Curable urethane resin composition and urethane resin

Abstract

The present invention addresses the problem of providing a high-permeability soft magnetic urethane resin material which has high permeability, excellent moldability and flexibility, and which can be easily produced. The present invention pertains to a curable urethane resin composition containing 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 represents a hydrogen atom, a C2-20 alkyl group, or a C2-20 alkenyl group, some of the hydrogen atoms in the alkyl group or alkenyl group may be substituted by halogen atoms, and R1 represents a hydrogen atom, a C2-20 alkyl group, or a C2-20 alkenyl group; in the formula, A1O is an alkylene oxy group having 2-3 carbon atoms, n1 represents the average number of moles of A1O added and is a number of 0-15, R2 is a hydrogen atom or-(A2O) n2R3 (R3 is an alkyl group having 2-20 carbon atoms or an alkenyl group having 2-20 carbon atoms, some of the hydrogen atoms in the alkyl group or the alkenyl group may be substituted by halogen atoms, A2O is an alkylene oxy group having 2-3 carbon atoms, and n2 represents the average number of moles of A2O added and is a number of 0-15). ].

Description

Technical Field

[0001] This invention relates to curable urethane resin compositions and urethane resins. Background Technology

[0002] With the miniaturization and increasing performance of electronic components, there are growing demands for high performance, high reliability, and low cost in magnetic composite materials.

[0003] As a component of the boost circuit in a power supply system, there is an inductor that can store electrical energy in the form of magnetic energy. The composite magnetic material used in the core of the inductor can be obtained, for example, by filling a mixture of soft magnetic powder and resin powder and pressing it into shape as a powder-pressed body.

[0004] In addition, methods for sealing components and parts such as coils include, for example, compression molding, which involves pressing powdered sealing material and the sealed component under high pressure, and molding, which involves covering the sealed component with a sealing material composition and allowing the composition to cure or harden. Magnetic composite materials that impart electromagnetic functionality by filling these sealing materials with magnetic particles are also known.

[0005] Patent documents 1 to 4 disclose resin compositions containing curable resin and magnetic particles, and magnetic composite materials obtained by curing the resin compositions.

[0006] However, existing magnetic composite materials lack flexibility and are prone to cracking due to vibration and impact on electronic components. In addition, if magnetic particles are highly packed into the resin, the flowability decreases, making it difficult to fully increase the content of magnetic particles, and sometimes the magnetic permeability becomes insufficient.

[0007] Furthermore, because the pressed powder molding process involves molding at pressures exceeding 10 MPa, typically several hundred MPa, the soft magnetic powders are pressed together, damaging the insulating coating and increasing coercivity due to stress and strain. Damage to the insulating coating leads to increased eddy current losses in the molded body due to the electrical connections between the soft magnetic powders. This increased coercivity results in increased iron losses, necessitating a stress-strain relief process. In addition, the pressing process is time-consuming and increases costs.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent No. 4692768

[0011] Patent Document 2: Japanese Patent No. 5700298

[0012] Patent Document 3: Japanese Patent No. 7211727

[0013] Patent Document 4: Japanese Patent No. 6813044 Summary of the Invention

[0014] The problem that the invention aims to solve

[0015] The present invention was made in view of the above-mentioned situation, and its object is to provide a high magnetic permeability soft magnetic urethane resin material with high magnetic permeability, excellent formability and flexibility, and easy manufacturing capability.

[0016] means for solving problems

[0017] This invention relates to a curable urethane resin composition comprising a polyol (A), a polyisocyanate (B), a phosphate ester (C) represented by the following general formula (1), and soft magnetic ferrite particles (D). [Chemical Formula 1]

[0018] In general formula (1), R 1 It is a hydrogen atom, an alkyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, wherein some of the hydrogen atoms of the alkyl or alkenyl group may be replaced by halogen atoms. A 1 O represents an alkyleneoxy group with 2 to 3 carbon atoms, and n1 represents A. 1 The average number of moles added by O is a number ranging from 0 to 15, R 2 For hydrogen atoms or -(A 2 O) n2 R 3 (R 3 It is an alkyl group or an alkenyl group having 2 to 20 carbon atoms, wherein some of the hydrogen atoms of the alkyl or alkenyl group may be replaced by halogen atoms. A 2 O represents an alkyleneoxy group with 2 to 3 carbon atoms, and n2 represents A. 2 The average number of moles of O added is in the range of 0 to 15. ]; A urethane resin, which is the cured product of the curable urethane resin composition.

[0019] Invention Effects

[0020] According to the present invention, a high-permeability soft magnetic urethane resin material with high magnetic permeability, excellent moldability and flexibility, and easy manufacturing capability can be provided. Detailed Implementation

[0021] [1. Curable urethane resin composition]

[0022] The curable urethane resin composition of the present invention comprises a polyol (A), a polyisocyanate (B), a phosphate ester (C) represented by the following general formula (1), and soft magnetic ferrite particles (D).

[0023] [Chemical Formula 2]

[0024] In general formula (1), R 1 It is a hydrogen atom, an alkyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, wherein some of the hydrogen atoms of the alkyl or alkenyl group may be replaced by halogen atoms. A 1 O represents an alkyleneoxy group with 2 to 3 carbon atoms, and n1 represents A. 1 The average number of moles added by O is a number ranging from 0 to 15, R 2 For hydrogen atoms or -(A 2 O) n2 R 3 (R 3 It is an alkyl group or an alkenyl group having 2 to 20 carbon atoms, wherein some hydrogen atoms of the alkyl or alkenyl group may be replaced by halogen atoms, A 2 O represents an alkyleneoxy group with 2 to 3 carbon atoms, and n2 represents A. 2 The average number of moles added to O (ranging from 0 to 15).

[0025] The curable urethane resin composition of the present invention can be either a first embodiment in which all of the polyol (A), polyisocyanate (B), phosphate ester (C), and soft magnetic ferrite particles (D) are contained in one agent; or a second embodiment in which the polyol (A), polyisocyanate (B), phosphate ester (C), and soft magnetic ferrite particles (D) are contained separately in two agents. First, the first embodiment will be described.

[0026] [First Method]

[0027] The first-method cured urethane resin composition comprises, in one agent, a polyol (A), a polyisocyanate (B), a phosphate ester (C), and soft magnetic ferrite particles (D).

[0028] The polyol (A) preferably contains at least one selected from polyether polyol (a1), polyester polyol (a2), polycarbonate polyol (a3), and polyolefin polyol (a4). The polyol (A) preferably contains polyether polyol (a1).

[0029] Examples of polyether polyols (a1) include aliphatic polyether polyols and aromatic polyether polyols.

[0030] Examples of aliphatic polyether polyols include diols obtained by adding polymerized epoxides (hereinafter referred to as AO) to aliphatic polyols with 2 to 20 carbon atoms.

[0031] Examples of aliphatic polyols with 2 to 20 carbon atoms include ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, dodecanediol, neopentyl glycol, and glycerol, with propylene glycol, 1,4-butanediol (tetramethylenediol), and glycerol being preferred.

[0032] Examples of AOs include ethylene oxide, 1,2- or 1,3-epoxypropane, and 1,2-, 1,3-, 1,4- or 2,3-epoxybutane.

[0033] These AOs can be used in combination of two or more types. When using two or more types of AOs, the combination method can be any one of block addition, random addition, or a combination of both.

[0034] As aliphatic polyether polyols, examples include polyoxyethylene polyols (such as polyethylene glycol), polyoxypropylene polyols (such as polypropylene glycol), polyoxyethylene / oxypropylene polyols, polytetramethylene glycol, and polyoxypropylene glycerol ethers.

[0035] It can also be obtained from the market as SANNIX PP-200, GP-3000 [manufactured by Sanyo Chemical Industries, Ltd.], PTMG250, 650 [manufactured by Mitsubishi Chemical Corporation], UNIOL PB-700 [manufactured by Nippon Oil Corporation], etc.

[0036] Examples of aromatic polyether polyols include compounds with 6 to 20 carbon atoms (bisphenol, resorcinol, hydroquinone, etc.) having an aromatic ring and two or more hydroxyl groups, and epoxide adducts with 2 to 4 carbon atoms.

[0037] Specifically, examples include ethylene oxide (hereinafter referred to as EO) adducts of bisphenol A [EO2 molar adduct of bisphenol A, EO4 molar adduct of bisphenol A, EO6 molar adduct of bisphenol A, EO8 molar adduct of bisphenol A, EO10 molar adduct of bisphenol A, and EO20 molar adduct of bisphenol A, etc.] and propylene oxide (hereinafter referred to as PO) adducts of bisphenol A [PO2 molar adduct of bisphenol A, PO3 molar adduct of bisphenol A, PO5 molar adduct of bisphenol A, etc.], as well as EO or PO adducts of resorcinol, etc.

[0038] From the viewpoint of excellent formability, aliphatic polyether polyols are preferred as polyether polyols (a1).

[0039] From the viewpoint of excellent formability, the number average molecular weight (Mn) of the polyether polyol (a1) is preferably 100 to 3000, more preferably 200 to 2000.

[0040] It should be noted that, in this specification, the number-average molecular weight (Mn) can be determined using gel permeation chromatography (hereinafter referred to as GPC) under the following conditions.

[0041] Device main body: HLC-8120 (manufactured by Tosoh Corporation)

[0042] Column: TSKgel α6000, G3000 PWXL manufactured by Tosoh Corporation

[0043] Detector: RI (Refractive Index)

[0044] Eluent: 0.5% sodium acetate - water / methanol (70 / 30 v / v)

[0045] Elution flow rate: 1.0 ml / min

[0046] Column temperature: 40℃

[0047] Sample concentration: 0.25% by weight

[0048] Injection volume: 200μl

[0049] Standard reference material: TSK standard polyoxyethylene manufactured by Tosoh Corporation

[0050] Data processing software: GPC-8020 II (manufactured by Tosoh Corporation)

[0051] Examples of polyester polyols (a2) include polyols [the aforementioned polyether polyols (a1), aliphatic diols, aliphatic polyols, alicyclic polyols, AO adducts of alicyclic polyols, etc.] and polycarboxylic acid condensates.

[0052] Examples of polycarboxylic acids include chain-like aliphatic polycarboxylic acids with 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-methyl adipic acid, heptapic acid, 2,2,6,6-tetramethylheptanepic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, pentadecanoic acid, tetradecanoic acid, heptadecanic acid, decadecanoic acid, etc.]. Octadecanedioic acid, nonadecanedioic acid, and eicosanoic acid, etc.; alicyclic polycarboxylic acids with 5 to 20 carbon atoms [cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid, and camphoric acid]; aromatic polycarboxylic acids with 8 to 20 carbon atoms [terephthalic acid, isophthalic acid, 2-methylterephthalic acid, 4,4-stilbenedicarboxylic acid, naphthalenedicarboxylic acid, 4,4-biphenyldicarboxylic acid, phthalic acid, and diphenyl etherdicarboxylic acid, etc.], etc., can be obtained from the market as Kuraray polyol P-2010 [manufactured by Kuraray Co., Ltd.], etc.

[0053] Examples of aliphatic diols include aliphatic diols with 2 to 20 carbon atoms, preferably 2 to 10, and more preferably 2 to 5.

[0054] Examples of aliphatic polyols include alcohols with 3 to 20 carbon atoms, such as glycerol and pentaerythritol, with glycerol being the preferred choice.

[0055] Examples of alicyclic polyols include those with 4 to 16 carbon atoms (1,4-cyclohexanediol, 1,4-cyclohexanediethanol and hydrogenated bisphenol A).

[0056] Examples of AO adducts of alicyclic polyols include compounds formed by adding AO to the aforementioned alicyclic polyols. The AO can be the same substance exemplified in the description of polyether polyols (a1), and the preferred substance is also the same.

[0057] As polycarbonate polyols (a3), examples include reactants of polyols [the aforementioned polyether polyols (a1), aliphatic diols, aliphatic polyols, alicyclic polyols, AO adducts of alicyclic polyols, etc.] with phosgene, which can be obtained from the market as Kuraray polyols C-590, C2090 [manufactured by Kuraray Co., Ltd.].

[0058] Examples of polyolefin polyols (a4) include polybutadiene polyols and hydrogenated polybutadiene diols.

[0059] As for the polyol (A), from the viewpoint of the physical properties of the cured resin, a polyol having an average of at least two hydroxyl groups per molecule is preferred.

[0060] Polyol (A) can be used alone or in combination of two or more.

[0061] From the viewpoint of excellent formability, the number average molecular weight of the polyol (A) is preferably 100 to 3000, more preferably 200 to 2000.

[0062] Examples of polyisocyanates (B) include chain aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and isocyanurates of these polyisocyanates.

[0063] Examples of chain-like aliphatic polyisocyanates include those with 4 to 20 carbon atoms, with preferred examples being ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. These can also be obtained commercially as A201H [a dimer of hexamethylene diisocyanate manufactured by Asahi Kasei Corporation].

[0064] Examples of alicyclic polyisocyanates include those with 6 to 17 carbon atoms, with isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, cyclohexene diisocyanate, methylcyclohexene diisocyanate, bis(2-isocyanate ethyl)-4-cyclohexene-1,2-dicarboxylic acid ester, and 2,5- or 2,6-norbornane diisocyanate being preferred. These alicyclic polyisocyanates are commercially available as Desmodur I [manufactured by Sumika Covestro Urethane Co., Ltd.] and similar products.

[0065] Examples of aromatic polyisocyanates include those with 8 to 22 carbon atoms, with preferred examples being 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-toluene diisocyanate (TDI), 4,4'- or 2,4'-diphenylmethane diisocyanate (MDI), meta- or p-isocyanate phenylsulfonyl isocyanate, 4,4'-diisocyanate biphenyl, 3,3'-dimethyl-4,4'-diisocyanate biphenyl, 3,3'-dimethyl-4,4'-diisocyanate diphenylmethane, 1,5-naphthalene diisocyanate, meta- or p-isocyanate phenylsulfonyl isocyanate, meta- or p-phenylene diisocyanate (XDI), and α,α,α',α'-tetramethylphenylene diisocyanate (TMXDI).

[0066] Examples of isocyanurates of polyisocyanates include trimers of polyisocyanates (such as the aforementioned chain aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates).

[0067] The isocyanurate form of polyisocyanates is available on the market as TLA-100 [a trimer of hexamethylene diisocyanate manufactured by Asahi Kasei Corporation] and others.

[0068] From the viewpoint of excellent formability, polyisocyanate (B) preferably contains at least one of the group consisting of isocyanurate body selected from chain aliphatic polyisocyanate, alicyclic polyisocyanate, chain aliphatic polyisocyanate and alicyclic polyisocyanate.

[0069] Polyisocyanates (B) can be used alone or in combination of two or more.

[0070] Based on the weight of the curable urethane resin composition, the total weight ratio of polyol (A) and polyisocyanate (B) in the curable urethane resin composition is preferably 2 to 30% by weight, more preferably 3 to 20% by weight.

[0071] The isocyanate index of polyol (A) and polyisocyanate (B) [total moles of isocyanate groups in polyisocyanate (B) / total moles of hydroxyl groups in polyol (A)] is preferably 0.8 to 1.2. If the isocyanate index is within the above range, the curability of the composition can be improved.

[0072] The content of isocyanate groups can be calculated according to the method in JIS K 1603-1:2007, etc.

[0073] Phosphate ester (C) is represented by the following general formula (1).

[0074] [Chemical Formula 3]

[0075] In general formula (1), R 1 It consists of hydrogen atoms, an alkyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, wherein some of the hydrogen atoms in the aforementioned alkyl or alkenyl groups may be replaced by halogen atoms. A 1 O represents an alkyleneoxy group with 2 to 3 carbon atoms, and n1 represents A. 1 The average number of moles added by O is a number ranging from 0 to 15, R 2 For hydrogen atoms or -(A 2 O) n2 R 3 (R 3It is an alkyl group or an alkenyl group having 2 to 20 carbon atoms, wherein some of the hydrogen atoms of the aforementioned alkyl or alkenyl group can be replaced by halogen atoms. A 2 O represents an alkyleneoxy group with 2 to 3 carbon atoms, and n2 represents A. 2 The average number of moles added to O (ranging from 0 to 15).

[0076] In general formula (1), R 1 It consists of hydrogen atoms, alkyl groups having 2 to 20 carbon atoms, or alkenyl groups having 2 to 20 carbon atoms, wherein some of the hydrogen atoms of the aforementioned alkyl or alkenyl groups may be replaced by halogen atoms.

[0077] Examples of alkyl groups with 2 to 20 carbon atoms include ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, and octadecyl, which can be either straight-chain or branched.

[0078] Examples of alkenyl groups with 2 to 20 carbon atoms include vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, heptadecenyl, and octadecenyl. They can be linear or branched, and the position of the double bond is not limited.

[0079] Fluorine atoms are preferred as halogen atoms.

[0080] R 1 It can be linear or branched, but linear is preferred. Furthermore, from the viewpoint of the mechanical strength of the cured product and the dispersibility of the filler, alkyl groups with 12 to 18 carbon atoms are preferred.

[0081] In general formula (1), A 1 O refers to an alkylene oxide with 2 to 3 carbon atoms, such as ethylene oxide and propylene oxide. From a dispersibility point of view, ethylene oxide is preferred.

[0082] n1 represents A 1 The average number of moles of O added is 0 to 15. From the viewpoint of good dispersibility of magnetic particles and good mechanical strength of the cured product, it is preferably 3 to 15, more preferably 3 to 13, and even more preferably 4 to 11.

[0083] R 2 For hydrogen atoms or -(A 2 O) n2 R 3 (R 3It is an alkyl group or an alkenyl group having 2 to 20 carbon atoms, wherein some of the hydrogen atoms of the aforementioned alkyl or alkenyl group may be replaced by halogen atoms. A 2 O represents an alkyleneoxy group with 2 to 3 carbon atoms, and n2 represents A. 2 The average number of moles added to O is between 0 and 15.

[0084] As R 3 Examples of R can be cited. 1 The same substances have the same preferred substances.

[0085] As A 2 O, can be cited as an example related to A 1 For the same substance, the preferred substance is also the same.

[0086] R 2 When the atom is hydrogen, the compound of general formula (1) is a monoester, R 2 For -(A 2 O) n2 R 3 At that time, the compound of general formula (1) is a diester. Additionally, R... 2 For -(A 2 O) n2 R 3 At that time, R 1 With R 3 They can be the same or different. n1 and n2 can be the same or different.

[0087] As a phosphate ester (C) represented by general formula (1), two or more Rs can be used in combination. 1 Different phosphate esters can also use monoesters (R 2 (H) and diester (R) 2 For -(A 2 O) n2 R 3 A mixture of phosphates. The phosphate ester (C) represented by general formula (1) is usually obtained in the form of a mixture of monoester and diester (mono / di mixture). Alternatively, salts of the phosphate ester represented by general formula (1) (such as metal salts of sodium, potassium and magnesium, ammonium salts, etc.) may also be used.

[0088] Preferred substances for 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, fluoroalkyl ether phosphate esters, fluoroalkyl phosphate esters, etc., with alkyl ether phosphate esters being more preferred.

[0089] The phosphate ester (C) represented by general formula (1) can be obtained by phosphorylation using polyether and phosphorus oxide. It is also available commercially as Chropol P-10A [manufactured by Sanyo Chemical Industry Co., Ltd.], DISPARLON DA-375 [manufactured by Kusumoto Chemical Co., Ltd.], PLYSURF A208N [manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.], Phosphhanol RL-210 [manufactured by Toho Chemical Industry Co., Ltd.], R 1 ,R 3 C18 alkyl group, A 1 O,A 2 O: Ethyleneoxy group, n1, n2: 2, mono / di mixture], Phosphhanol RS-710 [manufactured by Toho Chemical Industry Co., Ltd., (C12-15) alkanol polyether-9 phosphate ester, R 1 ,R 3 : C12-15 alkyl groups, A 1 O,A 2 O: Ethyleneoxy group, n1, n2: 9, mono / di mixture], Phosphhanol RS-410 [manufactured by Toho Chemical Industry Co., Ltd., (C12-15) alkanol polyether-3 phosphate ester, R 1 ,R 3 : C12-15 alkyl groups, A 1 O,A 2 O: Ethyleneoxy group, n1, n2: 3, mono / di mixture], Phosphhanol RB-410 [manufactured by Toho Chemical Industry Co., Ltd., oleyl alcohol polyether-4 phosphate ester, R 1 ,R 3 C18 alkenyl group, A 1 O,A 2 O: Ethyleneoxy group, n1, n2: 4, mono / di mixture], Phosphhanol RL-310 [manufactured by Toho Chemical Industry Co., Ltd., stearyl alcohol polyether-3 phosphate, R 1 ,R 3 C18 alkyl group, A 1 O,A 2 O: Ethyleneoxy, n1, n2: 3, mono / di mixture], JP-518-O [manufactured by Jōhoku Chemical Industry Co., Ltd., oleoyl acid phosphate, n1, n2: 0, mono / di mixture], JP-506H [manufactured by Jōhoku Chemical Industry Co., Ltd., butoxyethyl acid phosphate, n1, n2: 1, mono / di mixture], etc.

[0090] Phosphate esters (C) can be used alone or in combination of two or more.

[0091] From the viewpoint of the dispersibility of magnetic particles, the content of phosphate ester (C) is preferably 0.1 to 4% by weight based on the weight of soft magnetic ferrite particles (D) [0.1 to 4 parts by weight relative to 100 parts by weight of soft magnetic ferrite particles (D)], more preferably 0.2 to 4% by weight, and even more preferably 0.2 to 3% by weight.

[0092] Examples of materials that can be used as soft magnetic ferrite particles (D) include spinel-type soft magnetic ferrites. Examples of such soft magnetic ferrites include 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. Furthermore, for modification purposes, elements such as Co and Si can be added as constituent elements of the soft magnetic ferrite.

[0093] The magnetic material constituting the magnetic particles can be appropriately selected based on the desired magnetization characteristics (relative permeability) and volume resistivity.

[0094] Soft magnetic ferrites are available on the market 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), and FRX-843 (MnMgZn ferrite) [all manufactured by Toda Kogyo Co., Ltd.].

[0095] Soft magnetic ferrite particles (D) can be used alone or in combination of two or more.

[0096] There are no particular limitations on the shape of the soft magnetic ferrite particles (D), and fibrous and granular soft magnetic ferrite particles are preferred. In the case of particles, spherical, plate-like, needle-like, or irregularly shaped (obtained by crushing, etc.) particles can be used. Among these, spherical particles are preferred from the viewpoint of high resin filling performance, and particles with adjusted particle size distribution are more preferred.

[0097] When the soft magnetic ferrite particles (D) are spherical, from the viewpoint of magnetic permeability and filling properties, the volume average particle size [D50: the particle size that accounts for 50% of the cumulative particle amount in the particle size distribution based on volume] of the soft magnetic ferrite particles (D) is preferably 1 to 200 μm, more preferably 2 to 150 μm.

[0098] The volume average particle size of the soft magnetic ferrite particles (D) can be measured using a laser diffraction particle size distribution measuring device [such as the SALD-2000A manufactured by Shimadzu Corporation, or the LA-920 manufactured by Horiba Corporation]. When components other than the soft magnetic ferrite particles (D) are dissolved in a solvent, the solution of the composition can also be measured.

[0099] The soft magnetic ferrite particles (D) are preferably soft magnetic ferrite powder.

[0100] Soft magnetic ferrite powder can be obtained, for example, by mixing raw materials such as oxides, carbonates, hydroxides, and oxalates of the elements constituting soft magnetic ferrite in a specified composition ratio, or by precipitating the elements in an aqueous solution and then pulverizing the mixture after firing it in the atmosphere at 700–1300°C for 1–20 hours. From an environmental protection perspective, soft magnetic ferrite powder obtained by pulverizing waste generated during the manufacturing process of various ferrite cores and ferrite sintered plates can be reused.

[0101] The content of 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. When the content of soft magnetic ferrite particles (D) is 40% by volume or more, there is a tendency for the magnetic permeability to increase, while when it is 74% by volume or less, it is easy to ensure the molding processability of the cured product.

[0102] The curable urethane resin composition of the first embodiment may contain other components not belonging to polyols (A), polyisocyanates (B), phosphate esters (C), and soft magnetic ferrite particles (D), to a extent that does not affect the effects of the present invention. Examples of such other components include surfactants (E), plasticizers (F), urethane esterification catalysts (G), fillers (H), antioxidants (I), and dispersants (J). The curable urethane resin composition may also contain known additives used in urethane resins (such as ultraviolet absorbers described in Japanese Patent Application Publication No. 2018-076537) as other components.

[0103] As surfactants (E), polyoxyethylene type nonionic surfactants (E1), ester type nonionic surfactants (E2), anionic surfactants (E3) and cationic surfactants (E4) are preferred.

[0104] Examples of polyoxyethylene-type nonionic surfactants (E1) include aliphatic alcohols (4 to 30 carbon atoms), alkyl (1 to 30 carbon atoms) phenols, aliphatic (4 to 30 carbon atoms) amines, or aliphatic (4 to 30 carbon atoms) AO adducts (preferably with an addition molar ratio of 1 to 30).

[0105] The aliphatic alcohols constituting polyoxyethylene-type nonionic surfactants (E1) are preferably n-, iso-, secondary or tert-butanol, octanol and dodecanol, etc.; the alkylphenols are preferably phenol, methylphenol and nonylphenol, etc.; the aliphatic amines are preferably laurylamine and methylstearylamine, etc.; and the aliphatic amides are preferably stearamide, etc.

[0106] Examples of ester-type nonionic surfactants (E2) include ester compounds of fatty acids with 4 to 30 carbon atoms (such as lauric acid, stearic acid, and oleic acid) and polyols other than sucrose, sorbitol, and glycerol.

[0107] Examples of anionic surfactants (E3) include carboxylate, sulfate, and sulfonate types.

[0108] Examples of carboxylate-type ...

[0109] Examples of cationic surfactants (E4) include primary to tertiary amine salts and quaternary ammonium salts.

[0110] Examples of primary to tertiary amine salts include hydrochlorides of aliphatic amines (primary (laurylamine, etc.), secondary (dibutylamine, etc.) and tertiary amines (dimethylstearylamine, etc.)) with 4 to 30 carbon atoms, and inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, and phosphate, etc.) salts of triethanolamine and monoesters of fatty acids with 4 to 30 carbon atoms. Examples of quaternary ammonium salts include inorganic acid salts of quaternary ammonium (butyltrimethylammonium, diethyllaurylmethylammonium, dimethyldistearateammonium, etc.) with 4 to 30 carbon atoms. These are also available commercially as Nopco Sperse 092 [manufactured by SAN NOPCO Co., Ltd.].

[0111] Examples of plasticizers (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], epoxy plasticizers such as epoxidized soybean oil, trimellitate plasticizers, pyromellitic ester plasticizers, polyester plasticizers, and sulfonate plasticizers. It can also be obtained from the market as diisononyl phthalate [manufactured by Aekyung Petrochemical Co., Ltd., DINP], polyethylene glycol benzoate [manufactured by Sanyo Chemical Co., Ltd., EB-300], etc.

[0112] Examples of urethane esterification catalysts (G) include amine catalysts [triethylenediamine, N-ethylmorpholine, diethylethanolamine, and 1,8-diazabicyclo(5,4,0)undec-7-ene, etc.] and metal catalysts [bismuth tris(2-ethylhexanoate), stannous octoate, dibutyltin dilaurate, and lead 2-ethylhexanoate, etc.]. Inorganic bismuth catalysts [manufactured by Nitto Kasei Corporation, NEOSTANN U-600, etc.] are also available commercially.

[0113] Examples of fillers (H) include zeolites and thermally conductive fillers (nitrides such as boron nitride and aluminum nitride, oxides such as aluminum oxide, silicon dioxide, and magnesium oxide, and hydroxides such as aluminum hydroxide). By using thermally conductive fillers, the cured product of the curable urethane resin composition (i.e., urethane resin) can be made suitable for heat dissipation components.

[0114] The filler (H) can be obtained from the market as molecular sieve 3A-B powder [manufactured by Resonac Universal Co., Ltd.], AZ10-75 [manufactured by Nippon Steel Chemical Materials Co., Ltd.], HF-10 [manufactured by Tokuyama Co., Ltd.], CW-310LV [manufactured by Sumitomo Chemical Co., Ltd.], RF-10CS-SC [manufactured by Ube Materials Co., Ltd.], etc.

[0115] Other fillers than those mentioned above can also be used. By changing the type of filler, it is possible to obtain urethane resin compositions and urethane resins with various functions corresponding to the type of filler.

[0116] For example, highly conductive urethane resins can be obtained by including conductive carbon or metal as fillers; highly insulating urethane resins can be obtained by including insulating metal oxides and / or metal hydroxides; low-dielectric urethane resins can be obtained by including low-dielectric polyimide or polyethylene; high-dielectric urethane resins can be obtained by including high-dielectric barium titanate and / or lead zirconate titanate; highly flame-retardant urethane resins can be obtained by including flame-retardant ammonium polyphosphate salts and / or halides; highly opaque urethane resins can be obtained by including titanium black; highly refractive urethane resins can be obtained by including titanium oxide and / or zirconium oxide; high-strength urethane resins can be obtained by including glass fiber, carbon fiber, or Kevlar (registered trademark) fiber; highly antibacterial urethane resins can be obtained by including silver salts, copper salts, or zinc salts with antibacterial properties; and lightweight urethane resins can be obtained by including microspheres.

[0117] Examples of antioxidants (I) include hindered phenolic antioxidants [IRGANOX 1135, IRGANOX 1010 and IRGANOX 1076 (all manufactured by BASF Japan)] and hindered amine antioxidants [Tinuvin 770 (manufactured by BASF Japan)].

[0118] Examples of dispersants (J) include sorbitan fatty acid esters, fatty acids with 12 to 24 carbon atoms, sucrose fatty acid esters, and glycerol fatty acid esters.

[0119] Examples of sorbitan fatty acid esters include mono- and tri-esters of sorbitan and fatty acids with 8 to 22 carbon atoms. Specifically, examples include sorbitan palmitate (such as RHEODOL SP-P10 (HLB=6.7) manufactured by Kao Corporation and RIKEMAL P-300 (HLB=5.6) manufactured by Riken Vitamins Co., Ltd.), mono-fatty acid sorbitan esters (such as IONET S-80 manufactured by Sanyo Chemical Industries Co., Ltd.), and polyoxyethylene sorbitan fatty acid esters (such as IONET T-60V manufactured by Sanyo Chemical Industries Co., Ltd.).

[0120] Examples of fatty acids with 12 to 24 carbon atoms include saturated fatty acids (such as dodecanoic acid, hexadecanoic acid, eicosanoic acid, and tetracosanoic acid) and unsaturated fatty acids (such as hexadecenoic acid, octadecenoic acid, and octadecadienoic acid).

[0121] Examples of sucrose fatty acid esters include esters of sucrose with fatty acids having 8 to 22 carbon atoms. Specifically, examples include sucrose stearates [such as DK ESTER F-50 (HLB=6), F-70 (HLB=8), and F-110 (HLB=11) manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., and RYOTO sucrose esters S-770 (HLB approx. 7), S-970 (HLB approx. 9), S-1170 (HLB approx. 11), and S-1170F (HLB approx. 11) manufactured by Mitsubishi Chemical Co., Ltd.].

[0122] Examples of glycerol fatty acid esters include mono- and triesters of polymers of glycerol or polyglycerol (degree of polymerization 2-20) and fatty acids with 8-22 carbon atoms. Specifically, examples include diglyceride monolaurate [e.g., POEM DL-100 (HLB=9.4) manufactured by Riken Vitamins Co., Ltd.], diglyceride monomyristate [e.g., POEM DM-100 (HLB=8.7) manufactured by Riken Vitamins Co., Ltd.], diglyceride monostearate [e.g., POEM DS-100A (HLB=7.7) manufactured by Riken Vitamins Co., Ltd.], diglyceride monooleate [e.g., POEM DO-100V (HLB=7.3), RIKEMAL DO-100 (HLB=7.4) manufactured by Riken Vitamins Co., Ltd.], and decaglyceride stearate [e.g., POEM...]. J-0081HV (HLB=12), POEMJ-0381V (HLB=12), etc.

[0123] When the curable urethane resin composition of the first embodiment contains a surfactant (E), it is preferable to contain 0.001 to 30 parts by weight of surfactant (E) relative to 100 parts by weight of soft magnetic ferrite particles (D), more preferably 0.01 to 10 parts by weight, and particularly preferably 0.1 to 4 parts by weight.

[0124] When the curable urethane resin composition of the first embodiment contains a plasticizer (F), the amount of plasticizer (F) 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, relative to 100 parts by weight of the total weight of the polyol (A) and the polyisocyanate (B).

[0125] When the curable urethane resin composition of the first embodiment contains a urethane esterification catalyst (G), the amount of the urethane esterification catalyst (G) relative to 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.

[0126] When the curable urethane resin composition of the first embodiment contains filler (H), the amount of 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, relative to 100 parts by weight of soft magnetic ferrite particles (D).

[0127] When the curable urethane resin composition of the first embodiment contains an antioxidant (I), the amount of antioxidant (I) 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, relative to 100 parts by weight of the total weight of the polyol (A) and the polyisocyanate (B).

[0128] The first-method curable urethane resin composition is obtained by uniformly mixing a polyol (A), a polyisocyanate (B), a phosphate ester (C), and soft magnetic ferrite particles (D), along with other components (surfactants (E), plasticizers (F), urethane esterification catalysts (G), fillers (H), antioxidants (I), dispersants (J), etc.) as needed, using a known mixing apparatus (a mixing tank with a stirring device, etc.). In the manufacture of the curable urethane resin composition, the components can be mixed all at once, or any two or more components can be pre-mixed before mixing the remaining components (the remaining components can be a mixture).

[0129] By subjecting the curable urethane resin composition of the first method to a urethane esterification reaction on any substrate or in a molding die having a shape corresponding to the purpose using a known method, urethane resin as a cured product can be easily produced.

[0130] [Second Method]

[0131] The second curable urethane resin composition comprises a first agent and a second agent, consisting of a polyol (A), a polyisocyanate (B), a phosphate ester (C), and soft magnetic ferrite particles (D). The composition, immediately after mixing the first and second agents, exhibits fluidity, and from the viewpoint of improved adhesion to the substrate, the second method is preferred.

[0132] As a second approach, the following approach can be cited: the soft magnetic ferrite particles (D) include a first magnetic particle (D1) contained in a first agent and a second magnetic particle (D2) contained in a second agent, wherein the first agent contains a polyol (A), a phosphate ester (C) and the first magnetic particle (D1), and the second agent contains a polyisocyanate (B) and the second magnetic particle (D2).

[0133] The second method will be explained below.

[0134] In the second curable urethane resin composition, the polyol (A), phosphate ester (C), and first magnetic particles (D1) included as the first agent can be the same substances as those described in the first embodiment, including the polyol (A), phosphate ester (C), and soft magnetic ferrite particles (D). The preferred substances are also the same.

[0135] In the second embodiment, the content of phosphate ester (C) (total weight) relative to 100 parts by weight of soft magnetic ferrite particles (D) 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.

[0136] In the second method, the content (total weight) of 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.

[0137] The content of the first magnetic particle (D1) in the first agent is preferably 40 to 74% by volume, more preferably 45 to 65% by volume, based on the volume of the first agent. By making the content of the first magnetic particle (D1) in the first agent 40% by volume or more, there is a tendency for the magnetic permeability to increase, while when it is 74% by volume or less, it is easy to ensure the molding processability of the cured product.

[0138] The content of phosphate ester (C) in the first agent is preferably 0.1 to 4 parts by weight relative to 100 parts by weight of the first magnetic particles (D1), more preferably 0.2 to 4 parts by weight, and even more preferably 0.2 to 3 parts by weight. When the total weight of phosphate ester (C) relative to 100 parts by weight of the first magnetic particles (D1) is 0.1 parts by weight or more, the dispersibility of the magnetic particles is good. When the total weight of phosphate ester (C) relative to 100 parts by weight of the first magnetic particles (D1) is 4 parts by weight or less, the physical properties of the cured resin are good.

[0139] The polyisocyanate (B) and the second magnetic particle (D2) contained in the second agent can be the same substances as the polyisocyanate (B) and soft magnetic ferrite particles (D) described in the first method, and preferably the same substances as well. The first magnetic particle (D1) and the second magnetic particle (D2) can be the same or different. The first magnetic particle (D1) and the second magnetic particle (D2) being different means that when the first magnetic particle (D1) and the second magnetic particle (D2) each contain two or more fillers, this also includes cases where only the mixing ratio is different.

[0140] The content of the second magnetic particles (D2) in the second agent is preferably 40 to 74% by volume, more preferably 45 to 65% by volume, based on the volume of the second agent. By making the content of the second magnetic particles (D2) in the second agent 40% by volume or more, there is a tendency for the magnetic permeability to increase, while when it is 74% by volume or less, it is easy to ensure the molding processability of the cured product.

[0141] The second agent may further contain phosphate ester (C). When the second agent contains phosphate ester (C), the content of phosphate ester (C) in the second agent is preferably 4 parts by weight or less, more preferably 0.2 to 4 parts by weight, relative to 100 parts by weight of the second magnetic particle (D2).

[0142] Based on the weight of the curable urethane resin composition (i.e., the total weight of the first agent and the second agent), the ratio of the total weight of the polyol (A) and the polyisocyanate (B) is preferably 3 to 30% by weight, more preferably 3 to 20% by weight.

[0143] In the second curable urethane resin composition, the isocyanate index of the second agent relative to the first agent, i.e., the isocyanate index of the polyol (A) contained in the first agent and the polyisocyanate (B) contained in the second agent [total molar number of isocyanate groups in polyisocyanate (B) / total molar number of hydroxyl groups in polyol (A)], is preferably 0.8 to 1.2. When the isocyanate index is within this range, the cured resin has good physical properties.

[0144] The first and second agents may contain, to a extent that does not affect the effects of the present invention, other components (surfactants (E), plasticizers (F), urethane esterification catalysts (G), fillers (H), antioxidants (I), dispersants (J), etc.) as illustrated in the description of the curable urethane resin composition of the first embodiment, except for polyols (A), polyisocyanates (B), phosphate esters (C) and soft magnetic ferrite particles (D).

[0145] When the first and / or second agents contain surfactant (E), the surfactant (E) is preferably contained in total of 0.001 to 30 parts by weight relative to 100 parts by weight of soft magnetic ferrite particles (D) in the curable urethane resin composition, more preferably 0.01 to 10 parts by weight, and particularly preferably 0.1 to 5 parts by weight.

[0146] When the first agent and / or the second agent contain plasticizer (F), the total weight of plasticizer (F) 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, relative to 100 parts by weight of the total weight of polyol (A) and polyisocyanate (B).

[0147] When the first and / or second agents contain a carbamate catalyst (G), the total weight of the carbamate catalyst (G) is preferably 10 parts by weight or less relative to 100 parts by weight of the total weight of the polyol (A) and the polyisocyanate (B), more preferably 0.001 to 8 parts by weight, and particularly preferably 0.005 to 8 parts by weight.

[0148] When the first agent and / or the second agent contain filler (H), the total weight of 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, relative to 100 parts by weight of soft magnetic ferrite particles (D).

[0149] When the first and / or second agents contain antioxidant (I), the total weight of antioxidant (I) 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, relative to 100 parts by weight of the total weight of polyol (A) and polyisocyanate (B).

[0150] The viscosity of the first and second agents at 25°C is preferably 1–3000 Pa·s, more preferably 5–2000 Pa·s. This viscosity is a value measured according to ASTM D 2556 using MCR92 (manufactured by Anton Paar).

[0151] In the second method, the first agent is obtained by uniformly mixing polyol (A), phosphate ester (C), and first magnetic particles (D1), along with other components (surfactant (E), plasticizer (F), carbamate catalyst (G), filler (H), antioxidant (I), dispersant (J), etc.) as needed, using a known mixing device (mixing tank with stirring device, etc.). The components can be mixed all at once, or any two or more components can be pre-mixed before mixing the remaining components (the remaining components can be a mixture).

[0152] In the second method, the second agent is obtained by uniformly mixing the polyisocyanate (B), the second magnetic particles (D2), and other components (surfactant (E), plasticizer (F), carbamate catalyst (G), filler (H), antioxidant (I), dispersant (J), etc.) using a known mixing device (mixing tank with stirring device, etc.). The components can be mixed all at once, or any two or more components can be pre-mixed before mixing the remaining components (the remaining components can be a mixture).

[0153] The second type of curable urethane resin composition can be easily produced as a cured urethane resin by mixing a first agent and a second agent and carrying out a urethane reaction on any substrate or in a molding die having a shape corresponding to the purpose using a known method.

[0154] The mixing of the first and second agents can be done manually or with a known mixing device (such as a container with a stirring device), or it can be done continuously using a known two-liquid mixing supply device.

[0155] [2. Carbamate resin]

[0156] 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 obtained by curing the above-described curable urethane resin composition of the first or second embodiment using a known method.

[0157] The urethane resin of this invention has high magnetic permeability, excellent flexibility, impact resistance, and vibration resistance, and therefore can be used in applications such as wire-wound inductors, electromagnetic wave shielding, and wireless power transmission (WPT).

[0158] The following information is disclosed in this specification.

[0159] This disclosure (1) is a curable urethane resin composition containing a polyol (A), a polyisocyanate (B), a phosphate ester (C) represented by the following general formula (1), and soft magnetic ferrite particles (D).

[0160] [Chemical Formula 4]

[0161] In general formula (1), R 1 It is a hydrogen atom, an alkyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, wherein some of the hydrogen atoms of the alkyl or alkenyl group may be replaced by halogen atoms. A 1 O represents an alkyleneoxy group with 2 to 3 carbon atoms, and n1 represents A. 1 The average number of moles added by O is a number ranging from 0 to 15, R 2 For hydrogen atoms or -(A 2 O) n2 R 3 (R 3 It is an alkyl group or an alkenyl group having 2 to 20 carbon atoms, wherein some of the hydrogen atoms of the alkyl or alkenyl group may be replaced by halogen atoms. A 2 O represents an alkyleneoxy group with 2 to 3 carbon atoms, and n2 represents A. 2 The average number of moles added to O (ranging from 0 to 15).

[0162] This disclosure (2) is the curable urethane resin composition described in this disclosure (1), wherein the content of soft magnetic ferrite particles (D) is 40 to 74% by volume based on the volume of the curable urethane resin composition.

[0163] The present invention (3) is the curable urethane resin composition described in the present invention (1) or (2), wherein the polyol (A) contains a polyether polyol (a1).

[0164] The present invention (4) is a curable urethane resin composition according to any one of the present invention (1) to (3), wherein the content of phosphate ester (C) is 0.1 to 4% by weight based on the weight of soft magnetic ferrite particles (D).

[0165] This disclosure (5) is a curable urethane resin composition according to any one of disclosures (1) to (4), wherein it comprises a first agent and a second agent, the soft magnetic ferrite particles (D) comprises a first magnetic particle (D1) contained in the first agent and a second magnetic particle (D2) contained in the second agent, the first agent contains a polyol (A), a phosphate ester (C) and the first magnetic particle (D1), and the second agent contains a polyisocyanate (B) and the second magnetic particle (D2).

[0166] This disclosure (6) is the curable urethane resin composition described in this disclosure (5), wherein the content of the first magnetic particles (D1) in the first agent is 40 to 74% by volume based on the volume of the first agent.

[0167] The present invention (7) is the curable urethane resin composition described in the present invention (5) or (6), wherein the content of phosphate ester (C) in the first agent is 0.1 to 4 parts by weight relative to 100 parts by weight of the first magnetic particles (D1).

[0168] This disclosure (8) is a curable urethane resin composition according to any one of disclosures (5) to (7), wherein the content of the second magnetic particles (D2) in the second agent is 40 to 74% by volume based on the volume of the second agent.

[0169] The present invention (9) is a curable urethane resin composition according to any one of the present invention (5) to (8), wherein the second agent further contains phosphate ester (C), and the content of phosphate ester (C) in the second agent is 4 parts by weight or less relative to 100 parts by weight of the second magnetic particles (D2).

[0170] The present invention (10) is a curable urethane resin composition according to any one of the present invention (5) to (9), wherein the isocyanate index of the second agent relative to the first agent is 0.8 to 1.2.

[0171] This disclosure (11) is a urethane resin, which is the cured product of the curable urethane resin composition described in any one of (1) to (10) of this disclosure.

[0172] Example

[0173] The present invention will be specifically described below through examples, but the present invention is not limited to these examples. It should be noted that parts in the following text refer to parts by weight. The components used in the examples and comparative examples are as described in Table 1.

[0174] In Table 1, NCO refers to isocyanate groups. The NCO content of polyisocyanates is expressed as the isocyanate group content (by weight %) as determined according to JIS K 1603-1:2007.

[0175] It should be noted that the phosphate ester (C) is a monoester (R in general formula (1)). 2 A mixture of hydrogen atoms and diester.

[0176] [Table 1]

[0177] <Examples 1-10 and Comparative Examples 1 and 2>

[0178] The components shown in Table 1 are mixed in the formulation shown in Table 2 to obtain a curable urethane resin composition.

[0179] Using the obtained cured urethane resin composition, urethane resin sheets are manufactured by the following manufacturing method.

[0180] Each composition was injected into a molding die (1 cm long × 1 cm wide × 0.2 cm deep). The urethane resin was pressed and allowed to react by standing at 25°C for 24 hours to obtain a urethane resin sheet.

[0181] The compositions of Comparative Examples 1 and 2 could not be molded, and urethane resin sheets could not be obtained.

[0182] For the moldable materials (Examples 1-10), the complex relative magnetic permeability, contamination / dust shedding, flexural properties, and thermal conductivity were evaluated using the methods described below. The results are shown in Table 2. For Comparative Examples 1 and 2, as described above, urethane resin sheets could not be obtained and therefore could not be evaluated; thus, they are shown as "unmoldable" in Table 2.

[0183] <Examples 11-37 and Comparative Examples 3-6>

[0184] The components shown in Table 1 are mixed according to the formulations shown in Tables 3 to 8 to prepare the first agent and the second agent. Next, the first agent and the second agent are mixed until homogeneous to obtain a curable urethane resin composition.

[0185] For the first and second agents, the viscosity at 25°C was measured using an MCR92 viscometer (Anton Paar) according to ASTM D 2556. The results are shown in Tables 3 to 8. It should be noted that in Comparative Examples 4 to 6, materials for which viscosity was difficult to measure are indicated as "not measurable" in Tables 5 and 8.

[0186] Using the obtained cured urethane resin composition, urethane resin sheets were manufactured using the same manufacturing method as in Example 1.

[0187] The compositions of Comparative Examples 3 to 6 could not be molded, and urethane resin sheets could not be obtained.

[0188] For the moldable materials (Examples 11-37), the complex relative magnetic permeability, contamination / dust shedding, flexural properties, and thermal conductivity were evaluated using the methods described below. The results are shown in Tables 3-8. For Comparative Examples 3-6, as described above, urethane resin sheets could not be obtained and therefore could not be evaluated; thus, they are shown as "unmoldable" in Tables 5 and 8.

[0189] [Evaluation Method]

[0190] <Complex relative permeability>

[0191] A urethane resin sheet was punched into a ring 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. The punched ring sample was placed on an impedance analyzer (Agilent Technologies E4991A). The inductance and resistance at frequencies from 1 to 1000 MHz were measured using a test fixture 16454. 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.

[0192] <Pollution / Dusting>

[0193] Using the pressing rollers specified in JIS Z 0237, adhesive tape (3M, polyethylene cloth tape 386, 25mm width) was adhered to the urethane resin sheet. The adhesive tape was peeled off relative to the sheet surface at a peeling speed of 50mm / sec in a 180° direction. The contamination / dusting of the adhesive surface was evaluated according to the following criteria to confirm the moldability of the molded article.

[0194] 5: No contamination or powdering was observed on the bonding surface.

[0195] 4: Contamination is visible on a portion of the adhesive surface, but no powder is falling off.

[0196] 3: Contamination and powdering are visible on a portion of the adhesive surface.

[0197] 2: Contamination and powdering are visible on the entire bonding surface.

[0198] 1: Contamination and powdering are clearly visible on the entire bonding surface.

[0199] <Flexibility>

[0200] The urethane resin sheet is wound around a diameter of 11 mm. On the round bar, the cracks / cracking of the sheet are evaluated according to the following criteria to confirm the flexibility of the molded article.

[0201] 5: No cracks or fissures were observed on the resin sheet.

[0202] 4: Cracks are visible on a portion of the resin sheet, but no open cracks have formed.

[0203] 3: Cracks are visible on a portion of the resin sheet.

[0204] 2: Cracks are visible throughout the resin sheet.

[0205] 1. The resin sheet is very brittle and cannot be used for testing.

[0206] Thermal conductivity

[0207] After the urethane resin sheet was left to stand at 25°C for 2 hours, the thermal conductivity (unit: W / m·K) was measured using a "Xenon Flash Analyzer LFA447NanoFlash" (manufactured by NETZSCH Co., Ltd., Japan) via laser flash method.

[0208] The higher the thermal conductivity, the better the heat dissipation.

[0209] [Table 2]

[0210] [Table 3]

[0211] [Table 4]

[0212] [Table 5]

[0213] [Table 6]

[0214] [Table 7]

[0215] [Table 8]

[0216] These results show that the curable urethane resin composition according to the present invention can provide urethane resin materials with high magnetic permeability, excellent moldability, and excellent flexibility.

Claims

1. A curable urethane resin composition comprising a polyol (A), a polyisocyanate (B), a phosphate ester (C) represented by the following general formula (1), and soft magnetic ferrite particles (D), [Chemical Formula 1] In general formula (1), R 1 It is a hydrogen atom, an alkyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, wherein some of the hydrogen atoms of the alkyl or alkenyl group are optionally substituted with halogen atoms; A 1 O represents an alkyleneoxy group with 2 to 3 carbon atoms, and n1 represents A. 1 The average number of moles added by O is a number ranging from 0 to 15, R 2 For hydrogen atoms or -(A 2 O) n2 R 3 R 3 It is an alkyl group having 2 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, wherein some hydrogen atoms of the alkyl or alkenyl group are optionally substituted with halogen atoms; A 2 O represents an alkyleneoxy group with 2 to 3 carbon atoms, and n2 represents A. 2 The average number of moles added to O is between 0 and 15.

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

3. The 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 phosphate ester (C) is 0.1% to 4% by weight based on the weight of soft magnetic ferrite particles (D).

5. The curable urethane resin composition according to claim 1 or 2, wherein, Includes first and second doses. The soft magnetic ferrite particles (D) include a first magnetic particle (D1) contained in the first agent and a second magnetic particle (D2) contained in the second agent. The first agent contains polyol (A), phosphate ester (C), and first magnetic particles (D1). The second agent contains polyisocyanate (B) and second magnetic particles (D2).

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

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

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

9. The curable urethane resin composition according to claim 5, wherein, The second dose also contains phosphate esters (C), The content of phosphate ester (C) in the second agent is less than 4 parts by weight relative to 100 parts by weight of the second magnetic particle (D2).

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