14, wherein in the aforementioned olefin-aromatic vinyl compound-aromatic polyene copolymer, the aforementioned aromatic polyene is divinylbenzene, and the content of the vinyl groups derived from the aforementioned divinylbenzene is 3.5 or more but less than 20 in terms of number average molecular weight.

16. A curable composition comprising an olefin-aromatic vinyl compound-aromatic polyene copolymer satisfying the conditions below (1) to (5), and a monomer comprising more than 0 parts by mass to less than 10 parts by mass relative to 100 parts by mass of the aforementioned olefin-aromatic vinyl compound-aromatic polyene copolymer; wherein the aforementioned monomer is one or more selected from the group consisting of aromatic vinyl compound monomers, aromatic polyene monomers, and polar monomers; (1) the number average molecular weight of the aforementioned olefin-aromatic vinyl compound-aromatic polyene copolymer is 5,000 or more to 100,000 or less; (2) the aromatic vinyl compound monomer in the aforementioned olefin-aromatic vinyl compound-aromatic polyene copolymer is an aromatic vinyl compound with 8 or more to 20 or less carbon atoms, and the content of the aromatic vinyl compound monomer unit in the aforementioned olefin-aromatic vinyl compound-aromatic polyene copolymer is 10% by mass to 55% by mass or less; (3) The aromatic polyene is selected from one or more polyenes having a plurality of vinyl and / or extended vinyl groups having 5 to 20 carbon atoms, and the content of vinyl and / or extended vinyl groups derived from the aromatic polyene unit is 3 to less than 20 based on the number average molecular weight; (4) The olefin is selected from one or more olefins having 2 to 20 carbon atoms, and the total of the olefin monomer unit, the aforementioned aromatic vinyl compound monomer unit, and the aromatic polyene monomer unit is 100% by mass; (5) In the aforementioned olefin-aromatic vinyl compound-aromatic polyene copolymer, the content of the aforementioned olefin monomer unit is 45% to 90% by mass.

17. The hardening composition as described in claim 16, wherein the aforementioned monomer is a polar monomer.

18. The curable composition as described in claim 16 or 17, wherein in the aforementioned olefin-aromatic vinyl compound-aromatic polyene copolymer, the aforementioned aromatic polyene is divinylbenzene, and the content of the vinyl groups derived from the aforementioned divinylbenzene is 3.5 or more but less than 20 in terms of number average molecular weight.

19. An electrical insulating material, which is a hardened body obtained by hardening a hardening composition as described in any one of claims 16 to 18; wherein the hardened body has a storage elastic modulus of 5 × 10⁵ Pa or more at 300°C, and a dielectric constant of 2.0 or more to 2.5 or less at 23°C and 10 GHz, and a dielectric loss tangent of 0.0005 or more to 0.003 or less.

20. A laminate comprising: a layer containing a hardening composition as described in any one of claims 1 to 8, 16 to 18; and copper foil.

21. A laminate comprising: a layer including a curable composition as described in any one of claims 1 to 8, 16 to 18; and a liquid crystal polymer layer.

22. A laminate comprising: a layer containing a curable composition as described in any one of claims 1 to 8, 16 to 18; a copper foil; and a liquid crystal polymer layer.

23. A hardened body formed by hardening a laminate as described in any one of claims 20 to 22.