Curable urethane resin composition and urethane resin

Abstract

The present invention addresses the problem of providing a high-magnetic-permeability soft magnetic urethane resin material that has high magnetic permeability and excellent moldability and flexibility and can be easily produced. The present invention pertains to a curable urethane resin composition comprising: a polyol (A); a polyisocyanate (B); a phosphoric acid ester (C) represented by general formula (1); and soft magnetic ferrite particles (D). [In general formula (1), R1 is a hydrogen atom, a C2-C20 alkyl group, or a C2-C20 alkenyl group, and some of hydrogen atoms of the alkyl group or the alkenyl group may be substituted with halogen atoms. A1O is a C2-C3 alkyleneoxy group, n1 represents the average addition molar number of A1O and is a number of 0-15, and R2 is a hydrogen atom or –(A2O)n2R3 (R3 is a C2-C20 alkyl group or a C2-C20 alkenyl group, and some of hydrogen atoms of the alkyl group or the alkenyl group may be substituted with halogen atoms. A2O is a C2-C3 alkyleneoxy group, and n2 represents the average addition molar number of A2O and is a number of 0-15).]

Description

Curable urethane resin composition and urethane resin

[0001] The present invention relates to a curable urethane resin composition and a urethane resin.

[0002] As electronic components become smaller and more powerful, magnetic composite materials are required to have higher performance, higher reliability, and lower cost. One component of a booster circuit in a power supply system is an inductor, which can store electrical energy as magnetic energy. Composite magnetic materials used in inductor cores can be obtained as powder compacts by, for example, filling a mixture of soft magnetic powder and resin and then pressurizing the mixture. Methods for encapsulating elements or components such as coils include, for example, press molding, in which a powdered encapsulating material and a member to be encapsulated are pressed under high pressure, and molding, in which a encapsulating material composition is coated on the member to be encapsulated and the composition is solidified or cured. Magnetic composite materials that have electromagnetic properties imparted by filling these encapsulating materials with magnetic particles are also known. Patent Documents 1 to 4 disclose resin compositions containing a curable resin and magnetic particles, and magnetic composite materials obtained by curing the resin compositions.

[0003] However, conventional magnetic composite materials suffer from poor flexibility and are prone to cracking due to vibration or impact on electronic components. Furthermore, when magnetic particles are heavily loaded into a resin, fluidity decreases, making it difficult to sufficiently increase the magnetic particle content, which can result in insufficient magnetic permeability. Furthermore, because powder compacts are formed at high pressures exceeding 10 MPa, typically several hundred MPa, the soft magnetic powder particles are pressed together, damaging their insulating coatings and increasing their coercivity due to stress distortion. Damage to the insulating coating increases the electrical connection between the soft magnetic powder particles, resulting in increased eddy current loss in the compact. Increased coercivity increases the core loss of the compact, necessitating a stress distortion removal process. Furthermore, powder compaction requires a significant number of manufacturing steps, resulting in increased costs.

[0004] Patent No. 4692768 Patent No. 5700298 Patent No. 7211727 Patent No. 6813044

[0005] The present invention has been made in light of the above circumstances, and aims to provide a high-magnetic-permeability, soft-magnetic urethane resin material that has high magnetic permeability, excellent moldability and flexibility, and can be easily produced.

[0006] The present invention relates to a polyol (A), a polyisocyanate (B), and a compound represented by the following general formula (1): [In general formula (1), R １ represents a hydrogen atom, an alkyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, and some of the hydrogen atoms of the alkyl group or alkenyl group may be substituted with halogen atoms. １ O is an alkyleneoxy group having 2 to 3 carbon atoms, and n1 is A １ represents the average number of moles of O added, and is a number from 0 to 15; R ２ is a hydrogen atom or -(A ２ O) ｎ２ R ３ (R ３ represents an alkyl group having 2 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, and some of the hydrogen atoms of the alkyl group or alkenyl group may be substituted with halogen atoms. ２ O is an alkyleneoxy group having 2 to 3 carbon atoms, and n2 is A ２ and a urethane resin that is a cured product of the curable urethane resin composition.

[0007] According to the present invention, it is possible to provide a high-permeability, soft-magnetic urethane resin material that has high magnetic permeability, excellent moldability and flexibility, and can be easily produced.

[0008] [1. Curable Urethane Resin Composition] The curable urethane resin composition of the present invention comprises a polyol (A), a polyisocyanate (B), and a hydroxyl group-containing urethane compound represented by the following general formula (1): [In general formula (1), R １ represents a hydrogen atom, an alkyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, and some of the hydrogen atoms of the alkyl group or alkenyl group may be substituted with halogen atoms. １O is an alkyleneoxy group having 2 to 3 carbon atoms, and n1 is A １ represents the average number of moles of O added, and is a number from 0 to 15; R ２ is a hydrogen atom or -(A ２ O) ｎ２ R ３ (R ３ represents an alkyl group having 2 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, and some of the hydrogen atoms of the alkyl group or alkenyl group may be substituted with halogen atoms. ２ O is an alkyleneoxy group having 2 to 3 carbon atoms, and n2 is A ２ and (C) represents the average number of moles of O added, and is a number from 0 to 15.] and soft magnetic ferrite particles (D).

[0009] The curable urethane resin composition of the present invention may be either an embodiment (first embodiment) in which all of the polyol (A), polyisocyanate (B), phosphate ester (C), and soft magnetic ferrite particles (D) are contained in one part, or an embodiment (second embodiment) in which the polyol (A), polyisocyanate (B), phosphate ester (C), and soft magnetic ferrite particles (D) are contained separately in two parts. First, the first embodiment will be described.

[0010] [First Aspect] The curable urethane resin composition of the first aspect contains, in one component, a polyol (A), a polyisocyanate (B), a phosphate ester (C), and soft magnetic ferrite particles (D).

[0011] The polyol (A) preferably contains at least one selected from the group consisting of polyether polyol (a1), polyester polyol (a2), polycarbonate polyol (a3), and polyolefin polyol (a4). Among these, the polyol (A) preferably contains polyether polyol (a1).

[0012] Examples of the polyether polyol (a1) include aliphatic polyether polyols and aromatic polyether polyols. Examples of the aliphatic polyether polyols include diols obtained by addition polymerization of an alkylene oxide (hereinafter referred to as AO) to an aliphatic polyhydric alcohol having 2 to 20 carbon atoms. Examples of the aliphatic polyhydric alcohol having 2 to 20 carbon atoms include ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, dodecanediol, neopentyl glycol, and glycerin, with propylene glycol, 1,4-butanediol (tetramethylene glycol), and glycerin being preferred. Examples of the AO include ethylene oxide, 1,2- or 1,3-propylene oxide, and 1,2-, 1,3-, 1,4-, or 2,3-butylene oxide. Two or more of these AOs may be used in combination, and when two or more of them are used in combination, the bonding mode of the AOs may be block addition, random addition, or a combination of these.

[0013] Specific examples of aliphatic polyether polyols include polyoxyethylene polyols (polyethylene glycol, etc.), polyoxypropylene polyols (polypropylene glycol, etc.), polyoxyethylene / oxypropylene polyols, polytetramethylene glycol, polyoxypropylene glyceryl ether, etc. These are also commercially available as Sannix PP-200, GP-3000 [manufactured by Sanyo Chemical Industries, Ltd.], PTMG250, 650 [manufactured by Mitsubishi Chemical Corporation], Uniol PB-700 [manufactured by NOF Corporation], etc.

[0014] Examples of aromatic polyether polyols include adducts of alkylene oxides having 2 to 4 carbon atoms with compounds having 6 to 20 carbon atoms and an aromatic ring and two or more hydroxyl groups (such as bisphenol, resorcinol, and hydroquinone). Specific examples include polyols having a bisphenol skeleton, such as ethylene oxide (hereinafter abbreviated as EO) adducts of bisphenol A (e.g., adducts of bisphenol A with 2 moles of EO, adducts of bisphenol A with 4 moles of EO, adducts of bisphenol A with 6 moles of EO, adducts of bisphenol A with 8 moles of EO, adducts of bisphenol A with 10 moles of EO, and adducts of bisphenol A with 20 moles of EO), and propylene oxide (hereinafter abbreviated as PO) adducts of bisphenol A (e.g., adducts of bisphenol A with 2 moles of PO, adducts of bisphenol A with 3 moles of PO, and adducts of bisphenol A with 5 moles of PO), as well as EO or PO adducts of resorcinol.

[0015] From the viewpoint of excellent moldability, the polyether polyol (a1) is preferably an aliphatic polyether polyol. From the viewpoint of excellent moldability, the number average molecular weight (Mn) of the polyether polyol (a1) is preferably 100 to 3,000, more preferably 200 to 2,000.

[0016] In this specification, the number average molecular weight (Mn) can be measured using gel permeation chromatography (hereinafter abbreviated as GPC) under the following conditions: Apparatus: HLC-8120 (manufactured by Tosoh Corporation) Column: TSKgel α6000, G3000 PWXL (manufactured by Tosoh Corporation) Detector: RI (Refractive Index) Eluent: 0.5% sodium acetate-water / methanol (volume ratio 70 / 30) Eluent flow rate: 1.0 ml / min Column temperature: 40°C Sample concentration: 0.25 wt% Injection volume: 200 μl Standard substance: TSK STANDARD POLYETHYLENE OXIDE (manufactured by Tosoh Corporation) Data processing software: GPC-8020model II (manufactured by Tosoh Corporation)

[0017] Examples of the polyester polyol (a2) include condensates of polyols (such as the polyether polyol (a1), aliphatic diols, aliphatic polyols, alicyclic polyols, and AO adducts of alicyclic polyols) with polycarboxylic acids. Examples of polycarboxylic acids include linear aliphatic polycarboxylic acids having 2 to 20 carbon atoms [oxalic acid, malonic acid, dipropylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, glutaric acid, 2-methylglutaric acid, 2,2-dimethylglutaric acid, 2,4-dimethylglutaric acid, 3-methylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, pentadecanedioic acid, tetradecanedioic acid, heptadecanedioic acid, octadecanedioic acid, and nonadecanedioic acid]. and eicosanedioic acid, etc.]; alicyclic polycarboxylic acids having 5 to 20 carbon atoms [cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid, and camphoric acid]; aromatic polycarboxylic acids having 8 to 20 carbon atoms [terephthalic acid, isophthalic acid, 2-methylterephthalic acid, 4,4-stilbenedicarboxylic acid, naphthalenedicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, and diphenyl ether dicarboxylic acid, etc.], and these polycarboxylic acids are commercially available as Kuraray Polyol P-2010 (manufactured by Kuraray Co., Ltd.), etc.

[0018] The aliphatic diol may be an aliphatic diol having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms.

[0019] Examples of the aliphatic polyol include trivalent or higher alcohols among aliphatic polyols having 3 to 20 carbon atoms, such as glycerin and pentaerythritol, with glycerin being preferred.

[0020] Examples of the alicyclic polyol include alicyclic polyols having 4 to 16 carbon atoms (1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and hydrogenated bisphenol A).

[0021] Examples of the AO adduct of an alicyclic polyol include compounds in which an AO is added to the above-mentioned alicyclic polyol. As the AO, the same AOs as those exemplified in the description of the polyether polyol (a1) can be used, and the preferred AOs are also the same.

[0022] Examples of the polycarbonate polyol (a3) ​​include reaction products of polyols [such as the above-mentioned polyether polyol (a1), aliphatic diols, aliphatic polyols, alicyclic polyols, and AO adducts of alicyclic polyols] with phosgene, and these are commercially available as Kuraray Polyol C-590, C2090 [manufactured by Kuraray Co., Ltd.], etc.

[0023] Examples of the polyolefin polyol (a4) include polybutadiene polyol and hydrogenated polybutadiene diol.

[0024] From the viewpoint of the physical properties of the resin after curing, the polyol (A) is preferably one having at least two hydroxyl groups per molecule on average. The polyol (A) may be used alone or in combination of two or more.

[0025] The number average molecular weight of the polyol (A) is preferably from 100 to 3,000, more preferably from 200 to 2,000, from the viewpoint of excellent moldability.

[0026] Examples of the polyisocyanate (B) include chain aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and isocyanurates of these polyisocyanates.

[0027] Examples of the chain aliphatic polyisocyanate include chain aliphatic polyisocyanates having 4 to 20 carbon atoms, and preferred examples include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. These are also commercially available as A201H [manufactured by Asahi Kasei Corporation, a dimer of hexamethylene diisocyanate].

[0028] Examples of the alicyclic polyisocyanate include alicyclic polyisocyanates having 6 to 17 carbon atoms, and preferred examples include isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, and 2,5- or 2,6-norbornane diisocyanate. Alicyclic polyisocyanates are commercially available as Desmodur I (manufactured by Sumika Covestro Urethane Co., Ltd.), and the like.

[0029] Examples of aromatic polyisocyanates include aromatic polyisocyanates having 8 to 22 carbon atoms, and preferred examples include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4'- or 2,4'-diphenylmethane diisocyanate (MDI), m- or p-isocyanatophenylsulfonyl isocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate, m- or p-xylylene diisocyanate (XDI), and α,α,α',α'-tetramethylxylylene diisocyanate (TMXDI).

[0030] Examples of the isocyanurate of polyisocyanate include trimers of polyisocyanates (such as the aforementioned chain aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates). The isocyanurate of polyisocyanate is commercially available as TLA-100 (manufactured by Asahi Kasei Corporation, a trimer of hexamethylene diisocyanate), etc.

[0031] From the viewpoint of excellent moldability, the polyisocyanate (B) preferably contains at least one selected from the group consisting of a chain aliphatic polyisocyanate, an alicyclic polyisocyanate, an isocyanurate of a chain aliphatic polyisocyanate, and an isocyanurate of an alicyclic polyisocyanate. The polyisocyanate (B) may be used singly or in combination of two or more.

[0032] The total weight proportion of the polyol (A) and the polyisocyanate (B) in the curable urethane resin composition is preferably 2 to 30% by weight, more preferably 3 to 20% by weight, based on the weight of the curable urethane resin composition.

[0033] The isocyanate index of the polyol (A) and the polyisocyanate (B) [total number of moles of isocyanate groups in the polyisocyanate (B) / total number of moles of hydroxyl groups in the polyol (A)] is preferably 0.8 to 1.2. When the isocyanate index is in this range, the curability of the composition can be improved. The content of isocyanate groups can be calculated by a method according to JIS K 1603-1:2007, for example.

[0034] The phosphate ester (C) is represented by the following general formula (1):

[0035] [In general formula (1), R １ represents a hydrogen atom, an alkyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, and some of the hydrogen atoms of the alkyl group or alkenyl group may be substituted with halogen atoms. １ O is an alkyleneoxy group having 2 to 3 carbon atoms, and n1 is A １ represents the average number of moles of O added, and is a number from 0 to 15; R ２ is a hydrogen atom or -(A ２ O) ｎ２ R ３ (R ３ represents an alkyl group having 2 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, and some of the hydrogen atoms of the alkyl group or alkenyl group may be substituted with halogen atoms. ２O is an alkyleneoxy group having 2 to 3 carbon atoms, and n2 is A ２ represents the average number of moles of O added, and is a number from 0 to 15).

[0036] In general formula (1), R １ is a hydrogen atom, an alkyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, and some of the hydrogen atoms of the alkyl group or alkenyl group may be substituted with halogen atoms. Examples of the alkyl group having 2 to 20 carbon atoms include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group, and each of these may be linear or branched. Examples of alkenyl groups having 2 to 20 carbon atoms include ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, and octadecenyl groups, each of which may be linear or branched, and the position of the double bond is not limited. As the halogen atom, a fluorine atom is preferred.

[0037] R １ The alkyl group may be linear or branched, but is preferably linear. From the viewpoints of the mechanical strength of the cured product and the dispersibility of the filler, alkyl groups having 12 to 18 carbon atoms are preferred.

[0038] In general formula (1), A １ O represents an alkyleneoxy group having 2 to 3 carbon atoms, and examples thereof include an ethyleneoxy group and a propyleneoxy group. Among these, an ethyleneoxy group is preferred from the viewpoint of dispersibility. n1 represents A １ This represents the average number of moles of O added, and is a number from 0 to 15, and from the viewpoint of good dispersibility of magnetic particles and mechanical strength of the cured product, it is preferably 3 to 15, more preferably 3 to 13, and even more preferably 4 to 11.

[0039] R ２is a hydrogen atom or -(A ２ O) ｎ２ R ３ (R ３ represents an alkyl group having 2 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, and some of the hydrogen atoms of the alkyl group or alkenyl group may be substituted with halogen atoms. ２ O is an alkyleneoxy group having 2 to 3 carbon atoms, and n2 is A ２ represents the average number of moles of O added, and is a number from 0 to 15. ３ As for R １ The same can be mentioned as above, and the preferred examples are also the same. ２ As O, A １ The same as those for O can be mentioned, and the preferred ones are also the same. ２ is a hydrogen atom, the compound of general formula (1) is a monoester, and R ２ But-(A ２ O) ｎ２ R ３ In this case, the compound of general formula (1) is a diester. ２ But-(A ２ O) ｎ２ R ３ In the case of １ and R ３ may be the same or different. n1 and n2 may be the same or different.

[0040] As the phosphate ester (C) represented by the general formula (1), R １ Two or more different types may be mixed and used, or a monoester (R ２ H) and diester (R ２ But-(A ２ O) ｎ２ R ３ A mixture of monoesters and diesters (mono-di mixture) may also be used. The phosphoric acid ester (C) represented by general formula (1) is generally obtained as a mixture of monoesters and diesters (mono-di mixture). Salts of the phosphoric acid ester represented by general formula (1) (metal salts such as sodium, potassium, and magnesium, ammonium salts, etc.) may also be used.

[0041] Preferred examples of the phosphate ester (C) represented by general formula (1) include alkyl ether phosphate esters, alkenyl ether phosphate esters, alkenyl ether alkyl ether phosphate esters, alkyl phosphate esters, alkenyl phosphate esters, fluorinated alkyl ether phosphate esters, and fluorinated alkyl phosphate esters, with alkyl ether phosphate esters being more preferred. The phosphate ester (C) represented by general formula (1) can be obtained by phosphate esterification using a polyether and phosphorus oxide. Also available on the market are Cropol P-10A [manufactured by Sanyo Chemical Industries, Ltd.], Disparlon DA-375 [manufactured by Kusumoto Chemicals Co., Ltd.], Plysurf A208N [manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.], Phosphanol RL-210 [manufactured by Toho Chemical Industry Co., Ltd.], and the like. １ , R ３ : C18 alkyl group, A １ O.A. ２ O: ethyleneoxy group, n1, n2: 2, mono-di-mixture], Phosphanol RS-710 [manufactured by Toho Chemical Industry Co., Ltd., (C12-15) Pareth-9 phosphate, R １ , R ３ : C12-15 alkyl group, A １ O.A. ２ O: ethyleneoxy group, n1, n2: 9, mono- and di-mixture], Phosphanol RS-410 [manufactured by Toho Chemical Industry Co., Ltd., (C12-15) Pareth-3 phosphate, R １ , R ３ : C12-15 alkyl group, A １ O.A. ２ O: ethyleneoxy group, n1, n2: 3, mono-di-mixture], Phosphanol RB-410 [manufactured by Toho Chemical Industry Co., Ltd., oleth-4 phosphate, R １ , R ３ : C18 alkenyl group, A １ O.A. ２ O: ethyleneoxy group, n1, n2: 4, mono-di-mixture], Phosphanol RL-310 [manufactured by Toho Chemical Industry Co., Ltd., steareth-3 phosphate, R １ , R ３ : C18 alkyl group, A １ O.A. ２O: ethyleneoxy group, n1, n2: 3, mono- and di-mixture], JP-518-O [manufactured by Johoku Chemical Industry Co., Ltd., oleyl acid phosphate, n1, n2: 0, mono- and di-mixture], JP-506H [manufactured by Johoku Chemical Industry Co., Ltd., butoxyethyl acid phosphate, n1, n2: 1, mono- and di-mixture], etc. The phosphate ester (C) may be used alone or in combination of two or more.

[0042] From the viewpoint of dispersibility of the magnetic particles, the content of the phosphate ester (C) is preferably 0.1 to 4 wt % based on the weight of the soft magnetic ferrite particles (D) [0.1 to 4 parts by weight per 100 parts by weight of the soft magnetic ferrite particles (D)], more preferably 0.2 to 4 wt %, and even more preferably 0.2 to 3 wt %.

[0043] Examples of the material for the soft magnetic ferrite particles (D) include spinel-type soft magnetic ferrites, such as NiCuZn-based ferrites, MnZn-based ferrites, NiZn-based ferrites, MnMgZn-based ferrites, MgZn-based ferrites, MgZnCu-based ferrites, LiZn-based ferrites, and LiZnCu-based ferrites. Co, Si, and the like may be further added as elements constituting the soft magnetic ferrite for modification.

[0044] The magnetic material constituting the magnetic particles may be appropriately selected depending on the desired magnetization characteristics (relative magnetic permeability) and volume electrical resistivity.

[0045] Soft magnetic ferrites are commercially available as BSN-125 (NiCuZn ferrite), BSN-714 (NiZn ferrite), BSN-828 (NiCuZn ferrite), BSF-547 (MnZn ferrite), BSF-029 (MnZn ferrite), KSN-415 (MnZn ferrite), FRX-843 (MnMgZn ferrite) [all manufactured by Toda Kogyo Co., Ltd.], etc. The soft magnetic ferrite particles (D) may be used alone or in combination of two or more.

[0046] The shape of the soft magnetic ferrite particles (D) is not particularly limited, and fibrous and particulate particles can be preferably used. In the case of particles, spherical, plate-like, needle-like, or amorphous particles (obtained by crushing, etc.) can be used. Among these, spherical particles are preferred from the viewpoint of high fillability in resin, and particles with an adjusted particle size distribution are more preferred.

[0047] When the soft magnetic ferrite particles (D) are spherical particles, the volume average particle diameter [D50: particle diameter at which the cumulative particle amount in the particle size distribution on a volume basis becomes 50%] of the soft magnetic ferrite particles (D) is preferably 1 to 200 μm, more preferably 2 to 150 μm, from the viewpoint of magnetic permeability and packing property. The volume average particle diameter of the soft magnetic ferrite particles (D) can be measured using a laser diffraction particle size distribution measuring device [SALD-2000A manufactured by Shimadzu Corporation, LA-920 manufactured by Horiba, Ltd., etc.]. When components other than the soft magnetic ferrite particles (D) are dissolved in a solvent, a solution of the composition may be measured.

[0048] The soft magnetic ferrite particles (D) are preferably soft magnetic ferrite powder. The soft magnetic ferrite powder can be obtained, for example, by firing a raw material mixture obtained by mixing raw materials such as oxides, carbonates, hydroxides, and oxalates of each element constituting the soft magnetic ferrite in a predetermined composition ratio, or by precipitating each element in an aqueous solution to obtain a precipitate, in the air at 700 to 1300°C for 1 to 20 hours, and then pulverizing the mixture. From the viewpoint of environmental protection, soft magnetic ferrite powder obtained by pulverizing waste generated in the manufacturing process of various ferrite cores and ferrite sintered plates may be reused.

[0049] The content of the soft magnetic ferrite particles (D) is preferably 40 to 74% by volume, and more preferably 45 to 65% by volume, based on the volume of the curable urethane resin composition. When the content of the soft magnetic ferrite particles (D) is 40% by volume or more, magnetic permeability tends to increase, while when it is 74% by volume or less, moldability of the cured product is easily ensured.

[0050] The curable urethane resin composition of the first aspect may contain other components that do not fall under the category of polyol (A), polyisocyanate (B), phosphate ester (C), and soft magnetic ferrite particles (D), as long as the effects of the present invention are not affected. Examples of such other components include surfactants (E), plasticizers (F), urethanization catalysts (G), fillers (H), antioxidants (I), and dispersants (J). The curable urethane resin composition may further contain known additives used in urethane resins (such as the ultraviolet absorbers described in JP 2018-076537 A) as other components.

[0051] As the surfactant (E), polyoxyalkylene type nonionic surfactants (E1), ester type nonionic surfactants (E2), anionic surfactants (E3) and cationic surfactants (E4) can be preferably used.

[0052] Examples of the polyoxyalkylene type nonionic surfactant (E1) include AO adducts (preferably with an addition mole of 1 to 30) of aliphatic alcohols (having 4 to 30 carbon atoms), alkyl (having 1 to 30 carbon atoms) phenols, aliphatic (having 4 to 30 carbon atoms) amines or aliphatic (having 4 to 30 carbon atoms) amides. Preferred aliphatic alcohols constituting the polyoxyalkylene type nonionic surfactant (E1) include n-, i-, sec- or t-butanol, octanol, and dodecanol. Preferred alkylphenols include phenol, methylphenol, and nonylphenol. Preferred aliphatic amines include laurylamine and methylstearylamine. Preferred aliphatic amides include stearic acid amide.

[0053] Examples of the ester-type nonionic surfactant (E2) include ester compounds of fatty acids having 4 to 30 carbon atoms (such as lauric acid, stearic acid, and oleic acid) with polyhydric alcohols other than sucrose, sorbitol, and glycerin.

[0054] Examples of the anionic surfactant (E3) include carboxylate, sulfate, and sulfonate types. Examples of the carboxylate type include alkali metal salts of the above-mentioned fatty acids having 4 to 30 carbon atoms and alkali metal salts of polyoxyalkylene alkyl ether carboxylic acids. Examples of the sulfate type include alkali metal sulfates of the above-mentioned aliphatic alcohols having 4 to 30 carbon atoms or AO adducts of aliphatic alcohols. Examples of the sulfonate type include alkali metal sulfonates of alkylphenols. These surfactants are also commercially available as polyether carboxylic acids (manufactured by Kao Corporation, Kao Akipo RLM-100), etc.

[0055] Examples of the cationic surfactant (E4) include primary to tertiary amine salt types and quaternary ammonium salt types. Examples of the primary to tertiary amine salt types include hydrochlorides of aliphatic amines having 4 to 30 carbon atoms [primary (such as laurylamine), secondary (such as dibutylamine), and tertiary amines (such as dimethylstearylamine)], and inorganic acid (such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid) salts of triethanolamine and monoesters of fatty acids having 4 to 30 carbon atoms. Examples of the quaternary ammonium salt type include inorganic acid salts of quaternary ammonium having 4 to 30 carbon atoms (such as butyltrimethylammonium, diethyllaurylmethylammonium, and dimethyldistearylammonium). These surfactants are commercially available as Nopcosperse 092 (manufactured by San Nopco Ltd.), etc.

[0056] Examples of the plasticizer (F) include phthalic acid plasticizers [diisononyl phthalate, di-(2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, etc.], fatty acid ester plasticizers [diisononyl adipate, di-n-decyl adipate, di-(2-ethylhexyl) azelate, dibutyl sebacate, di-(2-ethylhexyl) sebacate, etc.], phosphate ester plasticizers [tributyl phosphate, tri-(2-ethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, etc.], benzoic acid plasticizers [polyethylene glycol benzoate ester], epoxy plasticizers such as epoxidized soybean oil, trimellitate plasticizers, pyromellitate plasticizers, polyester plasticizers, and sulfonate ester plasticizers. These compounds are also commercially available as diisononyl phthalate (DINP, manufactured by Aekyung Petrochemical Co., Ltd.) and polyethylene glycol benzoate (EB-300, manufactured by Sanyo Chemical Industries, Ltd.).

[0057] Examples of the urethanization catalyst (G) include amine catalysts (triethylenediamine, N-ethylmorpholine, diethylethanolamine, 1,8-diazabicyclo(5,4,0)undecene-7, etc.) and metal catalysts (bismuth tris(2-ethylhexanoate), stannous octoate, dibutyltin dilaurate, lead 2-ethylhexanoate, etc.) and are also commercially available as inorganic bismuth catalysts (manufactured by Nitto Kasei Co., Ltd., Neostan U-600, etc.).

[0058] Examples of filler (H) include zeolites and thermally conductive fillers (nitrides such as boron nitride and aluminum nitride, oxides such as aluminum oxide, silica, and magnesium oxide, and hydroxides such as aluminum hydroxide). The use of a thermally conductive filler can make the cured product of the curable urethane resin composition (i.e., the urethane resin) suitable for heat dissipation components. Filler (H) is commercially available as molecular sieve 3A-B powder (manufactured by Resonac Universal Co., Ltd.), AZ10-75 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), HF-10 (manufactured by Tokuyama Corporation), CW-310LV (manufactured by Sumitomo Chemical Co., Ltd.), RF-10CS-SC (manufactured by Ube Material Industries, Ltd.), and the like. Fillers other than those mentioned above can also be used, and by changing the type of filler, urethane resin compositions and urethane resins with various functions can be obtained depending on the type of filler. For example, by including conductive carbon or metal as a filler, a highly conductive urethane resin can be obtained; by including insulating metal oxides and / or metal hydroxides, a highly insulating urethane resin can be obtained; by including low-dielectric polyimide or polyethylene, a low-dielectric urethane resin can be obtained; by including highly dielectric barium titanate and / or lead titanium zirconate, a high-dielectric urethane resin can be obtained; by including ammonium polyphosphate and / or halide having flame retardant properties, a highly flame-retardant urethane resin can be obtained; by including titanium black, a highly light-blocking urethane resin can be obtained; by including titanium oxide and / or zirconium oxide, a highly refractive urethane resin can be obtained; by including glass fiber, carbon fiber, or Kevlar (registered trademark) fiber, a high-strength urethane resin can be obtained; by including antibacterial silver salts, copper salts, or zinc salts, a highly antibacterial urethane resin can be obtained; and by including microballoons, a highly lightweight urethane resin can be obtained.

[0059] Examples of the antioxidant (I) include hindered phenol-based antioxidants [Irganox 1135, Irganox 1010, and Irganox 1076 (all manufactured by BASF Japan Ltd.)] and hindered amine-based antioxidants [Tinuvin 770 (manufactured by BASF Japan Ltd.)].

[0060] Examples of the dispersant (J) include sorbitan fatty acid esters, fatty acids having 12 to 24 carbon atoms, sucrose fatty acid esters, and glycerin fatty acid esters. Examples of the sorbitan fatty acid esters include mono- to tri-esters of sorbitan with fatty acids having 8 to 22 carbon atoms, and specific examples thereof include sorbitan palmitate [e.g., Rheodol SP-P10 (HLB=6.7) manufactured by Kao Corporation, and Rikemal P-300 (HLB=5.6) manufactured by Riken Vitamin Co., Ltd.], mono-fatty acid sorbitan esters [e.g., Ionet S-80 manufactured by Sanyo Chemical Industries, Ltd.], and polyoxyethylene sorbitan fatty acid esters [e.g., Ionet T-60V manufactured by Sanyo Chemical Industries, Ltd.]. Examples of fatty acids having 12 to 24 carbon atoms include saturated fatty acids having 12 to 24 carbon atoms (dodecanoic acid, hexadecanoic acid, eicosanoic acid, tetracosanoic acid, etc.) and unsaturated fatty acids having 12 to 24 carbon atoms (hexadecenoic acid, octadecenoic acid, octadecanedienoic acid, etc.). Examples of sucrose fatty acid esters include esters of sucrose and fatty acids having 8 to 22 carbon atoms, and specific examples thereof include sucrose stearic acid esters [DK Ester F-50 (HLB=6), F-70 (HLB=8), and F-110 (HLB=11), manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., and Ryoto Sugar Ester S-770 (HLB=approximately 7), S-970 (HLB=approximately 9), S-1170 (HLB=approximately 11), and S-1170F (HLB=approximately 11), manufactured by Mitsubishi Chemical Corporation]. Examples of glycerin fatty acid esters include mono- to tri-esters of glycerin or polyglycerin polymers (degree of polymerization 2 to 20) and fatty acids having 8 to 22 carbon atoms. Specific examples include diglycerin monolaurate [Poem DL-100 (HLB=9.4) manufactured by Riken Vitamin Co., Ltd., etc.], diglycerin monomyristate [Poem DM-100 (HLB=8.7) manufactured by Riken Vitamin Co., Ltd., etc.], diglycerin monolaurate ... Examples of such glycerol stearate include Poem DS-100A (HLB=7.7) manufactured by Riken Vitamin Co., Ltd., diglycerol monooleate (Poem DO-100V (HLB=7.3), Rikemal DO-100 (HLB=7.4) manufactured by Riken Vitamin Co., Ltd., etc.), and decaglycerol stearate (Poem J-0081HV (HLB=12), Poem J-0381V (HLB=12) manufactured by Riken Vitamin Co., Ltd., etc.).

[0061] When the curable urethane resin composition of the first aspect contains a surfactant (E), the surfactant (E) is preferably contained in an amount of 0.001 to 30 parts by weight, more preferably 0.01 to 10 parts by weight, and particularly preferably 0.1 to 4 parts by weight, per 100 parts by weight of the soft magnetic ferrite particles (D).

[0062] When the curable urethane resin composition of the first aspect contains a plasticizer (F), the amount of the plasticizer (F) relative to 100 parts by weight of the total weight of the polyol (A) and the polyisocyanate (B) is preferably 40 parts by weight or less, more preferably 1 to 35 parts by weight, and particularly preferably 5 to 30 parts by weight.

[0063] When the curable urethane resin composition of the first aspect contains the urethanization catalyst (G), the amount of the urethanization catalyst (G) relative to 100 parts by weight of the total weight of the polyol (A) and the polyisocyanate (B) is preferably 10 parts by weight or less, more preferably 0.001 to 8 parts by weight, and particularly preferably 0.005 to 8 parts by weight.

[0064] When the curable urethane resin composition of the first aspect contains a filler (H), the amount of the filler (H) is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, and particularly preferably 33.8 parts by weight or less, per 100 parts by weight of the soft magnetic ferrite particles (D).

[0065] When the curable urethane resin composition of the first aspect contains an antioxidant (I), the amount of the antioxidant (I) per 100 parts by weight of the total weight of the polyol (A) and the polyisocyanate (B) is preferably 10 parts by weight or less, more preferably 1.0 to 8.0 parts by weight, and particularly preferably 1.5 to 7.0 parts by weight.

[0066] The curable urethane resin composition of the first embodiment can be obtained by uniformly mixing the polyol (A), polyisocyanate (B), phosphate ester (C), soft magnetic ferrite particles (D), and other components used as needed (such as surfactant (E), plasticizer (F), urethanization catalyst (G), filler (H), antioxidant (I), and dispersant (J)) using a known mixer (such as a mixing tank equipped with a stirrer). In producing the curable urethane resin composition, the components may be mixed all at once, or any two or more components may be mixed in advance and then the remaining components (which may be a mixture) may be mixed.

[0067] The curable urethane resin composition of the first aspect can be subjected to a urethane reaction on any substrate or in a mold having a shape appropriate for the purpose by a known method, thereby easily producing a cured urethane resin.

[0068] [Second Aspect] The curable urethane resin composition of the second aspect contains the polyol (A), polyisocyanate (B), phosphate ester (C), and soft magnetic ferrite particles (D) as two separate components, a first part and a second part. The second aspect is preferred from the viewpoint that the composition immediately after mixing the first part and the second part has flowability and exhibits high adhesion to the substrate.

[0069] In a second embodiment, the soft magnetic ferrite particles (D) are composed of first magnetic particles (D1) contained in a first agent and second magnetic particles (D2) contained in a second agent, the first agent contains polyol (A), phosphate ester (C), and the first magnetic particles (D1), and the second agent contains polyisocyanate (B) and the second magnetic particles (D2). The second embodiment will be described below.

[0070] In the curable urethane resin composition of the second embodiment, the polyol (A), the phosphate ester (C), and the first magnetic particles (D1) contained in the first agent can be the same as the polyol (A), the phosphate ester (C), and the soft magnetic ferrite particles (D) described in the first embodiment, and the preferred ones are also the same.

[0071] In the second embodiment, the content (total weight) of the phosphate ester (C) is preferably 0.1 to 4 parts by weight, more preferably 0.2 to 4 parts by weight, and even more preferably 0.2 to 3 parts by weight, per 100 parts by weight of the soft magnetic ferrite particles (D).

[0072] In the second embodiment, the content (total weight) of the soft magnetic ferrite particles (D) is preferably 40 to 74% by volume, more preferably 45 to 65% by volume, based on the volume of the curable urethane resin composition.

[0073] The content of the first magnetic particles (D1) in the first agent is preferably 40 to 74% by volume, and more preferably 45 to 65% by volume, based on the volume of the first agent. When the content of the first magnetic particles (D1) in the first agent is 40% by volume or more, magnetic permeability tends to be high, and when it is 74% by volume or less, moldability of the cured product is easily ensured.

[0074] The content of the phosphate ester (C) in the first agent is preferably 0.1 to 4 parts by weight, more preferably 0.2 to 4 parts by weight, and even more preferably 0.2 to 3 parts by weight, per 100 parts by weight of the first magnetic particles (D1). When the total weight of the phosphate ester (C) per 100 parts by weight of the first magnetic particles (D1) is 0.1 part by weight or more, the dispersibility of the magnetic particles can be improved. When the total weight of the phosphate ester (C) per 100 parts by weight of the first magnetic particles (D1) is 4 parts by weight or less, the physical properties of the resin after curing can be improved.

[0075] The polyisocyanate (B) and second magnetic particles (D2) contained in the second agent can be the same as the polyisocyanate (B) and soft magnetic ferrite particles (D) described in the first embodiment, and the preferred ones are also the same. The first magnetic particles (D1) and the second magnetic particles (D2) may be the same or different. When the first magnetic particles (D1) and the second magnetic particles (D2) are each composed of two or more fillers, the difference in the compounding ratio also includes cases where the first magnetic particles (D1) and the second magnetic particles (D2) are each composed of two or more fillers.

[0076] The content of the second magnetic particles (D2) in the second agent is preferably 40 to 74% by volume, and more preferably 45 to 65% by volume, based on the volume of the second agent. When the content of the second magnetic particles (D2) in the second agent is 40% by volume or more, magnetic permeability tends to be high, and when it is 74% by volume or less, moldability of the cured product is easily ensured.

[0077] The second agent may further contain a phosphate ester (C). When the second agent contains the phosphate ester (C), the content of the phosphate ester (C) in the second agent is preferably 4 parts by weight or less, and more preferably 0.2 to 4 parts by weight, per 100 parts by weight of the second magnetic particles (D2).

[0078] The total weight ratio of the polyol (A) and the polyisocyanate (B) is preferably 3 to 30% by weight, more preferably 3 to 20% by weight, based on the weight of the curable urethane resin composition (i.e., the total weight of the first and second parts).

[0079] In the curable urethane resin composition of the second aspect, the isocyanate index of the second part relative to the first part, i.e., the isocyanate index of the polyol (A) contained in the first part and the polyisocyanate (B) contained in the second part [total number of moles of isocyanate groups in the polyisocyanate (B) / total number of moles of hydroxyl groups in the polyol (A)] is preferably 0.8 to 1.2. When the isocyanate index is in this range, the physical properties of the resin after curing can be improved.

[0080] The first agent and the second agent may contain components other than the polyol (A), polyisocyanate (B), phosphate ester (C), and soft magnetic ferrite particles (D) exemplified in the description of the curable urethane resin composition of the first embodiment (surfactant (E), plasticizer (F), urethanization catalyst (G), filler (H), antioxidant (I), dispersant (J), etc.), as long as the effects of the present invention are not adversely affected.

[0081] When the first agent and / or the second agent contains the surfactant (E), the surfactant (E) is contained in an amount of preferably 0.001 to 30 parts by weight in total, more preferably 0.01 to 10 parts by weight, and particularly preferably 0.1 to 5 parts by weight, per 100 parts by weight of the soft magnetic ferrite particles (D) in the curable urethane resin composition.

[0082] When the first agent and / or the second agent contains a plasticizer (F), the total weight of the plasticizer (F) relative to 100 parts by weight of the total weight of the polyol (A) and the polyisocyanate (B) is preferably 40 parts by weight or less, more preferably 1 to 35 parts by weight, and particularly preferably 5 to 30 parts by weight.

[0083] When the first agent and / or the second agent contains the urethanization catalyst (G), the total weight of the urethanization catalyst (G) relative to 100 parts by weight of the total weight of the polyol (A) and the polyisocyanate (B) is preferably 10 parts by weight or less, more preferably 0.001 to 8 parts by weight, and particularly preferably 0.005 to 8 parts by weight.

[0084] When the first agent and / or the second agent contains a filler (H), the total weight of the filler (H) is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, and particularly preferably 33.8 parts by weight or less, per 100 parts by weight of the soft magnetic ferrite particles (D).

[0085] When the first agent and / or the second agent contains an antioxidant (I), the total weight of the antioxidant (I) per 100 parts by weight of the total weight of the polyol (A) and the polyisocyanate (B) is preferably 10 parts by weight or less, more preferably 1.0 to 8.0 parts by weight, and particularly preferably 1.5 to 7.0 parts by weight.

[0086] The viscosity of the first and second parts at 25°C is preferably 1 to 3000 Pa·s, and more preferably 5 to 2000 Pa·s, as measured using an MCR92 (manufactured by Anton Paar) in accordance with ASTM D 2556.

[0087] In the second embodiment, the first agent is obtained by uniformly mixing the polyol (A), the phosphate ester (C), the first magnetic particles (D1), and other components used as needed (surfactant (E), plasticizer (F), urethanization catalyst (G), filler (H), antioxidant (I), dispersant (J), etc.) using a known mixer (such as a mixing tank equipped with a stirrer). The components may be mixed all at once, or any two or more components may be mixed in advance and then the remaining components (which may be a mixture) may be mixed.

[0088] In the second embodiment, the second agent is obtained by uniformly mixing the polyisocyanate (B) and the second magnetic particles (D2), as well as other components used as needed (surfactant (E), plasticizer (F), urethanization catalyst (G), filler (H), antioxidant (I), dispersant (J), etc.) using a known mixer (such as a mixing tank equipped with a stirrer). The components may be mixed all at once, or any two or more components may be mixed in advance and then the remaining components (which may be a mixture) may be mixed.

[0089] The curable urethane resin composition of the second aspect can be easily produced as a cured product by mixing the first and second components and carrying out a urethanization reaction on any substrate or in a mold having a shape appropriate for the purpose using a known method. The first and second components may be mixed manually or using a known mixing device (such as a container equipped with a stirrer), or may be mixed continuously using a known two-component mixing and supplying device.

[0090] [2. Urethane Resin] The urethane resin of the present invention is a cured product of the curable urethane resin composition of the present invention. The urethane resin of the present invention is a urethane resin obtained by curing the curable urethane resin composition of the first or second aspect described above by a known method.

[0091] The urethane resin of the present invention has high magnetic permeability and excellent flexibility, impact resistance, and vibration resistance, and can therefore be used in applications such as wire-wound inductors, electromagnetic wave shields, and wireless power transmission (WPT).

[0092] The present specification discloses the following:

[0093] The present disclosure (1) relates to a polyol (A), a polyisocyanate (B), and a polyisocyanate having the following general formula (1): [In general formula (1), R １ represents a hydrogen atom, an alkyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, and some of the hydrogen atoms of the alkyl group or alkenyl group may be substituted with halogen atoms. １ O is an alkyleneoxy group having 2 to 3 carbon atoms, and n1 is A １ represents the average number of moles of O added, and is a number from 0 to 15; R ２ is a hydrogen atom or -(A ２ O) ｎ２ R ３ (R ３ represents an alkyl group having 2 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, and some of the hydrogen atoms of the alkyl group or alkenyl group may be substituted with halogen atoms. ２ O is an alkyleneoxy group having 2 to 3 carbon atoms, and n2 is A ２ and (C) represents the average number of moles of O added, and is a number from 0 to 15.] and soft magnetic ferrite particles (D).

[0094] The present disclosure (2) is the curable urethane resin composition according to the present disclosure (1), in which the content of the soft magnetic ferrite particles (D) is 40 to 74 volume % based on the volume of the curable urethane resin composition.

[0095] The present disclosure (3) is the curable urethane resin composition according to the present disclosure (1) or (2), in which the polyol (A) contains a polyether polyol (a1).

[0096] The present disclosure (4) is the curable urethane resin composition according to any one of the present disclosures (1) to (3), wherein the content of the phosphate ester (C) is 0.1 to 4 wt % based on the weight of the soft magnetic ferrite particles (D).

[0097] The present disclosure (5) is a curable urethane resin composition according to any one of the present disclosures (1) to (4), which comprises a first agent and a second agent, the soft magnetic ferrite particles (D) comprising first magnetic particles (D1) contained in the first agent and second magnetic particles (D2) contained in the second agent, the first agent containing polyol (A), phosphate ester (C), and first magnetic particles (D1), and the second agent containing polyisocyanate (B) and second magnetic particles (D2).

[0098] The present disclosure (6) is the curable urethane resin composition according to the present disclosure (5), in which the content of the first magnetic particles (D1) in the first agent is 40 to 74 volume % based on the volume of the first agent.

[0099] The present disclosure (7) is the curable urethane resin composition according to the present disclosure (5) or (6), in which the content of the phosphate ester (C) in the first agent is 0.1 to 4 parts by weight per 100 parts by weight of the first magnetic particles (D1).

[0100] The present disclosure (8) is a curable urethane resin composition according to any one of the present disclosures (5) to (7), in which the content of the second magnetic particles (D2) in the second agent is 40 to 74 volume % based on the volume of the second agent.

[0101] The present disclosure (9) is the curable urethane resin composition according to any one of the present disclosures (5) to (8), wherein the second agent further contains a phosphate ester (C), and the content of the phosphate ester (C) in the second agent is 4 parts by weight or less per 100 parts by weight of the second magnetic particles (D2).

[0102] The present disclosure (10) is the curable urethane resin composition according to any one of the present disclosures (5) to (9), wherein the isocyanate index of the second agent relative to the first agent is 0.8 to 1.2.

[0103] The present disclosure (11) is a urethane resin that is a cured product of the curable urethane resin composition according to any one of the present disclosures (1) to (10).

[0104] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following, "parts" refers to "parts by weight." The components used in the examples and comparative examples are as shown in Table 1.

[0105] In Table 1, NCO means an isocyanate group. The NCO content of the polyisocyanate indicates the isocyanate group content (wt%) measured in accordance with JIS K 1603-1:2007. The phosphate ester (C) is a monoester (R ２ It is a mixture of esters (where hydrogen atoms are present) and diesters.

[0106]

[0107] Examples 1 to 10 and Comparative Examples 1 and 2 The components shown in Table 1 were mixed in the formulation shown in Table 2 to obtain curable urethane resin compositions. Urethane resin sheets were produced using the obtained curable urethane resin compositions by the following manufacturing method. Each composition was poured into a molding die (1 cm long x 1 cm wide x 0.2 cm deep) to fill it. The mixture was pressed using a press and allowed to stand at 25°C for 24 hours to react, yielding urethane resin sheets. The compositions of Comparative Examples 1 and 2 could not be molded, and urethane resin sheets could not be obtained. The molded compositions (Examples 1 to 10) were evaluated for complex relative magnetic permeability, staining / powder shedding, flexibility, and thermal conductivity using the methods described below. The results are shown in Table 2. For Comparative Examples 1 and 2, no urethane resin sheets could be obtained and evaluation could not be performed, as described above, and therefore these are indicated as "unmoldable" in Table 2.

[0108] Examples 11 to 37 and Comparative Examples 3 to 6 The components shown in Table 1 were mixed in the formulations shown in Tables 3 to 8 to prepare a first part and a second part. The first part and the second part were then mixed until uniform, yielding a curable urethane resin composition. The viscosity of the first and second parts was measured at 25°C using an MCR92 viscometer (manufactured by Anton Paar) in accordance with ASTM D 2556. The results are shown in Tables 3 to 8. In Comparative Examples 4 to 6, those for which viscosity measurement was difficult are indicated as "unmeasurable" in Tables 5 and 8. Using the resulting curable urethane resin compositions, urethane resin sheets were produced using the same manufacturing method as in Example 1. The compositions of Comparative Examples 3 to 6 could not be molded, and urethane resin sheets could not be obtained. The molded products (Examples 11 to 37) were evaluated for complex relative magnetic permeability, staining / dusting resistance, flexibility, and thermal conductivity using the following methods. The results are shown in Tables 3 to 8. For Comparative Examples 3 to 6, as described above, no urethane resin sheet could be obtained and evaluation could not be performed, and therefore, in Tables 5 and 8, they are indicated as "unmoldable."

[0109] [Evaluation Method] <Complex Relative Permeability> A urethane resin sheet was punched into a ring shape with an outer diameter of 18±1 mm, an inner diameter of 9±0.5 mm, and a thickness of 2.0±0.5 mm, and the punched ring sample was set in an impedance analyzer (Agilent Technologies: E4991A). Inductance and resistance were measured at frequencies of 1 to 1000 MHz using Test Fixture 16454, and the real part μ' and imaginary part μ'' of the complex relative permeability at a frequency of 10 MHz were determined. The real part μ' is shown in Tables 2 to 8.

[0110] <Staining and Powder Falling> An adhesive tape (3M, polyethylene cloth tape 386, width 25 mm) was attached to a urethane resin sheet using a pressure roller as specified in JIS Z 0237. The adhesive tape was peeled off in a direction 180° from the sheet surface at a peeling speed of 50 mm / sec, and the staining and powder falling off of the adhesive surface was evaluated according to the following criteria to confirm the moldability of the molded product. 5: No staining or powder falling off was observed on the adhesive surface. 4: Staining was observed on part of the adhesive surface, but no powder falling off was observed. 3: Staining and powder falling off were observed on part of the adhesive surface. 2: Staining and powder falling off were observed over the entire adhesive surface. 1: Significant staining and powder falling off were observed over the entire adhesive surface.

[0111] <Flexibility> The urethane resin sheet was wrapped around a round rod with an outer diameter of 11 mm, and the flexibility of the molded product was confirmed by evaluating the cracks and tears in the sheet according to the following criteria: 5: No cracks or tears were observed in the resin sheet. 4: Cracks were observed in some parts of the resin sheet, but no tears were observed. 3: Tears were observed in some parts of the resin sheet. 2: Tears were observed throughout the resin sheet. 1: The resin sheet was very brittle and could not be tested.

[0112] <Thermal Conductivity> After leaving the urethane resin sheet at rest for 2 hours at 25°C, the thermal conductivity (unit: W / m K) was measured by the laser flash method using a thermal conductivity meter "Xenon Flash Analyzer LFA447 NanoFlash" (manufactured by Netsch Japan Co., Ltd.). Higher thermal conductivity indicates better heat dissipation properties.

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120] These results demonstrate that the curable urethane resin composition of the present invention can provide a urethane resin material that has high magnetic permeability and is excellent in moldability and flexibility.

Claims

1. A mixture of polyol (A), polyisocyanate (B), and a compound represented by the following general formula (1): [In general formula (1), R １ A is a hydrogen atom, an alkyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, and a portion of the hydrogen atoms of the alkyl group or alkenyl group may be substituted with a halogen atom. １ O is an alkyleneoxy group having 2 to 3 carbon atoms, and n1 is A １ represents the average number of moles of O added, which is a number from 0 to 15; R ２ is a hydrogen atom or -(A ２ O) ｎ２ R ３ (R ３ A is an alkyl group having 2 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, and some of the hydrogen atoms of the alkyl group or the alkenyl group may be substituted with halogen atoms. ２ O is an alkyleneoxy group having 2 to 3 carbon atoms, and n2 is A ２ and m represents the average number of moles of O added, and is a number from 0 to 15.] and soft magnetic ferrite particles (D).

2. The curable urethane resin composition according to claim 1, wherein the content of the soft magnetic ferrite particles (D) is 40 to 74 volume % based on the volume of the curable urethane resin composition.

3. A curable urethane resin composition according to claim 1 or 2, wherein the polyol (A) contains a polyether polyol (a1).

4. The curable urethane resin composition according to claim 1 or 2, wherein the content of the phosphate ester (C) is 0.1 to 4% by weight based on the weight of the soft magnetic ferrite particles (D).

5. A curable urethane resin composition according to claim 1 or 2, which comprises a first agent and a second agent, the soft magnetic ferrite particles (D) comprising first magnetic particles (D1) contained in the first agent and second magnetic particles (D2) contained in the second agent, the first agent containing polyol (A), phosphate ester (C) and first magnetic particles (D1), and the second agent containing polyisocyanate (B) and second magnetic particles (D2).

6. The curable urethane resin composition according to claim 5, wherein the content of the first magnetic particles (D1) in the first agent is 40 to 74 volume % based on the volume of the first agent.

7. The curable urethane resin composition according to claim 5, wherein the content of the phosphate ester (C) in the first agent is 0.1 to 4 parts by weight per 100 parts by weight of the first magnetic particles (D1).

8. The curable urethane resin composition according to claim 5, wherein the content of the second magnetic particles (D2) in the second agent is 40 to 74 volume % based on the volume of the second agent.

9. The curable urethane resin composition according to claim 5, wherein the second agent further contains a phosphate ester (C), and the content of the phosphate ester (C) in the second agent is 4 parts by weight or less per 100 parts by weight of the second magnetic particles (D2).

10. The curable urethane resin composition according to claim 5, wherein the isocyanate index of the second part relative to the first part is 0.8 to 1.

2.

11. A urethane resin which is a cured product of the curable urethane resin composition according to claim 1 or 2.

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