JPWO2008123362A1 - Polymerizable composition and molded body - Google Patents

Abstract

The present invention makes it possible to produce a molded body having excellent magnetic properties, particularly magnetic permeability, and excellent stain resistance with high productivity by uniformly dispersing and filling a soft magnetic material having shape anisotropy. An object of the present invention is to provide a soft magnetic substance-containing polymerizable composition. The polymerizable composition according to the present invention comprises a soft magnetic material having shape anisotropy and a bulk polymerizable monomer having one or more reactive unsaturated bonds in the molecule. The ratio (X / Y) of the major axis length (X) to the minor axis length (Y) is preferably 2 or more and 10,000 or less.

Description

  The present invention relates to a molded body containing a soft magnetic body having shape anisotropy and having a high magnetic permeability, a polymerizable composition suitable for obtaining the molded body, and a method for producing the molded body.

  With the remarkable development of electronic and communication fields in recent years, materials having high magnetic permeability at high frequencies are used for electric and electronic devices. In particular, in the fields of inductor elements, transformer elements, high frequency filters, magnetic heads, noise countermeasure components, motors, electromagnetic wave absorbers, and the like, composite materials of resin and magnetic material are required from the viewpoint of improving moldability.

  For example, Patent Document 1 discloses that a resin composite material is formed by melt-kneading a resin such as polyphenylene sulfide and ferrite powder. In this method, the resin and ferrite powder are mechanically mixed under high viscosity conditions where the resin is heated and melted. Once the pellet is prepared by mixing the resin and ferrite powder, the pellet is injection molded. Therefore, workability, productivity, and uniform dispersibility of the magnetic material were low.

  In addition, the use of a cycloolefin polymer, which is a polymer having an alicyclic structure, having low water absorption, excellent electrical properties, processability, and the like as a resin has been studied. For example, Patent Document 2 discloses a technique in which a magnetic material is dispersed in a varnish containing a carboxyl group-containing cycloolefin polymer and a solvent to obtain a slurry, and a molded product is obtained using the slurry. However, in this technique, since a large amount of solvent is used, a drying process is required, the process becomes complicated, and the shape of the molded body is limited.

  Patent Documents 3 and 4 disclose a polymerizable composition containing a norbornene that is a cycloolefin monomer, a metathesis polymerization catalyst, a chain transfer agent, and a crosslinking agent, and a method for obtaining a resin molded body using the same. . These documents describe blending a magnetic material or the like into the polymerizable composition in order to impart ferromagnetism to the resin molded body. However, in these patent documents, there is no specific teaching about the powder properties of the magnetic material.

Patent Document 5 discloses a technique for obtaining an electromagnetic wave absorber by mixing magnetic powder with an acrylic copolymer.
JP 10-326707 A WO 2004/029153 Publication Japanese Patent Laid-Open No. 2004-244609 WO 2005/014690 JP 2007-31695 A

  As described above, even when a polymer in a molten state and a magnetic material are mechanically mixed, the uniform dispersion of the magnetic material is low, it is difficult to mix a large amount of the magnetic material, and workability and productivity are sufficient. is not. In addition, when the polymer and magnetic material are mixed while applying high stress using a roll, kneader, etc., the crystal structure or surface of the magnetic material is damaged and accumulated, resulting in deterioration of magnetic properties was there. On the other hand, when a solvent is used, a drying process is required and productivity is low. Moreover, there existed problems, such as a void generate | occur | produced in the resin molding obtained by the process.

  Patent Documents 3 and 4 describe that various kinds of blends may be mixed in the polymerizable composition. However, when powdered (spherical or granular) magnetic powder such as carbonyl iron is used, the blending amount has to be very large, and not only the specific gravity of the resulting molded body is increased, but also sufficient It was difficult to provide excellent magnetic properties, particularly high magnetic permeability.

  Furthermore, in the resin composition disclosed in Patent Document 5, in the case where a large amount of magnetic powder is added, it is necessary to use an epoxy resin and a low molecular weight copolymer in order to adjust the viscosity. There was also a problem that the body was fragile and dirt easily adhered.

  Therefore, the present invention provides a polymerizing property capable of producing a molded product with excellent magnetic properties, particularly magnetic permeability and excellent contamination resistance by uniformly dispersing and filling the soft magnetic material with high productivity. It is intended to provide a composition.

  The present inventor, in a polymerizable composition containing a soft magnetic material and a block polymerizable monomer (hereinafter sometimes referred to as a block polymerizable monomer), highly fills the soft magnetic material, and has high productivity and high magnetic permeability. As a result of intensive studies to find a prescription that can produce a molded product of the present invention, it was found that a molded product having high magnetic permeability can be obtained by using a magnetic powder having shape anisotropy as a soft magnetic material. Moreover, it discovered that a soft magnetic body could be uniformly disperse | distributed and filled by using the block polymerizable monomer which has a 1 or more reactive unsaturated bond in a molecule | numerator as a monomer to superpose | polymerize. Furthermore, it has been found that a molded article having excellent stain resistance can be obtained by bulk polymerization of such a polymerizable composition, and the present invention has been completed based on these findings.

  That is, the gist of the present invention to solve the above problems is as follows.

(1) A polymerizable composition comprising a soft magnetic material having shape anisotropy and a bulk polymerizable monomer having one or more reactive unsaturated bonds in the molecule.

(2) The polymerizable composition according to (1), wherein the soft magnetic material has a major axis length (X) to minor axis length (Y) ratio (X / Y) of 2 or more and 10,000 or less. object.

(3) The polymerizable composition according to (2), wherein the soft magnetic material has a flat shape.

(4) The polymerizable composition as set forth in (1), wherein 0.1 to 80 volume of the soft magnetic material is contained in the total polymerizable composition.

(5) The polymerizable composition according to any one of (1) to (4), further comprising a polymerization catalyst.

(6) The polymerizable composition as described in (5), wherein the polymerization catalyst is a radical polymerization initiator.

(7) The polymerizable composition as described in (6), wherein the bulk polymerizable monomer is an acrylic monomer.

(8) The polymerizable composition according to (5), wherein the polymerization catalyst is a metathesis polymerization catalyst.

(9) The polymerizable composition as described in (8), wherein the bulk polymerizable monomer is a cycloolefin monomer.

(10) The polymerizable composition according to (9), further comprising a chain transfer agent.

(11) The polymerizable composition according to (9) or (10), further comprising a crosslinking agent.

(12) The polymerizable composition according to any one of (9) to (11), further comprising a dispersant.

(13) A molded product obtained by bulk polymerization of the polymerizable composition according to any one of (1) to (12).

(14) The molded article according to (13), wherein the magnetic permeability at 100 MHz is 10 or more.

(15) A method for producing a molded body, in which the polymerizable composition according to any one of (1) to (12) is applied or impregnated on a support and bulk polymerization is performed.

(16) A method for producing a molded body in which the polymerizable composition according to any one of (1) to (12) is injected into a mold and bulk polymerization is performed.

(17) A molded product obtained by the production method according to (15) or (16).

(18) A laminate comprising the molded product according to (17).

  According to the present invention, it is possible to obtain a molded body that is highly filled with a soft magnetic material, has a high magnetic permeability, and is excellent in stain resistance. Furthermore, since it is not necessary to use a solvent in the polymerizable composition of the present invention, high-speed molding such as reaction injection molding is possible, and a solvent drying step is not necessary. Therefore, if the polymerizable composition of the present invention is used, a magnetic molded body can be obtained with high productivity. The molded body of the present invention can be suitably used for various magnetic application products.

  The polymerizable composition of the present invention contains a soft magnetic material having shape anisotropy and a bulk polymerizable monomer having one or more unsaturated bonds in the molecule. By using a soft magnetic body having shape anisotropy, the obtained molded body can have a high magnetic permeability.

  Here, “shape anisotropy” means that the width of the soft magnetic powder particles is the largest when the shape of the soft magnetic powder particles is observed three-dimensionally with a scanning electron microscope (SEM) or the like. An aspect ratio (X / Y) between a long axis length (X) that is the length of the long axis and a short axis length (Y) that is the length of the short axis that has the shortest width is the long axis as the long axis. ) Is preferably 2 or more, 10,000 or less, more preferably 2 or more and 1,000 or less, still more preferably 5 or more and 500 or less, and particularly preferably 10 or more and 100 or less.

  If it is larger than this range, the viscosity of the polymerizable composition may be too high when blended, and if it is smaller than this range, a molded product or laminate having sufficient magnetic permeability may not be obtained.

  In the above, the major axis length (X) is preferably 0.01 to 1,000 μm, more preferably 0.01 to 500 μm, particularly preferably 0.1 to 100 μm, and the minor axis length (Y). Is preferably in the range of 0.001 to 100 μm, more preferably 0.01 to 10 μm, and particularly preferably 0.1 to 5 μm.

  When the long axis length (X) is larger than this range, the viscosity of the polymerizable composition may be excessively increased. When the major axis length (X) is smaller than this range, the obtained molded body or laminate has a sufficient magnetic permeability. There is a risk that it will not be obtained. If the minor axis length (Y) is larger than this range, the obtained molded product or laminate may not be able to obtain sufficient magnetic permeability. If the minor axis length (Y) is smaller than this range, the viscosity of the polymerizable composition becomes too high at the time of blending. There is a fear.

  The major axis length (X) and minor axis length (Y) are obtained by obtaining an average value for 100 arbitrary particles in a photographic image obtained by observing soft magnetic powder particles with an electron microscope (SEM) or the like. It is determined.

  Here, “observing three-dimensionally” means grasping the three-dimensional shape of the entire particle by rotating the sample stage of the SEM, etc., and the long axis length (X) and short axis of each soft magnetic particle. This represents obtaining the maximum value of the length (Y).

  More specific shapes of the soft magnetic material used in the present invention include needle shapes, rod shapes, flat shapes, tree shapes, etc., more preferably needle shapes, rod shapes, flat shapes, and particularly preferred. Is flat. The flat shape is a plate shape by SEM observation.

  The soft magnetic material used in the present invention is not particularly limited as long as the shape anisotropic powder having soft magnetism is properly used in the application. Soft magnetism is a property in which internal magnetization easily aligns in the direction of the magnetic field with respect to a magnetic field applied from the outside, that is, it is easily magnetized. On the other hand, hard magnetism is a property in which internal magnetization hardly occurs even when an external magnetic field is applied, and a property in which a magnetic field can be created outside.

  Typical examples of such a soft magnetic material include at least one of Fe, Ni, and Co, and specifically include soft magnetic ferrite and soft magnetic metal.

The soft magnetic ferrite is a compound (MO · Fe ₂ O ₃ ) of ferric oxide (Fe ₂ O ₃ ) and a divalent metal oxide (MO). Here, M represents a divalent metal. Specifically, depending on the type of the divalent metal oxide, Mn—Zn, Mg—Zn, Ni—Zn, Cu, Cu—Zn, Cu—Zn—Mg, Cu—Ni—Zn Type, spinel type ferrite such as Li-Fe type, YFe type garnet type ferrite represented by R ₃ Fe ₅ O ₁₂ (R is trivalent Y or rare earth element), Me is Fe, Ni, Co, It is classified into a ferro-spreader type ferrite such as a BaFe system having a hexagonal structure in which the composition of MeO, BaO, and Fe ₂ O ₃ when Cu is used. Here, expressions such as Mn—Zn-based mean that Mn and Zn are contained as the divalent metal M.

  Among these, ferrite containing Ni, Mn, Zn, Y, or Ba is preferable, and spinel type ferrite such as Mn—Zn type and Ni—Zn type and ferro-spreader type ferrite such as BaFe type are particularly preferable. By using these, the magnetic permeability can be greatly increased.

The Ni—Zn ferrite has a composition represented by the general formula (NiO) _a (ZnO) _b .Fe ₂ O ₃ (a and b are arbitrary numerical values satisfying 0 ≦ a + b ≦ 1). However, a part of Ni may be substituted with another divalent metal such as Cu, Mg, Co, or Mn. The Ni—Zn ferrite may contain other elements as long as the effects of the present invention are not impaired.

The Mg—Zn based ferrite has a composition represented by the general formula (MgO) _c (ZnO) _d · Fe ₂ O ₃ (where c and d are arbitrary numerical values satisfying 0 ≦ c + d ≦ 1). However, a part of Mg may be substituted with another divalent metal such as Ni, Cu, Co, or Mn. The Mg—Zn based ferrite may contain other elements as long as the effects of the present invention are not impaired.

The Mn—Zn-based ferrite has a composition represented by the general formula (MnO) _e (ZnO) _f · Fe ₂ O ₃ (e and f are arbitrary numerical values satisfying 0 ≦ e + f ≦ 1). However, a part of Mn may be substituted with another divalent metal such as Ni, Cu, Co, or Mg. The Mn—Zn ferrite may contain other elements as long as the effects of the present invention are not impaired.

Cu-based ferrite means a material having a composition represented by the general formula (CuO) _g · Fe ₂ O ₃ (g is an arbitrary value satisfying 0 ≦ g ≦ 1), but a part of Cu May be substituted with other divalent metals such as Ni, Zn, Mg, Co, and Mn. Cu-based ferrite may contain other elements as long as the effects of the present invention are not impaired.

Soft magnetic ferrite can be obtained by a known method. Typical examples of the raw materials for ferrite, which is an oxide-based magnetic material, include metal oxides such as Fe ₂ O ₃ , MnO ₂ , MnCO ₃ , CuO, NiO, MgO, ZnO, Y ₂ O, BaO, and the like. Such as carbonates. Examples of the method for producing soft magnetic ferrite include a dry method, a coprecipitation method, and a spray pyrolysis method.

  In the dry method, the raw materials such as oxides and carbonates of the above elements are calculated so as to have a predetermined blending ratio, mechanically mixed, baked and then pulverized. In the dry method, the raw material mixture may be pre-fired, pulverized into fine particles, granulated into granules, further baked, and then pulverized again to obtain a soft magnetic ferrite powder. In the coprecipitation method, a strong alkali is added to an aqueous metal salt solution to precipitate a hydroxide, which is oxidized to obtain fine ferrite powder. The ferrite powder may be granulated, fired and then pulverized. In the spray pyrolysis method, an aqueous solution of a metal salt is pyrolyzed to obtain a particulate oxide. The oxide powder may be granulated, fired and then pulverized. The fired ferrite is pulverized by a hammer mill, a rod mill, a ball mill or the like to obtain a ferrite powder.

  Among these, methods such as a dry method, a coprecipitation method, and a spray pyrolysis method are preferable because particles having direct shape anisotropy can be obtained uniformly.

  Soft magnetic metals include single metal magnetic bodies and composite metal magnetic bodies. The single metal magnetic body is made of Fe, Ni, and Co, and specifically includes iron powder, nickel powder, cobalt powder, and the like. The composite metal magnetic body is a composite of two or more metals, and includes at least one of Fe, Ni, and Co. In addition to these, Si, Al, Co, Cr, B, Nb, Mo, P , Zr, Ti, Hf, Ti, Cu, and the like, alloys, amorphous alloys or nanocrystalline metals.

  Specifically, metallic crystalline materials such as FeSi material (silicon steel), FeNi material (permalloy), FeNiMo material (supermalloy), FeCo material, FeCr material, FeAl material, FeAlSi material (Sendust), FeSiNi material; Examples thereof include a metal amorphous material containing at least one of Co and the like; a metal nanocrystalline material containing at least one of Fe, Co and the like.

  Here, the Fe-containing amorphous material includes Fe-Si-B-based, Fe-B-based, Fe-PC-based Fe-semi-metallic amorphous metal materials, Fe-Zr-based, Fe- Examples thereof include Fe-removed metal-based amorphous metal materials such as -Hf-based and Fe-Ti-based materials. Examples of the amorphous metal material containing Co include amorphous metal materials such as Co—Si—B and Co—B. The nanocrystalline material obtained by crystallizing the amorphous metal material into nanosize by heat treatment includes Fe—Si—B—Cu—Nb, Fe—B—Cu—Nb, Fe—Zr—B—. (Cu) series, Fe-Zr-Nb-B- (Cu) series, Fe-Zr-P- (Cu) series, Fe-Zr-Nb-P- (Cu) series, Fe-Ta-C series, Fe -Al-Si-Nb-B system, Fe-Al-Si-Ni-Nb-B system, Fe-Al-Nb-B system, Co-Ta-C system, etc. are mentioned. Here, expressions such as Fe-Si-B-Cu-Nb system mean containing Fe, Si, B, Cu and Nb as main constituent elements. “(Cu)” means that Cu is contained as a trace component. These may be used alone or in combination of two or more.

  Among these, preferably, those containing at least Fe atoms, specifically, FeNi material (permalloy), FeNiMo material (supermalloy), FeAl material, FeAlSi material (Sendust); Metal amorphous material containing Fe; It is a metal nanocrystalline material containing Fe. By using these, the magnetic permeability can be further increased.

  The manufacturing method of these soft magnetic metals can adopt a well-known method, and is not specifically limited. Examples thereof include CVD, sol-gel, electroreduction method, laser ablation method, gas atomization method, water atomization method, chemical reduction method using a reducing agent, and composite method using mechanical alloying.

  The soft magnetic metal thus obtained can be used as it is when it has shape anisotropy, but a soft magnetic material having a predetermined shape and size can also be produced. As a method for producing a soft magnetic material having a predetermined shape and size, a powder obtained by roughly pulverizing an ingot having a required composition with a vibration mill or the like is prepared, and then rolling or stretching, or a grinding media such as a ball mill having a shearing action is used. Examples of the ingot crushing method include crushing with the used crusher or attritor. Further, instead of the coarse pulverization method by the ingot pulverization method, powders obtained by pulverization by a gas atomization method, a water atomization method, a rotating disk method, or a chatter vibration method may be used. Thereby, a needle-like or flat soft magnetic metal is preferably obtained.

  These soft magnetic materials may be used alone or in combination of two or more.

  The surface of these soft magnetic materials is coated with an inorganic material such as silica or alumina, or a coupling agent such as a silane coupling agent, a titanate coupling agent, a zirconate coupling agent, or an aluminate coupling agent; silazanes It is preferable that the surface treatment is performed with a known surface treatment agent such as polysiloxane.

  A well-known thing can be used for a silane coupling agent. Specifically, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropylmethoxysilane, N-β- (N-vinylbenzyl) Aminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane, cyclohexylmethyldimethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride Id, trimethylmethoxysilane, trimethylethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane, n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane, 1.6 bis (trimethoxysilyl) hexane, γ-ureidopropyltriethoxysilane, γ-dibutylaminopropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, tetraethoxysilane, perfluorooctylethyltriethoxysilane, trimethoxystyrylsilane, norbornyltrimethoxysilane Etc.

  Moreover, a titanate coupling agent can use a well-known thing. Specifically, triisostearoyl isopropyl titanate, di (dioctyl phosphate) diisopropyl titanate, didodecylbenzenesulfonyl diisopropyl titanate, diisostearyl diisopropyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate Bis (dioctyl pyrophosphate) ethylene titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, and the like.

  Examples of silazanes include hexamethyldisilazane, tetramethyldivinyldisilazane, tetramethyldibutyldisilazane, and tetramethyldiphenyldisilazane.

  Among these, those having a radical reactive group or a metathesis reactive group are preferable, those having at least one substituent which is a hydrocarbon group are more preferable, those having a substituent having a ring structure are more preferable, Those having a double bond are most preferred. By using these, compatibility with the block polymerizable monomer described later is improved.

  Therefore, particularly preferred surface treatment agents include vinyl methoxysilane, allyltrimethoxysilane, hexenyltrimethoxysilane, styryltrimethoxysilane, norbornyltrimethoxysilane, methacryloxytrimethoxysilane, acryloxytrimethoxysilane, hexyltri And silane coupling agents such as methoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane; and silazanes such as hexamethyldisilazane and tetramethyldivinyldisilazane.

  These surface treatment agents may be used alone or in combination of two or more. The amount of the surface treatment agent is not particularly limited as long as the magnetic properties and heat resistance are not impaired, but usually 0.01 to 30 parts by weight, preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the soft magnetic material, More preferably, it is 0.5 to 10 parts by weight. If it is less than this range, sufficient effects may not be obtained due to compatibility with the bulk polymerizable monomer, and if it is more than this range, it may not be excellent in terms of economy.

  The blending amount of the soft magnetic material is usually 0.1 to 80% by volume, preferably 1.0 to 70% by volume, more preferably 5.0 to 60% by volume, particularly preferably based on the total volume of the polymerizable composition. Is 10 to 50% by volume. The blending amount of the soft magnetic material is usually 0.1 to 99.9% by weight, preferably 10 to 95% by weight, more preferably 50 to 93% by weight, particularly preferably based on the total weight of the polymerizable composition. Is 65 to 90% by weight.

  These soft magnetic materials may be heat-treated. The heat treatment conditions are not particularly limited, but it is usually preferably performed at 300 to 1,000 ° C. for 0.5 to 10 hours in an inert gas atmosphere such as nitrogen, argon or helium or in a hydrogen atmosphere.

  Here, the total volume and the total weight of the polymerizable composition are a composition comprising all of these components when a soft magnetic material, a block polymerizable monomer described later, and optional components added as desired are included. It means the volume and weight of an object. If the blending amount of the soft magnetic material is less than the above range, sufficient magnetic properties may not be obtained, and if it is more than this range, the moldability may be deteriorated. An example of an index of the magnetic characteristics of the soft magnetic material is magnetic permeability. In the present invention, the magnetic permeability at 100 MHz of the finally obtained molded body is preferably 2 or more, more preferably 5 or more, and particularly preferably 10 or more. Further, the magnetic permeability at 1 GHz is preferably 2 or more, more preferably 3 or more. If the magnetic permeability is too low, sufficient magnetic properties may not be obtained. Further, when the magnetic permeability of the molded body is high at a high frequency of 1 GHz or higher, it can be suitably used in applications using high frequency such as wireless LAN, ETC, and in-vehicle radar. Since the magnetic permeability is high, a molded body having sufficient magnetic properties can be obtained even if the thickness is small. In this specification, unless otherwise specified, the magnetic permeability refers to the real part of the complex magnetic permeability.

  The polymerizable composition of the present invention comprises the soft magnetic material and a bulk polymerizable monomer having one or more unsaturated bonds in the molecule. By using a polymerizable composition containing a soft magnetic material and a bulk polymerizable monomer and subjecting this to a bulk polymerization, the resulting molded body has a highly filled soft magnetic material and is highly filled.

  The unsaturated bond in the bulk polymerizable monomer is a carbon-carbon double bond (C = C), a carbon-carbon triple bond (C≡C), an isocyanate group (which imparts addition or ring-opening polymerizability to the monomer). N = C = O). Among these, from the viewpoint of reaction control, a carbon-carbon double bond (C═C) and a carbon-carbon triple bond (C≡C) are preferable, and a carbon-carbon double bond (C═C) is more preferable.

  Here, bulk polymerization is a polymerization method in which a polymerizable monomer is polymerized substantially without a diluting solvent. Bulk polymerization includes thermal polymerization, photopolymerization using ultraviolet rays and gamma rays, polymerization using a polymerization catalyst, etc. From the viewpoint of ease of operation and uniformity of reaction, thermal polymerization and a polymerization catalyst are preferably used. More preferred is polymerization using a polymerization catalyst.

The polymerization format is not particularly limited, and examples thereof include the following formats.
(I) Addition polymerization in which only unsaturated bonds react and have no elimination component (ii) Ring-opening polymerization in which polymerization is accompanied by ring-opening of a cyclic monomer and (iii) Polycondensation with elimination component (iv) Polyaddition without elimination components

  Among the above, (i), (ii) and (iv) are preferable, and (i) and (ii) are more preferable. According to these, low molecular weight by-products are not generated and remain after the reaction, and the obtained molded article is excellent in reliability and heat resistance.

  The polymerization reaction mechanism includes radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization using a transition metal catalyst, and metathesis ring-opening polymerization, and is not particularly limited. In view of the easiness of the reaction, radical polymerization, coordination polymerization using a transition metal catalyst, and metathesis ring-opening polymerization are preferable, and radical polymerization and metathesis ring-opening polymerization are more preferable.

  Specific examples of such bulk polymerizable monomers include aromatic vinyl monomers, acrylic monomers, cycloolefin monomers, urethane monomers, silane monomers, acetylene derivatives such as tolanes, and the like.

  Among these bulk polymerizable monomers, monomers that undergo addition polymerization and those that undergo ring-opening polymerization are preferable from the viewpoints of availability, uniformity of reaction, and physical properties of the resulting molded article. Specifically, an aromatic vinyl monomer, an acrylic monomer, a cycloolefin monomer, a urethane monomer, and a silane monomer are preferable, an aromatic vinyl monomer, an acrylic monomer, and a cycloolefin monomer are more preferable, and an acrylic monomer and a cycloolefin monomer are particularly preferable. preferable. These may be used alone or in combination of two or more.

  Specific examples of the aromatic vinyl monomer include monofunctional aromatics such as styrene, α-methylstyrene, vinyltoluene, vinylethylbenzene, vinylxylene, pt-butylstyrene, α-methyl-p-methylstyrene, and vinylnaphthalene. Examples thereof include polyfunctional aromatic vinyl monomers such as vinyl monomers, divinylbenzene, divinylbiphenyl, and divinylnaphthalene. These may be used alone or in combination of two or more.

  In the present invention, the acrylic monomer represents acrylic acid, methacrylic acid, acrylic acid or methacrylic acid ester. The acrylic acid or methacrylic acid ester is preferably an alkyl ester, and the alkyl group of the ester group preferably has 4 to 18 carbon atoms, more preferably 4 to 12 carbon atoms, and particularly preferably 4 to 8 carbon atoms. Specific examples of acrylic acid or methacrylic acid ester include acrylic acid or methyl methacrylate, acrylic acid or ethyl methacrylate, acrylic acid or n-butyl methacrylate, acrylic acid or 2-ethylhexyl methacrylate, acrylic acid Or acrylic acid or methacrylic acid alkyl ester such as methacrylic acid n-octyl ester, acrylic acid or methacrylic acid isooctyl ester, acrylic acid or methacrylic acid n-decyl ester, acrylic acid or methacrylic acid n-dodecyl ester; acrylic acid or Acrylic acid or methacrylic acid hydroxyalkyl ester such as methacrylic acid hydroxyethyl ester, acrylic acid or methacrylic acid hydroxypropyl ester; Acrylic acid or methacrylic acid N, N-dimethylaminoalkyl ester, such as lauric acid or methacrylic acid N, N-dimethylaminomethyl ester, acrylic acid or methacrylic acid N, N-dimethylaminoethyl ester; acrylic acid or glycidyl methacrylate Epoxy group-containing acrylic acid or methacrylic acid ester such as ester; dimethacrylic acid ester such as ethylene dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate; trimethacrylic acid ester such as trimethylolpropane trimethacrylate; polyethylene glycol diacrylate , 1,3-butylene glycol diacrylate and other diacrylates; trimethylolpropane triacrylate and other triacrylates Such as acrylic acid esters. These may be used singly or in combination of two or more.

  The cycloolefin monomer is a compound having a ring structure formed of carbon atoms in the molecule and having a carbon-carbon double bond in the ring. A cycloolefin resin is obtained by polymerizing a cycloolefin monomer.

  Examples of the alicyclic structure constituting the cycloolefin monomer include structures such as a monocyclic ring, a polycyclic ring, a condensed polycyclic ring, a bridged ring, and a combination thereof. Although there is no special restriction | limiting in carbon number which comprises an alicyclic structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces.

  Examples of the cycloolefin monomer include a monocyclic cycloolefin monomer and a norbornene monomer, and a norbornene monomer is preferable. The norbornene-based monomer is a cycloolefin monomer having a norbornene ring structure in the molecule. These may be substituted with a hydrocarbon group such as an alkyl group, an alkenyl group, an alkylidene group or an aryl group, or a polar group. Further, the norbornene-based monomer may have a double bond in addition to the double bond of the norbornene ring. These may be used alone or in combination of two or more.

  Examples of the monocyclic cycloolefin monomer include cyclobutene, cyclopentene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, and the like.

Specific examples of the norbornene-based monomer include dicyclopentadiene such as dicyclopentadiene and methyldicyclopentadiene;
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-phenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4-carboxylic acid, tetracyclo [6.2.1.1 ^3,6 . ^{Tetracyclododecenes} such as 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic anhydride;
2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-phenyl-2-norbornene, 5-norbornen-2-yl acrylate, 5-norbornen-2-yl methacrylate, 5- Norbornenes such as norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic anhydride;
Oxanorbornenes such as 7-oxa-2-norbornene and 5-ethylidene-7-oxa-2-norbornene;
Tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8] tetradec -3,5,7,12- tetraene (1,4-methano -1,4,4a, also referred to as a 9a- tetrahydro -9H- fluorene), pentacyclo [6.5.1.1 ^{3 , 6} . 0 ^2,7 . 0 ^9,13] pentadeca-4,10-diene, pentacyclo ^{[9.2.1.0 2,10.} 0 ^3,8] pentadeca-5,12 cycloolefins four or more rings, such as dienes; and the like.

Of these cycloolefin monomers, a cycloolefin monomer having no polar group is preferable because a molded article having a low dielectric loss tangent can be obtained. The tetracyclo ^{[9.2.1.0 2,10.} [0 ^3,8 ] It is preferable to use those having a condensed ring having an aromatic ring such as tetradeca-3,5,7,12-tetraene because the viscosity of the polymerizable composition can be lowered.

  Urethane monomers are compounds in which an amino group and an alcohol group are dehydrated and condensed via a carbonyl. It corresponds to an ester of carbamic acid and is also called carbamate.

  Specific examples include triisocyanate and diisocyanate. Diisocyanates include aromatic diisocyanates such as diphenylmethane diisocyanate, tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, 2,6-naphthalene diisocyanate; alicyclic diisocyanates such as methylenebis (cyclohexyl isocyanate) isophorone diisocyanate, methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,6-diisocyanate, cyclohexane 1,4-diisocyanate, hexahydroxylylene diisocyanate, hexahydrotolylene diisocyanate, octahydro 1,5-naphthalene diisocyanate and the like can be used. These diisocyanates may be used alone or in combination of two or more.

  As the silane monomers, various silane compounds are used. Specifically, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltrimethoxysilane, cyclo Hexenylethyltrimethoxysilane, norbornyltrimethoxysilane, norbornyltriethoxysilane, bis (allylphenyldimethylsiloxy) tetramethyldisiloxane, bis (phenylethynyl) dimethylsilane, allyltrimethylsilane, t-butyldimethylsiloxystyrene , Divinyldimethoxysilane, divinyltetramethyldisilane, divinyltetramethyldisiloxane, dodecenyltriethoxysilane, methacryloxymethyltrimeth Sisilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltris (trimethylsiloxy) silane, methacryloxypropyltris (vinyldimethylsiloxy) silane, octavinyl-T8-silsesquioxane, tetravinylsilane, tetraallylsilane, tetravinyldimethoxydisiloxane , Trimethylsilylpropylene, trivinyltrimethylcyclotrisiloxane, vinylbenzyloxytrimethoxysilane, vinylphenyldimethylsilane, vinyltrimethoxysilane and the like.

  These silane monomers may be used alone or in combination of two or more.

  The polymerizable composition of the present invention contains the soft magnetic material and the bulk polymerizable monomer, but may contain a polymerization catalyst, a chain transfer agent, a crosslinking agent, a dispersing agent and the like in addition to these. Further, a polymer may be included for adjusting the viscosity of the polymerizable composition.

  The polymerization catalyst is appropriately selected according to the type of bulk polymerizable monomer to be used. Such polymerization catalysts include photopolymerization initiators, radical polymerization initiators, cationic polymerization initiators, polymerization initiators such as anionic polymerization initiators, transition metals such as platinum catalysts, metallocene catalysts, phenoxyimine catalysts, and metathesis polymerization catalysts. A catalyst is mentioned.

  For example, when the bulk polymerizable monomer is an aromatic vinyl monomer, examples of the polymerization catalyst include radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators, metallocene catalysts, phenoxyimine catalysts, etc. Agents, metallocene catalysts, phenoxyimine catalysts and the like are preferred.

  When the bulk polymerizable monomer is an acrylic monomer, a radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator are preferably used as the polymerization catalyst. Particularly preferred is a radical polymerization initiator.

  When the bulk polymerizable monomer is a cycloolefin monomer, a metathesis polymerization catalyst is preferably used as the polymerization catalyst.

  When the bulk polymerizable monomer is a silane monomer, a platinum catalyst and a radical polymerization initiator are preferably used as the polymerization catalyst.

  More preferable specific combinations of the polymerization catalyst and the bulk polymerizable monomer include 1) a radical polymerization initiator and an aromatic vinyl monomer, 2) a radical polymerization initiator and a methacrylic monomer, 3) a radical polymerization initiator and a silane monomer, 4) Metathesis polymerization catalyst and cycloolefin monomer.

  These are appropriately selected according to the reaction system, and the amount used is also appropriately set according to the catalyst type and the reaction system. Preferably, a radical polymerization initiator, a cationic polymerization initiator, an anionic polymerization initiator, a platinum catalyst, and a metathesis polymerization catalyst are used, and more preferably, a radical polymerization initiator and a metathesis polymerization catalyst are used.

  Examples of photopolymerization initiators include acyloin ethers (eg, benzoin ethyl ether, benzoin isopropyl ether, anisoin ethyl ether and anisoin isopropyl ether), substituted acyloin ethers (eg, α-hydroxymethylbenzoin ethyl ether), Michael ketone (4,4′-tetramethyldiaminobenzophenone), 2,2-dimethoxy-2-phenylacetophenone (for example, KB-1 manufactured by Sartomer or Irgacure 651 manufactured by Ciba-Geigy) and the like are included.

  Known radical initiators can be used. For example, persulfates such as potassium persulfate and ammonium persulfate; hydrogen peroxide; organic peroxides such as lauroyl peroxide, benzoyl peroxide, di-2-ethylhexyl peroxydicarbonate, t-butylperoxypivalate, cumene hydroperoxide These can be used alone or in combination or as a redox system in combination with a reducing agent such as sodium acid sulfite, sodium thiosulfate or ascorbic acid. 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), Azo compounds such as dimethyl 2,2′-azobisisobutyrate, 4,4′-azobis (4-cyanopentanoic acid); 2,2′-azobis (2-aminodipropane) dihydrochloride, 2, Amidine compounds such as 2'-azobis (N, N'-dimethyleneisobutylamidine) and 2,2'-azobis (N, N'-dimethyleneisobutylamidine) dihydrochloride can also be used.

  Further, examples of the cationic polymerization initiator include alkylaluminum, and examples of the anionic polymerization initiator include butyllithium.

  Various known catalysts such as a non-metallocene catalyst such as a platinum catalyst, a metallocene catalyst, and a phenoxyimine catalyst can be used without particular limitation.

  The metathesis polymerization catalyst is not particularly limited as long as it can metathesis ring-opening polymerization of the cycloolefin monomer. Examples of the metathesis polymerization catalyst include a complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds with a transition metal atom as a central atom. The transition metal atom is a metal after the fifth period of the long-period periodic table, and includes Group 5, Group 6 and Group 8 atoms. The atoms in each group are not particularly limited. For example, the group 5 atom includes tantalum, the group 6 atom includes molybdenum and tungsten, and the group 8 atom includes ruthenium and osmium.

  Among these, a complex of ruthenium or osmium belonging to Group 8 of the long periodic table is preferable, and a ruthenium carbene complex is particularly preferable for the following reason. Since the ruthenium carbene complex is excellent in catalytic activity, the ring-opening polymerization conversion rate of the polymerizable composition can be increased and the productivity of the molded article of the present invention is excellent. Moreover, there is little odor (it originates in an unreacted cycloolefin monomer) in the molded object obtained. Further, the ruthenium carbene complex has a characteristic that it is relatively stable against oxygen and moisture in the air and hardly deactivates.

  The ruthenium carbene complex can be produced, for example, by a method described in Organic Letters, Vol. 1, page 953, 1999, Tetrahedron Letters, Vol. 40, page 2247, 1999, and the like.

Examples of ruthenium carbene complexes include benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesitylimidazolidine-2-ylidene) (3- Methyl-2-butene-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octahydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene) (tricyclohexyl) Phosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazol-5-ylidene) ruthenium dichloride, (1 , 3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesitylimidazolidine-2-ylidene) pyridine ruthenium dichloride A ruthenium carbene complex compound in which an atom-containing carbene compound and a neutral electron donating compound are bonded;
Carbene compounds containing two heteroatoms as ligands such as benzylidenebis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride, benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride Ruthenium carbene complex compound to which is bonded;
(1,3-Dimesityrylimidazolidin-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butylvinylidene) (1,3-diisopropyl-4-imidazoline-2-ylidene) (tri Cyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylideneruthenium dichloride, and the like.

  Among these ruthenium carbene complexes, a ruthenium carbene complex compound having, as a ligand, substituted imidazoline-2-ylidene substituted at the 4-position and 5-position with halogen atoms exemplified in JP-A-2005-104922 is preferable.

  These may be used alone or in combination of two or more. The amount of the metathesis polymerization catalyst is usually 1: 2,000 to 1: 2,000,000, preferably 1: 5,000 to 1 in terms of a molar ratio of (transition metal atom in the metathesis polymerization catalyst: cycloolefin monomer). : 1,000,000, more preferably in the range of 1: 10,000 to 1: 500,000.

  The metathesis polymerization catalyst can be used in combination with an activator. The activator is added for the purpose of controlling the polymerization activity or improving the polymerization conversion rate. Examples of the activator include aluminum, scandium, tin alkylates, halides, alkoxylates, and aryloxylates.

  Specifically, trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkylaluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium, tetraalkoxy Tin, tetraalkoxyzirconium, etc. are mentioned.

  When the activator is used, the amount used is usually a molar ratio of (metal atom in the metathesis polymerization catalyst: activator) of 1: 0.05 to 1: 100, preferably 1: 0.2 to 1: 20, more preferably in the range of 1: 0.5 to 1:10.

  Moreover, when using a complex of transition metal atoms of Group 5 and Group 6 as the metathesis polymerization catalyst, it is preferable that both the metathesis polymerization catalyst and the activator are dissolved in a cycloolefin monomer. If it does not impair the effect, it can be used by being suspended or dissolved in a small amount of solvent.

  A chain transfer agent may be blended in the polymerizable composition of the present invention. In particular, when a cycloolefin monomer is used, by adding a chain transfer agent, it is possible to prevent the reaction due to heat generation during the polymerization from proceeding and to adjust the molecular weight of the cycloolefin resin to be produced.

  The chain transfer agent is appropriately selected according to the type of bulk polymerizable monomer, but in the case of metathesis polymerization using a cycloolefin monomer, a compound having at least one vinyl group can be usually used.

As the chain transfer agent, those having a group that contributes to crosslinking described later in addition to the vinyl group are preferable. The group that contributes to the crosslinking is specifically a group having a carbon-carbon double bond, and examples thereof include a vinyl group, an acryloyl group, and a methacryloyl group. These groups are preferably at the end of the molecular chain. In particular, a compound having a structure represented by the formula (C): CH ₂ ═CH—QY is preferable. In the formula, Q represents a divalent hydrocarbon group, and Y represents a vinyl group, an acryloyl group, or a methacryloyl group. Examples of the divalent hydrocarbon group represented by Q include an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, and a group formed by bonding them. Among these, a phenylene group and an alkylene group having 4 to 12 carbon atoms are preferable. By using the chain transfer agent having this structure, it is possible to obtain a crosslinked body or crosslinked resin composite having higher strength.

  Preferred examples of such chain transfer agents include compounds in which Y is a methacryloyl group, such as allyl methacrylate, 3-buten-1-yl methacrylate, hexenyl methacrylate, undecenyl methacrylate, decenyl methacrylate; A compound in which Y is an acryloyl group such as 3-buten-1-yl acrylate; a compound in which Y is a vinyl group such as divinylbenzene; Of these, undecenyl methacrylate, hexenyl methacrylate and divinylbenzene are particularly preferred.

  In addition to the above, compounds that can be used as chain transfer agents include aliphatic olefins such as 1-hexene and 2-hexene; olefins having an aromatic group such as styrene; alicyclic hydrocarbons such as vinylcyclohexane Olefins having a group; vinyl ethers such as ethyl vinyl ether; vinyl ketones such as methyl vinyl ketone, 1,5-hexadien-3-one and 2-methyl-1,5-hexadien-3-one; styryl acrylate, ethylene Acrylic esters such as glycol diacrylate; silanes such as allyltrivinylsilane, allylmethyldivinylsilane, allyldimethylvinylsilane; glycidyl acrylate, allyl glycidyl ether; allylamine, 2- (diethylamino) ethanol vinyl ether, 2- Diethylamino) ethyl acrylate, 4-vinyl aniline; and the like.

  These chain transfer agents may be used singly or in combination of two or more. When a chain transfer agent is used, the amount used is usually 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts per 100 parts by weight of the bulk polymerizable monomer. Parts by weight. When the amount of the chain transfer agent used is within this range, the cross-linking reaction during ring-opening polymerization is sufficiently suppressed, so that a molded article having excellent fluidity can be obtained.

  The polymerizable composition of the present invention preferably contains a crosslinking agent. The crosslinking agent is appropriately selected according to the type of the bulk polymerizable monomer. When the polymerizable composition contains a crosslinking agent, the obtained molded product is a cross-linkable molded product. Crosslinking of the crosslinkable molded body proceeds by heating. Particularly in the case of metathesis polymerization using a cycloolefin monomer, the crosslinkable molded product after polymerizing a polymerizable composition containing a chain transfer agent has a temperature higher than the maximum temperature (peak temperature) when ring-opening polymerization proceeds. By heating to, the crosslinking reaction proceeds, and a molded body with a crosslinked body having excellent physical properties can be obtained. For this reason, when the crosslinkable molded body is superposed on another base material such as a metal foil and then heated, the degree of adhesion at the interface between the cross-linked body and the other base material is significantly improved.

  When a cycloolefin monomer is used, it is preferable to use a crosslinking agent that can form a crosslinked structure by a crosslinking reaction with a functional group of the resulting cycloolefin resin. Here, the functional group is an unsaturated bond such as a double bond in the main chain or side chain of the resin; a functional group in the side chain of the resin when a cycloolefin monomer having a functional group is polymerized; derived from a chain transfer agent Although there is a functional group at the end of the resin, it is not particularly limited.

  Examples of the functional group of the cycloolefin resin include a carbon-carbon double bond, a carboxylic acid group, an acid anhydride group, a hydroxyl group, an amino group, an active halogen atom, and an epoxy group.

  The crosslinking agent is used for crosslinking a cycloolefin resin polymerized by a metathesis reaction. Although the concept included in the polymerization catalyst described above partially overlaps, the usage conditions, particularly in the temperature range, are different and are used in different processes.

  Examples of such a crosslinking agent include a radical generator, an epoxy compound, an isocyanate group-containing compound, a carboxyl group-containing compound, an acid anhydride group-containing compound, an amino group-containing compound, and a Lewis acid. These crosslinking agents can be used alone or in combination of two or more. Among these, a radical generator, an epoxy compound, and an isocyanate group-containing compound are preferable, a radical generator and an epoxy compound are more preferable, and a radical generator is particularly preferable.

  The radical generator has a function of generating radicals by heating and thereby crosslinking the cycloolefin resin.

  The site where the radical generator undergoes a crosslinking reaction is mainly the carbon-carbon double bond of the cycloolefin resin, but it may also be crosslinked at the saturated bond portion.

  Examples of the radical generator include organic peroxides, diazo compounds, and nonpolar radical generators. Examples of the organic peroxide include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide; dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, 2, 5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, 1,3-di (t-butylperoxyisopropyl) ) Dialkyl peroxides such as benzene; Diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; Peroxy such as n-butyl 4,4-di- (t-butylperoxy) valerate and 1,1-di-t-butylperoxycyclohexane Ketals; t-butylperoxy And peroxyesters such as acetate and t-butylperoxybenzoate; peroxycarbonates such as t-butylperoxyisopropyl carbonate and di (isopropylperoxy) dicarbonate; alkylsilyl peroxides such as t-butyltrimethylsilyl peroxide; and the like. Of these, dialkyl peroxides are particularly preferable in that there are few obstacles to the metathesis polymerization reaction in bulk polymerization.

  Examples of the diazo compound include 4,4′-bisazidobenzal (4-methyl) cyclohexanone, 4,4′-diazidochalcone, 2,6-bis (4′-azidobenzal) cyclohexanone, and 2,6-bis. (4′-azidobenzal) -4-methylcyclohexanone, 4,4′-diazidodiphenylsulfone, 4,4′-diazidodiphenylmethane, 2,2′-diazidostilbene and the like.

  Non-polar radical generators include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diphenylbutane, 1,4-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1, 1,2,2-tetraphenylethane, 2,2,3,3-tetraphenylbutane, 3,3,4,4-tetraphenylhexane, 1,1,2-triphenylpropane, 1,1,2- Triphenylethane, triphenylmethane, 1,1,1-triphenylethane, 1,1,1-triphenylpropane, 1,1,1-triphenylbutane, 1,1,1-triphenylpentane, 1, Examples include 1,1-triphenyl-2-propene, 1,1,1-triphenyl-4-pentene, 1,1,1-triphenyl-2-phenylethane, and the like.

  An epoxy crosslinking agent advances a crosslinking reaction using a polar group such as a carboxyl group as a crosslinking point. Epoxy crosslinking agents include bisphenol A bis (ethylene glycol glycidyl ether) ether, bisphenol A bis (diethylene glycol glycidyl ether) ether, bisphenol A bis (triethylene glycol glycidyl ether) ether, bisphenol A bis (propylene glycol glycidyl ether) ether, etc. Glycidyl ether type epoxy compounds such as bisphenol A glycidyl ether type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, cresol type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, hydrogenated bisphenol Glycidyl ether type epoxy compounds such as A type epoxy compounds; Cyclic epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compound, a polyvalent epoxy compound such as isocyanurate type epoxy compound; a compound having two or more epoxy groups in the molecule, and the like.

  Examples of the isocyanate group-containing compound include compounds having two or more isocyanate groups in the molecule, such as paraphenylene diisocyanate, 2,6-toluene diisocyanate, and hexamethylene diisocyanate.

  Examples of the carboxyl group-containing compound include compounds having two or more carboxyl groups in the molecule such as fumaric acid, phthalic acid, maleic acid, trimellitic acid, hymic acid, terephthalic acid, isophthalic acid, adipic acid, and sebacic acid. Can be mentioned.

  Examples of the anhydride group-containing compound include maleic anhydride, phthalic anhydride, pyroperitic acid, benzophenone tetracarboxylic acid anhydride, nadic acid anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, maleic anhydride modified polypropylene, etc. Is mentioned.

  Examples of the amino group-containing compound include aliphatic diamines such as trimethylhexamethylenediamine, ethylenediamine, and 1,4-diaminobutane; aliphatic polyamines such as triethylenetetramine, pentaethylenehexamine, and aminoethylethanolamine; phenylenediamine , 4,4′-methylenedianiline, toluenediamine, aromatic amines such as diaminoditolylsulfone; and the like, and compounds having two or more amino groups in the molecule.

  Examples of the Lewis acid include silicon tetrachloride, hydrochloric acid, sulfuric acid, ferric chloride, aluminum chloride, stannic chloride, titanium tetrachloride, and the like.

  You may use these individually by 1 type or in combination of 2 or more types. When the crosslinking agent is used, the amount is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the cycloolefin monomer. When there are too few crosslinking agents, there exists a possibility that bridge | crosslinking may become inadequate and a crosslinked resin molding with a high crosslinking density may not be obtained. On the contrary, if the amount of the crosslinking agent is too large, the productivity is inferior, and the crosslinking effect is saturated and only an insufficient effect may be obtained.

  Furthermore, the polymerizable composition of the present invention may contain a dispersant in order to improve the dispersibility of the soft magnetic material. Examples of the dispersant include a cationic dispersant, an anionic dispersant, a betaine dispersant, a nonionic dispersant, a titanate dispersant, an aluminate dispersant, and a zirconate dispersant. These may be used alone or in combination of two or more.

  Among these, nonionic dispersants are particularly preferably used. A nonionic dispersant is a compound containing at least one hydrophobic group and one hydrophilic group in the molecule. Hydrophobic groups are hydrocarbon groups that may contain fluorine and silicon, and long chain polypropylene oxide groups. The hydrophilic group has a polar group such as a hydroxyl group, an ester group, a phosphate ester group, an ether group, an ether ester group, an amide group, an amino group, an amine oxide group, an imide group, and a sulfoxide group, and does not become an ion in water. It is. Among these, those having an ester bond or an ether bond are preferable.

  In addition, these structures are usually random and block linear structures of hydrophilic and hydrophobic groups, branched structures having side chains in the main chain structure, star structures such as branch polymers and dendrimers, and cyclic structures. A block type straight chain structure and a branched structure are preferred. When the nonionic dispersant has the above structure, it is adsorbed on the surface of the composite metal magnetic body with a bulky structure, thereby improving the dispersion effect. In addition, the properties of these nonionic dispersants are not particularly limited, such as powder, paste, and oil.

  Nonionic dispersants are further divided into 1) nonionic dispersants having polyethylene glycol chains or polypropylene glycol chains, and 2) polyhydric alcohol type nonionic dispersants.

  1) Nonionic dispersants having a polyethylene glycol chain include alkyl and aryl addition polyethylene glycol, higher alcohol addition polyethylene glycol, alkylphenol addition polyethylene glycol, fatty acid addition polyethylene glycol, polyhydric alcohol fatty acid ester addition polyethylene glycol, higher alkyl amine. Examples include addition polyethylene glycol, fatty acid amide addition polyethylene glycol, oil and fat addition polyethylene glycol, fluorohydrocarbon addition polyethylene glycol, and a copolymer of polyethylene glycol and silicone. Examples of the nonionic dispersant having a polypropylene glycol chain include those having a structure in which part or all of the polyethylene glycol chain is substituted with the polypropylene glycol chain in the nonionic dispersant having the polyethylene glycol chain. . Examples of the nonionic dispersant having a polyethylene glycol chain include polyoxyethylene-polyoxypropylene block polymers having a long polyoxypropylene chain as an oleophilic group, and alkylthiopolyoxyethylene ethers.

In particular,
Alkyl polyoxyethylene ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyethylene alkylene allyl ether Kind;
Alkylaryl polyoxyethylene ethers such as polyoxyethylene distyrenated phenyl ether;
Glycerin ester polyoxyethylene ethers such as polyoxyethylene monoglycerin ester, polyoxyethylene diglycerin ester, polyoxyethylene triglycerin ester, polyoxyethylene tetraglycerin ester, polyoxyethylene pentaglycerin ester, polyoxyethylene hexaglycerin ester ;
Polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monopalmylate, polyoxyethylene sorbitan dilaurate, polyoxyethylene sorbitan dioleate, polyoxyethylene sorbitan Sorbitan ester polyoxyethylene ethers such as distearate, polyoxyethylene sorbitan dipalmylate, polyoxyethylene sorbitan trilaurate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan tripalmylate Kind;
Examples include polyoxyethylene fatty acid esters such as polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, and polyoxyethylene rosin ester.

  2) Polyhydric alcohol type nonionic dispersants include glycerin fatty acid esters, pentaerythritol fatty acid esters, sorbitol and sorbitan fatty acid esters, sucrose fatty acid esters, polyhydric alcohol alkyl ethers, fatty amides of alkalolamines, condensed fatty acids Examples thereof include esters, fluorohydrocarbon adducts, and copolymers with silicone.

Specifically,
Glycerin esters such as stearic acid monoglyceride, oleic acid monoglyceride, palmitic acid glyceride, stearic acid diglyceride, oleic acid diglyceride, palmitic acid diglyceride;
Sorbitan esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate ;
Monoglyceryl monostearate, diglyceryl monostearate, diglyceryl monostearate, hexaglyceryl monostearate, hexaglyceryl monooleate, hexaglyceryl monomyristate, hexaglyceryl monolaurate, hexaglyceryl mono-dicaprylate, Hexaglycerin hexastearate, hexaglyceryl octastearate, decaglyceryl monostearate, decaglyceryl distearate, decaglycerin pentastearate, decaglycerin decastearate, decaglycerin monooleate, decaglycerin pentaoleate, decaoleic acid deca Glycerin, monomyristic acid decaglycerin, monolauric acid decaglycerin, monolauric acid triglycerin, monomyristic acid Glycerin, monooleic acid triglycerin, monostearic acid triglycerin, monolauric acid pentaglycerin, monomyristic acid pentaglycerin, trimyristic acid pentaglycerin, monooleic acid pentaglycerin, trioleic acid pentaglycerin, monostearic acid pentaglycerin, tris Polyglycerol fatty acid esters such as pentaglycerol stearate and pentaglycerol hexastearate;
Polyglycerol condensed ricinoleic acid esters such as condensed ricinoleic acid tetraglycerin, condensed ricinoleic acid hexaglycerin, condensed ricinoleic acid pentaglycerin;
Self-condensed ester of ricinoleic acid obtained by condensing 2-6 molecules of ricinoleic acid, self-condensed ester of 12-hydroxystearic acid obtained by condensing 2-6 molecules of 12-hydroxystearic acid, and condensation obtained by condensing stearic acid and the like Examples include fatty acid esters.

  Among these, sorbitan esters, polyglycerin fatty acid esters, and condensed fatty acid esters are particularly preferable.

  By using these nonionic dispersants, a larger amount of soft magnetic material can be added to the polymerizable composition, and there are few unreacted monomers remaining in the molded product after polymerization, and the moldability is good. A polymerizable composition is obtained.

  Further, as the nonionic dispersant, those which are particularly soluble in the bulk polymerizable monomer are preferable. The working efficiency is improved by dissolving the nonionic dispersant in the monomer in advance. For example, the solubility in cycloolefin monomers is indicated by the HLB value of the Griffin method. The HLB value is a value representing the degree of affinity for water and oil, and is derived from the following equation in the Griffin method.

  HLB value (Griffin method) = 20 × (total formula weight of hydrophilic part / molecular weight)

  That is, a nonionic dispersant having an HLB value calculated by the Griffin method of 10 or less, preferably 7 or less is preferably selected. By using such a nonionic dispersant, dispersibility and solubility in a cycloolefin monomer are improved.

  The molecular weight of these nonionic dispersants is not particularly limited, but the weight average molecular weight (Mw) in terms of polystyrene is usually 100,000 or less, more preferably 50,000 or less, still more preferably 100 to 10,000, more preferably 200 to 5,000. Within this range, it is easily dissolved in the cycloolefin monomer and excellent in workability.

  These nonionic dispersants may be used alone or in combination of two or more.

  When a nonionic dispersant is used, the amount used is usually 0.1 to 50 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.1 to 100 parts by weight of the bulk polymerizable monomer. -10 parts by weight, particularly preferably 0.1-5 parts by weight. If it is less than this range, the dispersibility of the soft magnetic material may be poor and it may be difficult to mold, and if it exceeds this range, the physical properties of the molded product may be impaired.

  Furthermore, when using a metathesis polymerization catalyst, a metathesis polymerization retarder may be blended. The metathesis polymerization retarder is blended for the purpose of controlling the polymerization activity of the metathesis polymerization catalyst, extending the gelation time (pot life) of the polymerizable composition, and improving processability. Examples of such metathesis polymerization retarders include chain diene compounds such as 1,5-hexadiene and 2,5-dimethyl-1,5-hexadiene; (trans) -1,3,5-hexatriene, ( Cis) -1,3,5-hexatriene and other chain triene compounds; triphenylphosphine, tributylphosphine, trimethylphosphine, triethylphosphine and other phosphines; aniline, pyridine and other Lewis bases; and the like. Among these, phosphines are preferable because the pot life of the polymerizable composition of the present invention can be efficiently controlled and the polymerization reaction is hardly inhibited.

  Furthermore, a cycloolefin monomer having a diene structure or a triene structure serves as a polymerization reaction retarder as well as a cycloolefin monomer. Examples of such cycloolefin monomers include 1,5-cyclooctadiene and vinyl norbornene.

  These metathesis polymerization retarders may be used alone or in a combination of two or more. When a metathesis polymerization retarder is used, the amount is arbitrarily set depending on the compound used and the purpose, but it is usually 1: 0 in molar ratio of (transition metal atom in the metathesis polymerization catalyst: polymerization retarder). 0.05 to 1: 100, preferably 1: 0.2 to 1:20, more preferably 1: 0.5 to 1:10.

  When a radical generator is used as the crosslinking agent, a radical crosslinking retarder can be used. The radical crosslinking retarder is used for the purpose of suppressing the generation of radicals in the early stage of metathesis polymerization by decomposition of the radical generator as a crosslinking agent by heat of polymerization by metathesis polymerization and heat applied from the outside. Improves the fluidity and storage stability of the compact.

  Examples of the radical crosslinking retarder include hydroxyanisols, dialkoxyphenols, catechols, hydroquinones, benzoquinones, and hydroxyanisols such as 3,5-di-t-butyl-4-hydroxyanisole. preferable.

  These may be used alone or in combination of two or more. The content of the radical crosslinking retarder is usually 1: 0.001 to 1: 1, preferably 1: 0.01 to 1: 1 in terms of a molar ratio with (radical generator: radical crosslinking retarder).

  A polymer formed from a monomer or a derivative thereof contained in the polymerizable composition may be added to the polymerizable composition for further initial viscosity adjustment. For example, when an acrylic monomer is used as the bulk polymerizable monomer, the viscosity adjusting polymer is preferably a polymer obtained by polymerizing an acrylic monomer.

  The polymerizable composition may further contain a crosslinking aid, a solvent, a modifier, an antioxidant, a flame retardant, a filler, a colorant, a light stabilizer, and the like. These can be used by dissolving or dispersing in a bulk polymerizable monomer liquid or catalyst liquid described later.

  The crosslinking aid is used for the purpose of improving the crosslinking reaction rate when the resin molded body is crosslinked. The crosslinking aid can be suitably used when radical polymerization is selected as the polymerization method for the bulk polymerizable monomer or in radical crosslinking of the molded article after metathesis polymerization. Examples of crosslinking aids include dioxime compounds such as p-quinonedioxime; methacrylate compounds such as lauryl methacrylate and trimethylolpropane trimethacrylate; fumaric acid compounds such as diallyl fumarate: phthalic acid compounds such as diallyl phthalate, triallylcia And cyanuric acid compounds such as nurate; imide compounds such as maleimide; and the like. These may be used singly or in combination of two or more. The amount of the crosslinking aid is not particularly limited, but is usually 0 to 100 parts by weight, preferably 0 to 50 parts by weight with respect to 100 parts by weight of the bulk polymerizable monomer.

  A small amount of the solvent is used to dissolve the polymerization catalyst and other components as required. Usually, it is 10 parts by weight or less, preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and further preferably 2 parts by weight or less with respect to 100 parts by weight of the bulk polymerizable monomer. The solvent must be inert to the catalyst. Examples of such solvents include chain aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane; cycloaliphatic groups such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, hexahydroindenecyclohexane, and cyclooctane. Hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; oxygen-containing hydrocarbons such as diethyl ether and tetrahydrofuran;

  In the metathesis polymerization, aromatic hydrocarbons, chain aliphatic hydrocarbons, and alicyclic hydrocarbons, which are excellent in solubility of the metathesis polymerization catalyst and are widely used industrially, are preferable. In addition, a liquid antioxidant, a liquid plasticizer, or a liquid modifier may be used as a solvent as long as it does not decrease the activity of the metathesis polymerization catalyst. These may be used singly or in combination of two or more.

  Examples of the antioxidant include various hindered phenol-based, phosphorus-based and amine-based antioxidants for plastics and rubbers. These antioxidants may be used alone or in combination of two or more.

  Examples of the flame retardant include phosphorus flame retardants, nitrogen flame retardants, halogen flame retardants, metal hydroxide flame retardants such as aluminum hydroxide, and antimony compounds such as antimony trioxide. Although the flame retardant may be used alone, it is preferable to use a combination of two or more.

  Examples of the filler include glass powder, ceramic powder, silica, and metal powder. These fillers may be used alone or in combination of two or more. As the filler, one that has been surface-treated with a silane coupling agent or the like can also be used. The filler in the present invention does not include the concept of soft magnetic material.

  As the colorant, dyes, pigments and the like are used. There are various kinds of dyes, and known ones may be appropriately selected and used.

  The polymerizable composition of the present invention contains a soft magnetic material and a bulk polymerizable monomer, and optionally contains optional components such as the aforementioned catalyst.

  The polymerizable composition is not particularly limited by the method for preparing the polymerizable composition. That is, the polymerizable composition may be obtained by simply mixing the components. The polymerizable composition is preferably prepared by preparing a liquid in which a polymerization catalyst is dissolved or dispersed in an appropriate solvent (hereinafter sometimes referred to as “catalyst liquid”), and separately transferring a bulk transfer monomer, a chain transfer agent, and a crosslinking agent. It can be prepared by preparing a liquid (hereinafter sometimes referred to as “monomer liquid”) in which an additive such as an agent is blended as necessary, adding the catalyst liquid to the monomer liquid, and stirring. The catalyst solution is preferably added immediately before the polymerization described below. The soft magnetic material and the dispersant are preferably used by adding to the monomer solution.

  In the present invention, the temperature of the monomer solution when adding the metathesis polymerization catalyst solution is usually -10 ° C to 25 ° C, preferably -5 ° C to 20 ° C, more preferably -5 to 15 ° C, and particularly preferably -5. It is preferable to set it as 10 to 10 degreeC. If it is higher than this temperature, the polymerization proceeds abruptly at the moment when the polymerization catalyst is added, and the viscosity of the polymerizable composition may increase and the molding may become impossible.

  Further, the temperature of the polymerizable composition from the addition of the metathesis polymerization catalyst solution to the start of the polymerization is preferably -10 ° C to 25 ° C, more preferably -5 ° C to 20 ° C, and particularly preferably -5. It is preferable to set it as -10 degreeC. If it is higher than this temperature, the polymerization proceeds rapidly, and the viscosity of the polymerizable composition may increase, which may make molding impossible. If it is lower than this temperature, the monomer liquid may freeze or the economy may deteriorate. The addition of the catalyst solution is preferably performed in an inert gas atmosphere such as nitrogen.

  The method for cooling the monomer solution before the addition of the catalyst solution and the polymerizable composition after the addition of the catalyst solution is not particularly limited and is performed by a commonly used method. For example, it can cool with cold water, an ice bath, an ice salt bath, a methanol-dry ice bath, etc.

  When preparing the monomer liquid, the order in which the soft magnetic material and other optional components are added to the bulk polymerizable monomer is not particularly limited. Moreover, since the dispersibility of the soft magnetic material may be improved by adding the dispersant before adding the soft magnetic material, it is particularly preferable to add the soft magnetic material after the addition of the dispersant. Further, the polymerization catalyst is preferably added last because of excellent stability of the polymerizable composition.

  The mixing apparatus used for the preparation of the monomer liquid is not particularly limited, and may be appropriately selected depending on the viscosity of the monomer liquid. Examples thereof include wheel type, ball type, blade type, roll type devices such as a mix muller, ball mill, kneader, Henschel mixer, roll mill, Banbury mixer, ribbon mixer, homogenizer, twin screw extruder, rakai machine and the like.

  The molded product of the present invention is obtained by bulk polymerization of the polymerizable composition. The conditions for bulk polymerization are appropriately selected according to the properties of the catalyst used and the bulk polymerizable monomer.

  There is no limitation on the method for obtaining a molded product by bulk polymerization of the polymerizable composition of the present invention. For example, (a) a method in which a polymerizable composition is applied on a support and then bulk polymerization is performed, and (b) polymerization. Examples thereof include a method in which a fibrous reinforcing material support is impregnated with a fibrous reinforcing material, followed by bulk ring-opening polymerization, and (c) a method in which the polymerizable composition is injected into a space of a mold and then bulk polymerization.

  Since the polymerizable composition of the present invention has a low viscosity, the application in the method (a) can be carried out smoothly, and in the method (b), the fibrous reinforcing material can be impregnated quickly and uniformly. The injection in the method (c) can be performed quickly without causing foaming even in a space having a complicated shape, and a dense molded body can be obtained.

  According to the method (a), a resin molded body such as a film or plate can be obtained. The thickness of the molded body is usually 15 mm or less, preferably 10 mm or less, more preferably 5 mm or less.

  Examples of the support include films and plates made of a resin such as polyethylene terephthalate, polypropylene, polyethylene, polycarbonate, polyethylene naphthalate, polyarylate, and nylon; iron, stainless steel, copper, aluminum, nickel, chromium, gold, silver, and the like. Examples include films and plates made of metal materials. Especially, use of metal foil or a resin film is preferable. The thickness of these metal foils or resin films is usually 1 to 150 μm, preferably 2 to 100 μm, more preferably 3 to 75 μm from the viewpoint of workability and the like.

  Examples of the method for applying the polymerizable composition of the present invention on the support include known coating methods such as spray coating, dip coating, roll coating, curtain coating, die coating, and slit coating.

  The polymerizable composition coated on the support is dried as necessary, and then bulk polymerized. The polymerization may be thermal polymerization or photopolymerization, but thermal polymerization is preferably employed from the viewpoint of easy operation and uniform reaction. As a heating method at the time of thermal polymerization, a method in which a polymerizable composition coated on a support is placed on a heating plate and heated, a method in which heating is performed while using a press machine (hot pressing), and a heated roller And a method using a heating furnace.

  Examples of the resin molded body obtained by the method (b) include a prepreg formed by filling a polymer with a gap between fibrous reinforcing materials. As the fibrous reinforcing material, inorganic and / or organic fibers can be used, such as glass fibers, metal fibers, ceramic fibers, carbon fibers, aramid fibers, polyethylene terephthalate fibers, vinylon fibers, polyester fibers, amide fibers, Examples include known liquid crystal fibers such as polyarylate. These can be used alone or in combination of two or more. Examples of the shape of the fibrous reinforcing material include mat, cloth, and non-woven fabric.

  In order to impregnate the fibrous reinforcing material with the polymerizable composition of the present invention, for example, a predetermined amount of the polymerizable composition is poured onto a cloth reinforcing material cloth, mat, etc. It can be performed by stacking a protective film on top and pressing with a roller or the like from above. A prepreg impregnated with a resin can be obtained by impregnating the fibrous reinforcing material with the polymerizable composition and then heating to a predetermined temperature to polymerize the impregnated material. The polymerization method may be thermal polymerization or photopolymerization, but is preferably thermal polymerization. As a heating method, for example, a method in which an impregnated material is placed on a support and heated as in the method (a) above, a fibrous reinforcing material is set in a mold in advance, and a polymerizable composition is used. After impregnation, a method of heating as in the method (c) described later is used.

  The shape of the resin molding obtained by the method (c) can be arbitrarily set by a molding die. For example, a film shape, a column shape, other arbitrary three-dimensional shapes, etc. are mentioned. Therefore, according to this method, various structures can be easily produced.

  The shape, material, size, etc. of the mold are not particularly limited. As such a mold, a conventionally known mold, for example, a split mold structure, that is, a mold having a core mold and a cavity mold; a mold having a spacer between two plates; and the like can be used.

  The pressure (injection pressure) at which the polymerizable composition of the present invention is injected into the space (cavity) of the mold is usually 0.01 to 10 MPa, preferably 0.02 to 5 MPa. If the injection pressure is too low, the filling may be insufficient and the transfer surface formed on the inner surface of the cavity may not be transferred well.If the injection pressure is too high, the mold may have high rigidity. Needed and not economical. The mold clamping pressure is usually in the range of 0.01 to 10 MPa.

  The polymerizable composition filled in the space can be polymerized by heating. In this method, since a mold is used, thermal polymerization is performed. Examples of the method for heating the polymerizable composition include a method using a heating means such as an electric heater and steam disposed in a mold, and a method for heating the mold in an electric furnace.

  In any of the above methods (a), (b) and (c), the heating temperature for thermally polymerizing the polymerizable composition is usually 30 to 250 ° C., preferably 50 to 200 ° C. The polymerization time may be appropriately selected, but is usually 1 second to 120 minutes, preferably 5 seconds to 30 minutes, more preferably 10 seconds to 20 minutes. In particular, in bulk polymerization using a cycloolefin monomer, which is a preferred polymerization because the reaction proceeds rapidly, it is usually 1 second to 30 minutes, preferably 10 seconds to 20 minutes.

  A polymerization reaction is started by heating the polymerizable composition to a predetermined temperature. In particular, in bulk polymerization using a cycloolefin monomer, when the polymerization reaction starts, the temperature of the polymerizable composition rapidly increases due to the heat of reaction and reaches the peak temperature in a short time (for example, about 10 seconds to 5 minutes). Further, the polymerization reaction proceeds, but the polymerization reaction gradually stops and the temperature decreases. It is preferable to control the peak temperature so as to be equal to or higher than the glass transition temperature of the polymer constituting the molded product obtained by this polymerization reaction, since the polymerization proceeds completely. The peak temperature can be controlled by the heating temperature. Moreover, in the case of the molded object obtained from the polymeric composition which mix | blended the chain transfer agent, the polymerization conversion rate is 80% or more normally, Preferably it is 90% or more, More preferably, it is 95% or more. The polymerization conversion rate can be obtained, for example, by dissolving the molded body in a solvent and quantitatively analyzing the unreacted monomer by gas chromatography in the obtained solution. The molded body in which the polymerization has progressed almost completely has few unreacted monomers and little odor generation.

  In bulk polymerization using a cycloolefin monomer, which is a particularly preferable polymerization that proceeds rapidly, and the polymerizable composition contains a crosslinking agent, if the peak temperature during the polymerization reaction becomes too high, the polymerization reaction In addition, there is a risk that the crosslinking reaction may proceed at once. Therefore, in order to allow only the polymerization reaction to proceed completely and to prevent the crosslinking reaction from proceeding, it is necessary to control the peak temperature of the polymerizable composition in the polymerization to preferably less than 200 ° C. However, from the viewpoint of productivity and the like, the polymerization reaction and the crosslinking reaction may proceed simultaneously.

  For example, in bulk polymerization using a cycloolefin monomer, when a polymerizable composition containing a radical generator is used, it is preferable that the peak temperature during the polymerization is not more than the 1 minute half-life temperature of the radical generator. Here, the 1-minute half-life temperature is a temperature at which half of the radical generator decomposes in 1 minute.

  The molded product of the present invention may be a crosslinked product. For example, in bulk polymerization using a cycloolefin monomer, a crosslinked product can be obtained by heating and crosslinking a crosslinkable molded product obtained using a polymerizable composition containing a crosslinking agent. The temperature at which the crosslinkable molded body is heated to be crosslinked is usually 170 to 250 ° C, preferably 180 to 220 ° C. This temperature is preferably higher than the peak temperature during the polymerization, and more preferably 20 ° C. or higher. The time for crosslinking by heating is not particularly limited, but is usually from 1 minute to 10 hours.

  The method for heating and crosslinking the crosslinkable molded product is not particularly limited. When the crosslinkable molded product is in the form of a film, a method of laminating a plurality of sheets as necessary and applying pressure simultaneously with heating by a hot press is preferable. The pressure at the time of hot pressing is usually 0.5 to 20 MPa, preferably 3 to 10 MPa.

  As described above, from the viewpoint of productivity and the like, the polymerization reaction and the crosslinking reaction may be simultaneously performed to obtain a crosslinked product directly from the polymerizable composition. The method for heating, polymerizing and crosslinking the polymerizable composition is not particularly limited. For example, a method of injecting a polymerizable composition into a mold and applying pressure simultaneously with heating by a hot press is preferable. The pressure at the time of hot pressing is usually 0.5 to 20 MPa, preferably 3 to 10 MPa.

  The laminate of the present invention has a constituent layer composed of the above-mentioned molded body, more specifically, has at least two or more layers, and at least one layer is formed of the above-mentioned molded body. A more specific example of such a laminate includes a laminate including a base material such as a copper foil and a constituent layer formed from the molded article of the present invention. Further, the laminate of the present invention may be a composite material in which a base material such as a copper foil and a resin layer containing a soft magnetic material are alternately laminated like a multilayer laminate substrate. Here, when a plurality of resin layers containing a soft magnetic material are included, the composition of each resin layer may be the same or different.

  Examples of the base material include copper foils, aluminum foils, nickel foils, chrome foils, gold foils, silver foils and other metal foils; printed wiring board manufacturing substrates; resins such as polytetrafluoroethylene (PTFE) films and conductive polymer films Film: Noise suppression sheet, radio wave absorber and the like. The surface of the base material may be treated with a silane coupling agent, a thiol coupling agent, a titanate coupling agent, various adhesives, or the like.

  There is no particular limitation on the method for obtaining the laminate, and when obtaining a laminate comprising the molded article of the present invention in the constituent layers, for example, the molded article obtained using the polymerizable composition of the present invention is used as the base material. The laminate may be obtained by superimposing them on each other, or the laminate may be obtained by superposing the compacts on each other. Furthermore, a polymerizable composition can be coated on a suitable substrate material or molded body, and the polymerizable composition can be polymerized to obtain a laminate.

  Moreover, when obtaining the laminated body containing the structure layer which consists of a molded object by a crosslinked body, for example, (1) The crosslinkable molded object obtained using the polymeric composition containing a crosslinking agent is used for base material. Superposed, then heated to crosslink, (2) Laminate polymerizable composition on substrate material, proceed with bulk polymerization and crosslinking reaction, (3) Obtained using polymerizable composition containing crosslinking agent Two or more of the obtained cross-linkable molded bodies are superposed and then heated to be cross-linked. (4) The surface of the cross-linked body is applied to at least one surface of an adhesive such as a resin and adhered to the base material. (5) A method in which the cross-linked body is bonded to another base material using a base material having adhesive ability such as a double-sided tape.

  In order to obtain a laminate by the above method (1), for example, a crosslinkable molded body and a metal foil as a base material are overlapped and heated by hot pressing or the like to be cross-linked to be strong with the metal foil. An adhesive metal foil-clad laminate can be obtained. When the copper foil is used as the metal foil, the peel strength of the metal foil of the obtained metal foil-clad laminate is a value measured based on JIS C6481, and is 0.5 kN / m or more, preferably 0.8 kN / m or more, more preferably 1.2 kN / m or more.

  In order to obtain a laminate by the method (2), the bulk polymerization temperature of the polymerizable composition is set high, and heating is performed at a temperature at which a crosslinking reaction occurs. However, as in the method (1), the peel strength at the interface is increased once the cross-linked molded article is passed through.

  Since the laminated body of this invention does not require the process of volatilizing a large amount of solvent like the conventional casting method, it has the advantage which can be manufactured very simply.

  There is no limitation on the heating method for producing the laminate of the present invention, but productivity is improved by a method in which a crosslinkable molded body and a base material such as a metal foil or a printed wiring board manufacturing substrate are overlaid and hot pressed. Improved and preferred. The conditions for hot pressing are the same as in the case of producing the crosslinked product.

  In the polymerizable composition of the present invention, a soft magnetic material is uniformly dispersed, and further, since it is not necessary to use a solvent in the composition, a complex three-dimensional shaped product can be formed at high speed by reaction injection molding or the like. And the solvent drying step is unnecessary. Therefore, according to the polymerizable composition of the present invention, a molded product containing a soft magnetic material can be obtained with high productivity. Moreover, in the obtained molded body and laminate, the stain resistance is excellent and high magnetic permeability is achieved.

  The molded body according to the present invention having such characteristics is a magnetic application product such as an inductance, a choke coil, a high frequency transformer, a low frequency transformer, a reactor, a pulse transformer, a step-up transformer, a noise filter, a transformer for transformation, a magnetic impedance element, Magnetostrictive vibrator, magnetic sensor, magnetic head, electromagnetic shield, shield connector, shield package, radio wave absorber, electromagnetic wave shield, noise suppression sheet, motor, generator core, antenna core, magnetic disk, magnetic application transport system, magnetism It is suitably used for solenoids, actuator cores, printed circuit boards, RFID antennas, and the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following, parts and% are based on weight unless otherwise specified. Evaluation of the aspect ratio of the soft magnetic material, the permeability of the molded product, the stain resistance, and the dispersibility were performed as follows.

<Aspect ratio of soft magnetic material>
The major axis length (X) and minor axis length (Y) of 100 arbitrary particles are measured in a photographic image obtained by observing soft magnetic particles with a scanning electron microscope (SEM), and the aspect ratio ( X / Y).

<Permeability>
The permeability refers to the real part of the complex permeability, and was measured at 100 MHz and 1 GHz by a one-turn coil method using a network analyzer (manufactured by Agilent).
The evaluation criteria are as follows.
For 100 MHz:
A: 10 or more B: 5 or more and less than 10 C: less than 5 1 GHz:
A: 6 or more B: 3 or more and less than 6 C: less than 3

<Contamination resistance>
A line was drawn on the surface of the resin of the obtained molded body with oil-based ink and lipstick and wiped with alcohol after 20 hours at 20 ° C. It was visually confirmed whether or not a trace remained after wiping.
The evaluation criteria are as follows.
A: No trace is left.
B: A trace remains.
C: A trace remains.

<Dispersibility>
By polishing the side surface of the obtained molded body, the cross section was smoothed, and the dispersibility was evaluated by the orientation of 100 arbitrary soft magnetic bodies with a scanning electron microscope (SEM). For the orientation, the ratio of the soft magnetic material in which the angle between the long axis of the blended soft magnetic material and the cross section of the molded product is 60 ° or more was evaluated according to the following criteria.
A: Less than 10 B: 10 or more and less than 20 C: 20 or more

Example 1
<Preparation of catalyst solution>
In a glass flask, 51 parts of benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclophosphine) ruthenium dichloride as a metathesis polymerization catalyst, 79 parts of triphenylphosphine and tributylphosphine as metathesis polymerization retarders 2 parts was dissolved in 952 parts of toluene to prepare a catalyst solution.

<Preparation of monomer solution>
A polyethylene bottle, tetracyclo ^{[9.2.1.0 2,10} as cycloolefin monomers. 0 ^3,8 ] tetradeca-3,5,7,12-tetraene 22.5 parts and 2-norbornene 7.5 parts, non-ionic dispersant as a polyglycerin ester (trade name: Tyrabazole H-818, Taiyo It was confirmed that 0.9 parts by chemical), 0.5 parts divinylbenzene as a chain transfer agent and 0.5 parts 2,3-dimethyl-2,3-diphenylbutane as a crosslinking agent were added and dissolved. After that, Fe—Ni alloy (Ni 45 wt%, flat powder: major axis length X = 50.3 μm, minor axis length Y = 1.5 μm, aspect ratio X / Y = 33.5, Daido Technica, which is a soft magnetic material 60 parts) was mixed and a monomer solution was obtained.

<Preparation of polymerizable composition>
The monomer solution was cooled to 0 ° C., and while maintaining the monomer solution at 0 ° C., 0.12 part of the catalyst solution was added to 100 parts of the monomer solution and stirred to prepare a polymerizable composition.

<Preparation of cross-linked molded product>
The polymerizable composition was put into a square-shaped mold (thickness 0.5 mm) having an inner dimension of 10 mm × 100 mm, and hot-pressed at 150 ° C. for 2 minutes at a double-sided pressing pressure of 4.1 MPa. Then, it cooled, applying press pressure, and obtained the molded object which can be bridge | crosslinked after it becomes 100 degrees C or less.

  The obtained crosslinkable molded body was sandwiched between 100 μm aluminum plates and further hot pressed at 4.1 MPa at 220 ° C. for 60 minutes. Then, it cooled, applying press pressure, and obtained the laminated body, after becoming 100 degrees C or less. The aluminum plate of the obtained laminated body was removed, and various evaluations were performed on the obtained crosslinked molded body. The results are shown in Table 1.

(Example 2)
As a soft magnetic material, Fe—Ni alloy (Ni 45 wt%, flat powder: major axis length X = 17.9 μm, minor axis length Y = 1.5 μm, aspect ratio X / Y = 11.9, manufactured by Daido Technica Co., Ltd. ) Was used in the same manner as in Example 1 except that the above was used. The results are shown in Table 1.

(Example 3)
As a soft magnetic material, Fe—Ni alloy (Ni 45 wt%, flat powder: major axis length X = 11.0 μm, minor axis length Y = 1.5 μm, aspect ratio X / Y = 7.3, manufactured by Daido Technica Co., Ltd. ) Was used in the same manner as in Example 1 except that the above was used. The results are shown in Table 1.

Example 4
In a reactor, 94 parts of 2-ethylhexyl acrylate, 6 parts of acrylic acid, 0.03 part of 2,2′-azobisisobutyronitrile, and 700 parts of ethyl acetate were uniformly dissolved. The polymerization reaction is performed at 80 ° C. for 6 hours. The polymerization conversion is 97%. The resulting solution is dried under reduced pressure to evaporate ethyl acetate to obtain a viscous polymer. When the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer were measured by gel permeation chromatography (styrene conversion, tetrahydrofuran solvent), Mw was 280,000 and Mw / Mn was 3.1. is there.

  In a sealed Hobart mixer container, 20 parts of the polymer obtained above, 2 parts of methacrylic acid as an acrylic monomer, 98 parts of 2-ethylhexyl acrylate and 0.45 part of pentaerythritol triacrylate, 1,1- 1.6 parts of bis (t-butylperoxy) -3,3,5-trimethylcyclohexanone (1 minute half-life temperature: 149 ° C.) and Fe-Ni alloy (Ni 45 wt%, flat powder: long as soft magnetic material) (Axial length X = 50.3 μm, minor axis length Y = 1.5 μm, aspect ratio X / Y = 33.5, manufactured by Daido Technica Co., Ltd.) Thoroughly mix the ingredients in the mixer vessel at room temperature. Thereafter, the mixture was defoamed with stirring under reduced pressure to obtain a polymerizable composition. A polyester film with a release agent is laid on the bottom of a mold having a length of 400 mm, a width of 400 mm, and a depth of 0.6 mm, and then the polymerizable composition is poured into the mold to cover the mold with a polyester film with a release agent. cover. This is taken out from the mold and polymerized in a hot air oven at 155 ° C. for 30 minutes to obtain a molded body whose both surfaces are covered with a polyester film with a release agent. The polyester film is peeled off from the obtained molded body, and various evaluations are performed. The results are shown in Table 1.

(Example 5)
As a soft magnetic material, Fe—Ni alloy (Ni 45 wt%, flat powder: major axis length X = 17.9 μm, minor axis length Y = 1.5 μm, aspect ratio X / Y = 11.9, manufactured by Daido Technica Co., Ltd. The experiment is performed in the same manner as in Example 4 except that the above is used. The results are shown in Table 1.

(Comparative Example 1)
The experiment is performed in the same manner as in Example 1 except that a spherical Fe—Ni alloy (Ni 45 wt%, aspect ratio X / Y = 1.2, manufactured by Daido Steel Co., Ltd.) is used as the soft magnetic material. The results are shown in Table 1.

(Comparative Example 2)
The experiment was performed in the same manner as in Comparative Example 1 except that the blending amount of the soft magnetic material was changed to 300 parts. The results are shown in Table 1.

(Comparative Example 3)
In a reactor, 94 parts of 2-ethylhexyl acrylate, 6 parts of acrylic acid, 0.3 part of 2,2′-azobisisobutyronitrile, and 700 parts of ethyl acetate were dissolved uniformly. The polymerization reaction is performed at 80 ° C. for 6 hours. The polymerization conversion is 97%. The resulting solution is dried under reduced pressure to evaporate ethyl acetate to obtain a viscous polymer. Mw of the polymer is 3,000, and Mw / Mn is 3.7.

  20 parts of the resulting polymer, 100 parts of glycerin polyglycidyl ether (Denacol EX313 manufactured by Nagase Chemtech) as an epoxy monomer, and Fe—Ni alloy (Ni 45 wt%, flat powder: major axis length X = 50.3 μm, minor axis 240 parts of long Y = 1.5 μm, aspect ratio X / Y = 33.5, manufactured by Daido Technica Co., Ltd.) and degassed while stirring under reduced pressure to obtain a polymerizable composition. A polyester film with a release agent is laid on the bottom of a mold having a length of 400 mm, a width of 400 mm, and a depth of 2 mm, and then the polymerizable composition is poured into the mold, and the top is covered with a polyester film with a release agent. This is taken out of the mold and polymerized for 30 minutes in a hot air oven at 155 ° C. to obtain a molded body covered on both sides with a polyester film with a release agent. The polyester film is peeled off from the obtained molded body, and various evaluations are performed. The results are shown in Table 1.

  As can be seen from Examples 1 to 4 and Comparative Example 1 described above, according to the polymerizable composition of the present invention including a flat soft magnetic material, the magnetic permeability is higher than when a spherical soft magnetic material is used. Is obtained. In addition, the dispersibility of the soft magnetic material is also excellent. As can be seen from Examples 1 to 4 and Comparative Example 2, according to the polymerizable composition of the present invention, a higher magnetic permeability can be obtained despite a small filling amount. Further, as can be seen from Examples 1 to 4 and Comparative Example 3, according to the present invention, a molded article excellent in magnetic permeability, stain resistance and dispersibility can be obtained.

Claims (18)

  A polymerizable composition comprising a soft magnetic material having shape anisotropy and a bulk polymerizable monomer having one or more reactive unsaturated bonds in the molecule.   2. The polymerizable composition according to claim 1, wherein the soft magnetic material has a major axis length (X) to minor axis length (Y) ratio (X / Y) of 2 or more and 10,000 or less.   The polymerizable composition according to claim 2, wherein the soft magnetic material has a flat shape.   The polymerizable composition according to claim 1, wherein 0.1 to 80% by volume of the soft magnetic material is contained in the total polymerizable composition.   Furthermore, the polymeric composition in any one of Claims 1-4 containing a polymerization catalyst.   The polymerizable composition according to claim 5, wherein the polymerization catalyst is a radical polymerization initiator.   The polymerizable composition according to claim 6, wherein the bulk polymerizable monomer is an acrylic monomer.   The polymerizable composition according to claim 5, wherein the polymerization catalyst is a metathesis polymerization catalyst.   The polymerizable composition according to claim 8, wherein the bulk polymerizable monomer is a cycloolefin monomer.   Furthermore, the polymerizable composition of Claim 9 containing a chain transfer agent.   Furthermore, the polymeric composition of Claim 9 or 10 containing a crosslinking agent.   Furthermore, the polymeric composition in any one of Claims 9-11 containing a dispersing agent.   The molded object formed by carrying out block polymerization of the polymeric composition in any one of Claims 1-12.   The molded article according to claim 13, wherein the magnetic permeability at 100 MHz is 10 or more.   The manufacturing method of the molded object which apply | coats or impregnates the polymeric composition in any one of Claims 1-12 to a support body, and performs block polymerization.   The manufacturing method of the molded object which inject | pours the polymeric composition in any one of Claims 1-12 into a metal mold | die, and performs block polymerization.   The molded object obtained by the manufacturing method of Claim 15 or 16.   A laminate comprising the molded article according to claim 17.