JP5560709B2 - Manufacturing method of molded body - Google Patents

Description

  The present invention relates to a molded body containing an annealed magnetic body and having improved magnetic properties, 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 a resin molded body having soft magnetism, which is composed of a soft powder of soft magnetic metal having Fe as a mother alloy and a resin binder. Polyamide or the like is used as the resin binder, and a molded product is obtained by injection compression molding after kneading the soft magnetic metal flat powder and the resin binder. However, in this method, it is difficult to uniformly disperse the soft magnetic metal powder, and unnecessarily shearing stress is applied to the soft magnetic metal powder during kneading. If such stress remains in the soft magnetic metal powder, the magnetic properties of the soft magnetic metal powder may be deteriorated.

  Patent Document 2 forms a mixture of a soft magnetic flat powder from which stress strain has been removed by annealing, a binder, and a solvent that dissolves the binder, and removes the solvent to form a sheet. A method for producing a composite magnetic material is disclosed. According to this method, the residual distortion of the magnetic material is alleviated, so that a molded product having excellent magnetic properties can be obtained. However, in this method, since a large amount of solvent is used, a drying process is necessary, and the process is complicated. In addition, the thickness and shape of the obtained molded body were limited.

  Patent Document 2 describes that a magnetic molded body with little residual stress can be obtained. However, in this method, since a polymer having flexibility is used as a binder, the strength and heat resistance of the obtained molded product may be insufficient. In addition, although it is described that the packing density of the magnetic powder is increased by pressing after molding, the magnetic powder is stressed again at this time, and the magnetic characteristics of the resulting molded body may be further insufficient. .

  Patent Documents 3 and 4 disclose a polymerizable composition containing norbornenes that are cycloolefin monomers, a metathesis polymerization catalyst, a chain transfer agent, and a crosslinking agent, and a method for obtaining a molded body using the same. These documents describe that a magnetic material or the like can be blended in 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 pretreatment of the magnetic material.

Patent Document 5 discloses an epoxy resin composition containing an epoxy resin, a curing agent, a curing accelerator, a wax, a flat powder of a soft magnetic metal, and an inorganic filler, and an electromagnetic wave absorber formed by thermosetting the composition. Has been.
JP 2003-209010 A JP 2000-243615 A Japanese Patent Laid-Open No. 2004-244609 WO 2005/014690 Japanese Patent Laid-Open No. 2002-234988

  The magnetic body used for the composite material with the resin as described above is manufactured through high-temperature firing, alloying, pulverization process, and the like. In many cases, internal stress remains in the magnetic powder produced through such a process, and even if such magnetic powder is combined with resin, the expected magnetic properties are not achieved. Further, in the step of compounding with the resin, unnecessary stress is often applied to the magnetic material by kneading or the like, and such stress is also a factor of deterioration of magnetic characteristics.

  The present invention has been made on the basis of the above-described knowledge, and exhibits excellent magnetic properties inherent to magnetic powders, and even with the same kind of magnetic powder, a molded product with improved magnetic properties. It aims at providing the polymerizable composition which can give.

  As a result of intensive investigations, the inventors focused on the possibility that magnetic properties can be improved by reducing the stress remaining in the magnetic material in the polymerizable composition containing the magnetic material and the polymerizable monomer. By using a magnetic material that has been annealed as a magnetic material and using a polymer capable of bulk polymerization (hereinafter sometimes referred to as “bulk polymerizable monomer”) as a resin material, the magnetic powder inherently has excellent properties. The present inventors have found that a magnetic molded body with improved magnetic properties can be obtained, and the present invention has been completed.

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

(1) A polymerizable composition comprising an annealed magnetic material and a bulk polymerizable monomer.

(2) The polymerizable composition according to (1), wherein a temperature of the annealing treatment is 300 to 1,000 ° C.

(3) The polymerizable composition according to (1) or (2), wherein the annealing treatment is performed in a non-oxidizing gas atmosphere.

(4) The polymerizable composition according to any one of (1) to (3), wherein the magnetic body is a soft magnetic metal.

(5) The polymerizable composition according to any one of (1) to (4), wherein the magnetic body has shape anisotropy.

(6) The polymerizable composition according to any one of (1) to (5), wherein 0.1 to 80% by volume of the magnetic material is contained in the entire composition.

(7) The polymerizable composition according to any one of (1) to (6), further comprising a polymerization catalyst.

(8) The polymerizable composition according to any one of (1) to (7), wherein the bulk polymerizable monomer is an acrylic monomer.

(9) The polymerizable composition according to any one of (1) to (7), wherein the bulk polymerizable monomer is a cycloolefin monomer.

(10) The polymerizable composition according to any one of (1) to (9), further comprising a dispersant.

(11) A molded product obtained by bulk polymerization of the polymerizable composition according to any one of (1) to (10).

(12) A method for producing a molded body, in which the polymerizable composition according to any one of (1) to (10) is applied or impregnated on a support and bulk polymerization is performed.

(13) A method for producing a molded body in which the polymerizable composition according to any one of (1) to (10) is injected into a mold and bulk polymerization is performed.

(14) A laminate including the molded product according to (11) above.

  According to the present invention, since the annealed magnetic material is used as the magnetic material, and the bulk polymerizable monomer is used as the resin material, residual strain in the magnetic material is eliminated, and the magnetic material and the monomer are mixed. Sometimes it is difficult to apply extra stress to the magnetic material. As a result, the residual strain in the magnetic material in the resulting polymerizable composition is remarkably reduced, so that the excellent magnetic properties inherent in the magnetic material powder are sufficiently maintained. Therefore, the molded body obtained from the polymerizable composition of the present invention is magnetic compared to a molded body formed from a composition obtained by kneading the same kind of magnetic powder that has not been annealed with a polymer. The characteristics are greatly improved. In the polymerizable composition of the present invention, since the magnetic substance and the monomer are mixed, the viscosity is low, the magnetic substance can be filled more highly, the resulting molded article has no voids, and is excellent. Magnetic properties can be obtained. Furthermore, since it is not necessary to use a solvent for the polymerizable composition, a solvent drying step is unnecessary, and high-speed molding such as injection molding becomes possible. Therefore, according to the polymerizable composition of the present invention, a molded body containing a magnetic body can be obtained with high productivity.

  The polymerizable composition of the present invention contains an annealed magnetic material and a bulk polymerizable monomer.

  The magnetic body before annealing (hereinafter sometimes referred to as “untreated magnetic body”) is used without any particular restriction on various magnetic powders. However, since a high magnetic permeability can be achieved in the obtained molded body, a soft magnetic body is preferable, and a soft magnetic body having shape anisotropy is more preferably used.

  The annealing conditions for the untreated magnetic material are sufficient as long as the residual strain in the untreated magnetic material can be eliminated, and are appropriately determined depending on the manufacturing history and magnetic characteristics of the untreated magnetic material.

  The annealing treatment is usually 300 to 1,000 ° C., preferably 400 to 900 ° C., more preferably 500 to 800 ° C., usually 0.1 to 10 hours, preferably 0.5 to 2 hours. Done in a range of hours. When the annealing temperature is too low, the effect of improving the magnetic permeability by the annealing treatment may not be sufficiently obtained. In addition, when the annealing temperature is too high, the magnetic material may aggregate and the dispersibility of the magnetic material in the composition may be reduced. The temperature increase rate and temperature decrease rate at this time are not particularly limited. The annealing treatment is preferably performed in a non-oxidizing gas atmosphere. A non-oxidizing gas is a gas that does not contain oxygen atoms that can oxidize the surface of an untreated magnetic material, and specifically includes nitrogen, argon, helium, hydrogen, ammonia decomposition gas, and the like. The gas flow rate, gas mixing ratio, etc. at this time may be appropriately selected according to the type and amount of the magnetic material.

  Among these, nitrogen, argon, and hydrogen are preferable from the viewpoint of workability, and nitrogen is more preferable.

  The apparatus used for the annealing treatment is not particularly limited as long as the apparatus can raise the temperature to the above temperature and can achieve a predetermined atmosphere. Moreover, a batch type, a fluidized bed type, etc. are not limited. For example, an air-flow tempering furnace, an endothermic gas shift furnace, a gas soft nitriding furnace, a gas carburizing and quenching furnace, a nitrogen gas non-oxidizing furnace or the like is preferably used.

  When taking out the magnetic material from these furnaces, it is preferable to flow in and take out a gas in which oxygen or air and the non-oxidizing gas are mixed. According to this method, in particular, when a soft magnetic metal, which will be described later, is used as the magnetic material, the surface is appropriately oxidized, so that the stability and dispersibility of the magnetic material can be improved. The oxygen concentration of the mixed gas is not particularly limited, but is usually 80% or less, preferably 50%, more preferably 30%, and particularly preferably 20%. The temperature in the furnace and the contact time when contacting with the mixed gas are not particularly limited.

  In addition, when performing annealing of a magnetic body by a batch type, it is preferable to put in a container, such as stainless steel and an alumina, and to cover with a gap so that a magnetic body may not scatter.

  The untreated magnetic body to be subjected to the annealing treatment may be appropriately selected according to the use of the molded body. However, for the purpose of high magnetic permeability, a soft magnetic body is preferably used, and the shape anisotropy is reduced. A soft magnetic material having the same is more preferably used. Here, the soft magnetism is a property that the internal magnetization easily aligns in the direction of the magnetic field with respect to the magnetic field applied from the outside, that is, the property of being 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. In the present invention, a soft magnetic material is preferably used.

  Here, “shape anisotropy” means that the diameter (width) of the soft magnetic particles is the largest when the shape of the soft magnetic particles is observed three-dimensionally with a scanning electron microscope (SEM) or the like. The long axis is the long axis, the long axis length (X), which is the length of the long axis, and the shortest axis is the length of the shortest axis (width). The average value of the aspect ratio (X / Y) with the minor axis length (Y) is preferably 2 or more and 10,000 or less, more preferably 2 or more and 1,000 or less, still more preferably 5 or more and 500 or less, particularly preferably. A shape that is 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 determined by obtaining an average value for 100 arbitrary particles in a photographic image obtained by observing soft magnetic particles with an electron microscope (SEM) or the like. The

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

  More specific shapes of the soft magnetic material include needle shapes, rod shapes, flat shapes, tree shapes, and the like, more preferably needle shapes, rod shapes, and flat shapes, and particularly preferably flat shapes. The flat shape can be confirmed by a scanning electron microscope (SEM) or the like to have a plate shape.

  The shape anisotropy of the soft magnetic material used in the present invention is not particularly limited as long as it is properly used in the application.

  Examples of the soft magnetic material include at least one of Fe, Ni, and Co. Specific examples 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.

  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, those (the a and b is any number satisfying 0 ≦ a + b ≦ 1. ) General formula _{(NiO) a (ZnO) b} · Fe 2 O 3 having a composition represented by 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 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 other divalent metals such as Ni, Cu, Co, and 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 may be spherical, but preferably has shape anisotropy. In addition, as a method for producing a soft magnetic metal composite and soft magnetic metal powder of a predetermined shape and size, a powder obtained by roughly pulverizing an ingot of a required composition with a vibration mill or the like, and then rolling and a ball mill having a shearing action A method of pulverizing with a pulverizer or attritor using pulverization media such as the above can also be exemplified. Further, instead of the coarse pulverization method by the ingot pulverization method, it is also possible to use a gas atomization method, a water atomization method, a rotating disk method, a chatter vibration method, or the like. Thereby, a needle-like or flat soft magnetic metal is preferably obtained.

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

  The surface of these 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; silazane; poly The surface treatment is preferably performed with a known surface treatment agent such as siloxane.

  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 used 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, based on 100 parts by weight of the 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 magnetic substance 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 relative to the total volume of the polymerizable composition. 10-50% by volume. Further, the blending amount of the magnetic substance 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. 65 to 90% by weight.

  Here, the total volume and the total weight of the polymerizable composition are a composition comprising all of these components in the case where a magnetic substance, a block polymerizable monomer described later, and optional components added as desired are included. Mean volume and weight. If the blending amount of the 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 10 or more, more preferably 14 or more, and still more preferably 17 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 is high at a high frequency of 1 GHz or higher, it can be suitably used for applications using a high frequency such as wireless LAN, ETC, and on-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 above magnetic material and a bulk polymerizable monomer. Here, the bulk polymerization is a polymerization method in which a bulk polymerizable monomer is polymerized substantially without a diluting solvent. The bulk polymerizable monomer used in the present invention is not particularly limited as long as it is a monomer that can increase the polymerization conversion rate to the extent that it is solidified by bulk polymerization, but is preferably a monomer having one or more unsaturated bonds in the molecule. is there. The polymerization conversion rate in the bulk polymerization is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. By using a polymerizable composition containing a magnetic substance and a bulk polymerizable monomer and bulk polymerizing this, the resulting molded body has a highly dispersed magnetic body and is highly filled.

  The unsaturated bond in the bulk polymerizable monomer preferably used is a carbon-carbon double bond (C = C) or carbon-carbon triple bond (C≡C) that imparts addition polymerization or ring-opening polymerization to the monomer. , Refers to an isocyanate group (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.

  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 type is not particularly limited, but includes the following.
(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.

As a specific example of such a bulk polymerizable monomer,
Addition polymerization is possible by reaction of carbon-carbon unsaturated bonds such as olefin, halogenated olefin, conjugated or non-conjugated diene, acetylene which may have a substituent, aromatic vinyl monomer, vinyl ether, vinyl ester, acrylic acid, etc. Monomers;
Cyclic ether, lactone, lactam, cyclic amine, cyclic sulfide, cyclic carbonate, cyclic acid anhydride, cyclic imino ether, amino acid-N-carboxylic acid anhydride, cyclic imide, cyclic phosphorus-containing compound, cyclic silicon-containing compound, cycloolefin monomer Cyclic monomers capable of ring-opening polymerization, such as
Epoxy, phenol, melamine, urea, diamine, dicarboxylic acids, oxycarboxylic acid, aminocarboxylic acid, diol, diisocyanate, sulfur-containing compound, phosphorus-containing compound, aromatic ether, dihalogen compound, aldehyde, diketone compound, carbonic acid derivative, etc. Of polyfunctional monomers capable of polycondensation or polyaddition;
Examples thereof include aniline derivatives, silicon compounds, and macromers.

  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 epoxy monomer, an aromatic vinyl monomer, an acrylic monomer, a cycloolefin monomer, a urethane monomer, and an epoxy monomer and a silane monomer are preferable, an aromatic vinyl monomer, an acrylic monomer, and a cycloolefin monomer are more preferable, an acrylic monomer, And cycloolefin monomers are particularly preferred. These may be used alone or in combination of two or more.

  Specific examples of aromatic vinyl monomers include monofunctional aromatics such as styrene, α-methylstyrene, vinyltoluene, vinylethylbenzene, vinylxylene, pt-butylstyrene, α-methyl-p-methylstyrene, and vinylnaphthalene. And polyfunctional aromatic vinyl monomers such as aromatic 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 alkyl methacrylate 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, etc .; 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 acrylic 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 or ethylene glycol dimethacrylate; Trimethacrylic acid ester such as trimethylolpropane trimethacrylate; Polyethylene glycol diacrylate , 1,3-butylene glycol diacrylate and other diacrylate esters; trimethylolpropane triacrylate and the like Examples include acrylates, etc. 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.
As the epoxy monomer, an epoxy monomer having at least two epoxy groups in at least one molecule is preferable.

 In particular, use of an ortho-cresol novolak type, a naphthalene skeleton-containing type, or a biphenyl skeleton-containing type is preferable because of excellent heat resistance. These epoxy monomers may be used individually by 1 type, and may use 2 or more types together. The epoxy equivalent is preferably 100 to 400 g / eq. Specific examples of such an epoxy monomer include sorbitol polyglycidyl ether (SORPGE), polyglycerol polyglycidyl ether (PPGGE), pentaerythritol polyglycidyl ether (PETPGE), diglycerol polyglycidyl ether (DPGGE), glycerol polyglycidyl ether. (GREPGE), trimethylolpropane polyglycidyl ether (TMMPGE), resorcinol diglycidyl ether (RESDGE), neopentyl glycol diglycidyl ether (NPGDGE), 1,6-hexanediol diglycidyl ether (HDDGE), ethylene glycol diglycidyl Ether (EGDGE), polyethylene glycol diglycidyl ether (PEGDGE), pro Lenglycol diglycidyl ether (PGDGE), polypropylene glycol diglycidyl ether (PPGDGE), polybutadiene diglycidyl ether (PBDGE), phthalic acid diglycidyl ether (DGEP), halogenated neopentylglycerol diglycidyl ether, bisphenol A type diglycidyl ether (DGEBA), bisphenol F-type diglycidyl ether (DGEBF) and the like are used, and particularly preferred are trimethylolpropane polyglycidyl ether (TMMPGE), sorbitol polyglycidyl ether (SORPGE) and the like.

  The polymerizable composition of the present invention contains the magnetic substance 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. Examples include catalysts and organic acids, inorganic acids, inorganic alkalis, amines and the like.

  For example, when the bulk polymerizable monomer is an epoxy monomer, organic acids such as urea derivatives, amines, phosphines, carboxylic acids are preferably used as the polymerization catalyst.

  When the bulk polymerizable monomer is a urethane monomer, amines and polyhydric alcohols are preferably used as the polymerization catalyst.

  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, and the like, radical polymerization initiators, A metallocene catalyst, a phenoxyimine catalyst and the like are preferable, and a radical polymerization initiator is more preferably used.

  When the bulk polymerizable monomer is an acrylic monomer, the polymerization catalyst is preferably a radical polymerization initiator, a cationic polymerization initiator, or an anionic polymerization initiator, more preferably 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, a radical polymerization initiator, and an organic acid are preferably used.

  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, radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators, urea derivatives, organic acids, platinum catalysts, metathesis polymerization catalysts are used, more preferably organic acids, radical polymerization initiators, metathesis polymerization catalysts, Particularly 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.

  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;
Carbides 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 becomes a crosslinkable molded product, that is, a crosslinkable molded product. Crosslinking of the crosslinkable molded body proceeds by heating. In particular, 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 the ring-opening polymerization proceeds. By heating, a cross-linking reaction proceeds, and a molded body with a cross-linked body having excellent physical properties can be provided. 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 molded 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 The functional group at the end of the resin 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. The crosslinking agent and the polymerization catalyst described above are partially included in the range, but are different in the present specification because they are used in different processes under different conditions of use, particularly in the temperature range. .

  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 Peroxy esters 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, and the dispersion effect is improved. 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.

1) As a more specific example of a nonionic dispersant having a polyethylene glycol chain or a polypropylene glycol chain,
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.

  Also, 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, Examples include condensed fatty acid esters, fluorohydrocarbon adducts, and copolymers with silicone.

In addition, as a more specific example of 2) a polyhydric alcohol type nonionic dispersant,
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 ;
Mono-distearate diglycerin, monostearate diglycerin, mono-dioleate diglycerin, monostearate hexaglycerin, monooleic acid hexaglycerin, monomyristic acid hexaglycerin, monolauric acid hexaglycerin, mono-dicaprylic acid hexaglycerin, Hexastearic acid hexaglycerin, octastearic acid hexaglycerin, monostearic acid decaglycerin, distearic acid decaglycerin, pentastearic acid decaglycerin, decastearic acid decaglycerin, monooleic acid decaglycerin, pentaoleic acid decaglycerin, dekaoleic acid deca Glycerin, monomyristic acid decaglycerin, monolauric acid decaglycerin, monolauric acid triglycerin, monomyristic acid Glycerin, trioleic monooleate, triglyceryl monostearate, pentaglyceryl monolaurate, pentaglyceryl monomyristate, pentaglycerin trimyristate, pentaglyceryl monooleate, pentaglyceryl trioleate, pentaglyceryl monostearate, 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 magnetic substance can be blended in the polymerizable composition, and there are few unreacted monomers remaining in the molded article after polymerization, and the moldability is improved. A good polymerizable composition can be obtained.

  Moreover, as a nonionic dispersing agent, what melt | dissolves in a block polymerizable monomer is 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 magnetic material may be poor and molding may be difficult, and if it is more than 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 radical generation at the initial 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 body fluidity and storage stability.

  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 a molar ratio of (radical generator: radical crosslinking retarder) and is usually in the range of 1: 0.001-1: 1, preferably 1: 0.01-1: 1. is there.

  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. Cross-linking 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. In the present invention, the filler does not include the concept of 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 magnetic substance and a bulk polymerizable monomer, and optionally contains additives such as the above-described 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. Moreover, it is preferable to add and use a magnetic body and a dispersing agent to a monomer liquid.

  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 magnetic substance and other optional components are added to the bulk polymerizable monomer is not particularly limited. Moreover, since the dispersibility of a magnetic body may improve by adding a dispersing agent before adding a magnetic body, it is especially preferable to add a magnetic body after adding a dispersing agent. 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 resins 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. After impregnating the fibrous reinforcing material with the polymerizable composition, the prepreg impregnated with the cycloolefin resin can be obtained by heating to a predetermined temperature and polymerizing 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 of a polymer is 80% or more normally, Preferably it is 90% or more, More preferably, it is 95% or more. The polymerization conversion rate can be determined, for example, by quantitatively analyzing unreacted monomers by gas chromatography on a solution obtained by dissolving the molded body in a solvent. The molded body in which the polymerization has proceeded almost completely has few unreacted monomers and generates less odor.

  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 cross-linked molded article can be obtained by heating and cross-linking a cross-linkable molded article 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 1 minute to 10 hours.

  The method for heating and crosslinking the crosslinkable molded product is not particularly limited. In the case where the crosslinkable molded body 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 magnetic material are alternately laminated like a multilayer laminate substrate. Here, when a plurality of resin layers containing a 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 of 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 an appropriate substrate. A laminate may be obtained by superimposing on a material, or a laminate may be obtained by superposing molded bodies 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.

  Further, when obtaining a laminate including a constituent layer composed of a molded body of a crosslinked body, for example, (1) a crosslinkable molded body obtained by using a polymerizable composition containing a crosslinking agent is laminated on a base material. Obtained by using a polymerizable composition containing a crosslinking agent, (2) laminating the polymerizable composition on a substrate material, and proceeding bulk polymerization and crosslinking reaction. (2) Applying an adhesive such as a resin to at least one surface of the crosslinked body and bonding it 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 method (1), for example, a crosslinkable molded body and a metal foil as a base material are superposed and crosslinked by heating with a hot press or the like, so that the metal foil is firmly bonded. 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 increases once the crosslinkable molded article is passed.

  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.

  The heating method for producing the laminate of the present invention is not limited, but the method of superimposing a crosslinkable molded body and a base material such as a metal foil or a printed wiring board manufacturing substrate on a hot press is highly productive. Therefore, it is preferable. 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 magnetic material is uniformly dispersed. Further, since it is not necessary to use a solvent in the polymerizable composition, a molded product having a complicated three-dimensional shape is formed by reaction injection molding or the like. Molding can be performed at high speed, and a solvent drying step is not necessary. Therefore, according to the polymerizable composition of the present invention, a molded body containing a magnetic body can be obtained with high productivity. In the obtained molded body and laminate, no voids are generated 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 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 magnetic body, the complex permeability in the molded body, and the moldability was performed as follows.

<Aspect ratio of 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 magnetic particles with a scanning electron microscope (SEM), and the aspect ratio ( X / Y).

<Permeability>
The magnetic permeability refers to the real part of the complex magnetic permeability, and was measured at 100 MHz by a one-turn coil method using a network analyzer (manufactured by Agilent). The evaluation criteria are as follows.
100 MHz
A: 17 or more B: 14 or more and less than 17 C: less than 14

<Increase rate of magnetic permeability after annealing>
Moreover, the magnetic permeability was measured also about the molded object of the same composition which used the magnetic body which has not been annealed, and the increase rate of the magnetic permeability by annealing was evaluated according to the following criteria.
A: 40% or more B: 25% or more and less than 40% C: 5% or more and less than 25% D: less than 5%

<Moldability>
By polishing the side surface of the obtained molded body, the cross section was smoothed, the size of voids was observed with SEM, and the evaluation was performed according to the following criteria.
A: There is no void. Or the maximum diameter of a void is 3 micrometers or less.
B: There are voids larger than 3 μm and not larger than 10 μm.
C: There are voids larger than 10 μm.

Example 1
<Annealing treatment of magnetic material>
Fe-Al-Si alloy which is a soft magnetic material (Sendust alloy Si 6%, Al 9%, flat powder, major axis length X = 24.9 μm, minor axis length Y = 1.5 μm, aspect ratio X / Y = 16.6. 6, manufactured by Dowa Iron Powder Co., Ltd.) was annealed at 300 ° C. for 1 hour in a nitrogen atmosphere.

<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. Next, 60 parts of the annealed soft magnetic material was added and mixed to obtain a monomer solution.

<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 crosslinkable molded object after it became 100 degrees C or less.

  The obtained crosslinkable molded product 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 laminate was removed, and various evaluations were performed on the molded body obtained by the obtained crosslinked body. The results are shown in Table 1.

(Example 2)
The experiment was performed in the same manner as in Example 1 except that the annealing treatment was performed at 600 ° C. The results are shown in Table 1.

(Example 3)
The experiment was performed in the same manner as in Example 1 except that the annealing treatment was performed at 900 ° C. The results are shown in Table 1.

(Example 4)
Fe-Ni alloy (Ni 45%, 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) as soft magnetic material The experiment was performed in the same manner as in Example 2 except that it was used. The results are shown in Table 1.

(Example 5)
As a soft magnetic material, Fe-Al-Si alloy (Sendust alloy Si 6%, Al 9%, flat powder, major axis length X = 50.5 μm, minor axis length Y = 1.5 μm, aspect ratio X / Y = 33. 7 and manufactured by Mate) were used in the same manner as in Example 2. The results are shown in Table 1.

(Example 6)
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 240.9 parts of a soft magnetic material are charged all at once, under a nitrogen atmosphere. The raw materials in the Hobart mixer container are sufficiently mixed at room temperature under conditions. Thereafter, the mixture is defoamed with stirring under reduced pressure to obtain a polymerizable composition. As the soft magnetic material, the same Fe—Si—Al alloy annealed at 600 ° C. as that used in Example 2 is used.

  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 of the mold and polymerized in a hot air oven at 155 ° C. for 30 minutes to obtain a molded body which is an electromagnetic wave absorbing composition sheet 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 7)
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 polymer. Mw of the polymer is 3000, and Mw / Mn is 3.7.

  20 parts of this polymer, 100 parts of glycerin polyglycidyl ether (Denacol EX313 manufactured by Nagase Chemtech) as an epoxy monomer, and 240 parts of soft magnetic material are mixed and degassed while stirring under reduced pressure to obtain a polymerizable composition. . As the soft magnetic material, the same Fe—Si—Al alloy annealed at 600 ° C. as that used in Example 2 is used.

  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 from the mold and polymerized in a hot air oven at 155 ° C. for 30 minutes to obtain a molded body which is an electromagnetic wave absorbing composition sheet 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.

(Comparative Example 1)
The same procedure as in Example 1 was performed except that the soft magnetic material was not annealed.

(Comparative Example 2)
The same procedure as in Example 4 was performed except that the soft magnetic material was not annealed.

(Comparative Example 3)
The process was performed in the same manner as in Example 5 except that the soft magnetic material was not annealed.

(Comparative Example 4)
The same procedure as in Example 6 is performed except that the soft magnetic material is not annealed.

  As can be seen from the above Examples and Comparative Examples, according to the present invention, by using the annealed magnetic body, a polymerizable composition having excellent moldability can be obtained, and a molded body having high magnetic permeability. Is obtained.

Claims (10)

A method for producing a molded body, in which a polymerizable composition comprising an annealed magnetic body and a bulk polymerizable monomer is injected into a mold and bulk polymerization is performed. The method for producing a molded body according to claim 1, wherein a temperature of the annealing treatment is 300 to 1,000 ° C. The method for producing a molded body according to claim 1 or 2, wherein the annealing treatment is performed in a non-oxidizing gas atmosphere. The said magnetic body is a soft magnetic metal, The manufacturing method of the molded object in any one of Claims 1-3. The method for producing a molded body according to claim 1, wherein the magnetic body has shape anisotropy. The manufacturing method of the molded object in any one of Claims 1-5 which contain 0.1-80 volume% of said magnetic bodies in all the polymeric compositions. Furthermore , the manufacturing method of the molded object in any one of Claims 1-6 containing a polymerization catalyst. The method for producing a molded article according to any one of claims 1 to 7, wherein the bulk polymerizable monomer is an acrylic monomer. The method for producing a molded article according to any one of claims 1 to 7, wherein the bulk polymerizable monomer is a cycloolefin monomer. Furthermore , the manufacturing method of the molded object in any one of Claims 1-9 containing a dispersing agent.