WO2025053006A1 - Curable urethane resin composition and urethane resin - Google Patents

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

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

As electronic components become smaller and more powerful, magnetic composite materials are required to have higher performance, higher reliability, and lower cost.
Inductors, which can store electrical energy as magnetic energy, are one of the components in boost circuits in power supply systems. The composite magnetic material used in the core of an inductor can be obtained as a powder compact by, for example, filling a mixture of soft magnetic powder and resin and compacting it under pressure.
Methods for sealing elements or parts such as coils include, for example, press molding, in which a powdered sealing material and a member to be sealed are pressed under high pressure, and molding, in which a sealing material composition is coated on a member to be sealed and the composition is solidified or hardened. Magnetic composite materials that are imparted with electromagnetic functions by filling these sealing materials with magnetic particles are also known.
Patent Documents 1 to 4 disclose a resin composition containing a curable resin and magnetic particles, and a magnetic composite material obtained by curing the resin composition.

However, conventional magnetic composite materials have a problem of being poor in flexibility and susceptible to cracking when electronic components are subjected to vibration or impact. In addition, when magnetic particles are highly loaded into a resin, the fluidity decreases, making it difficult to sufficiently increase the magnetic particle content, and in some cases resulting in insufficient magnetic permeability.
In addition, since the powder compact is formed at a high pressure exceeding 10 MPa, usually several hundred MPa, the soft magnetic powder particles are pressed together, damaging the insulating coating of the soft magnetic powder, and the coercive force increases due to stress distortion. If the insulating coating is damaged, there is a problem that the eddy current loss of the compact increases due to the electrical connection between the soft magnetic powder particles. The increase in coercive force increases the iron loss of the compact, so a stress distortion removal process is necessary. Furthermore, powder compaction requires a large number of manufacturing steps, which increases the cost.

Patent No. 4692768 Patent No. 5700298 Patent No. 7211727 Patent No. 6813044

The present invention was made in light of the above situation, and aims to provide a high-permeability, soft magnetic urethane resin material that has high magnetic permeability, excellent moldability and flexibility, and can be easily manufactured.

［一般式（１）中、Ｒ^１は、水素原子、炭素数２～２０のアルキル基、又は、炭素数２～２０のアルケニル基であり、前記アルキル基、又は、アルケニル基の水素原子の一部がハロゲン原子で置換されていてもよい。Ａ^１Ｏは炭素数２～３のアルキレンオキシ基であり、ｎ１はＡ^１Ｏの平均付加モル数を表し、０～１５の数であり、Ｒ^２は、水素原子又は－（Ａ^２Ｏ）_ｎ２Ｒ^３（Ｒ^３は、炭素数２～２０のアルキル基、又は、炭素数２～２０のアルケニル基であり、前記アルキル基、又は、アルケニル基の水素原子の一部がハロゲン原子で置換されていてもよい。Ａ^２Ｏは炭素数２～３のアルキレンオキシ基であり、ｎ２はＡ^２Ｏの平均付加モル数を表し、０～１５の数である）である。］
で表されるリン酸エステル（Ｃ）と、軟磁性フェライト粒子（Ｄ）とを含有する硬化性ウレタン樹脂組成物；該硬化性ウレタン樹脂組成物の硬化物であるウレタン樹脂である。 The present invention relates to a polyol (A), a polyisocyanate (B), and a polyisocyanate represented by the following general formula (1):

[In the 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 a part of the hydrogen atoms of the alkyl group or the alkenyl group may be substituted with a halogen atom. ^{A 1} O is an alkyleneoxy group having 2 to 3 carbon atoms, n1 represents the average number of moles of A ¹ O added and is a number from 0 to 15, and R ² is a hydrogen atom or -(A ² O) _n2 R ³ (R ³ is an alkyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, and a part of the hydrogen atoms of the alkyl group or the alkenyl group may be substituted with a halogen atom. ^{A 2} O is an alkyleneoxy group having 2 to 3 carbon atoms, and n2 represents the average number of moles of A ² O added and is a number from 0 to 15).]
and soft magnetic ferrite particles (D). A urethane resin is a cured product of the curable urethane resin composition.

The present invention provides a high-permeability, soft magnetic urethane resin material that has high magnetic permeability, excellent moldability and flexibility, and can be easily manufactured.

［一般式（１）中、Ｒ^１は、水素原子、炭素数２～２０のアルキル基、又は、炭素数２～２０のアルケニル基であり、前記アルキル基、又は、アルケニル基の水素原子の一部がハロゲン原子で置換されていてもよい。Ａ^１Ｏは炭素数２～３のアルキレンオキシ基であり、ｎ１はＡ^１Ｏの平均付加モル数を表し、０～１５の数であり、Ｒ^２は、水素原子又は－（Ａ^２Ｏ）_ｎ２Ｒ^３（Ｒ^３は、炭素数２～２０のアルキル基、又は、炭素数２～２０のアルケニル基であり、前記アルキル基、又は、アルケニル基の水素原子の一部がハロゲン原子で置換されていてもよい。Ａ^２Ｏは炭素数２～３のアルキレンオキシ基であり、ｎ２はＡ^２Ｏの平均付加モル数を表し、０～１５の数である）である。］
で表されるリン酸エステル（Ｃ）と、軟磁性フェライト粒子（Ｄ）とを含有する。 [1. Curable urethane resin composition]
The curable urethane resin composition of the present invention comprises a polyol (A), a polyisocyanate (B), and a carboxylic acid derivative represented by the following general formula (1):

[In the 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 a part of the hydrogen atoms of the alkyl group or the alkenyl group may be substituted with a halogen atom. ^{A 1} O is an alkyleneoxy group having 2 to 3 carbon atoms, n1 represents the average number of moles of A ¹ O added and is a number from 0 to 15, and R ² is a hydrogen atom or -(A ² O) _n2 R ³ (R ³ is an alkyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, and a part of the hydrogen atoms of the alkyl group or the alkenyl group may be substituted with a halogen atom. ^{A 2} O is an alkyleneoxy group having 2 to 3 carbon atoms, and n2 represents the average number of moles of A ² O added and is a number from 0 to 15).]
The composition contains a phosphate ester (C) represented by the formula (I) and soft magnetic ferrite particles (D).

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 agent, or an embodiment (second embodiment) in which the components polyol (A), polyisocyanate (B), phosphate ester (C) and soft magnetic ferrite particles (D) are separated into two agents. First, the first embodiment will be described.

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

The polyol (A) preferably contains at least one selected from polyether polyol (a1), polyester polyol (a2), polycarbonate polyol (a3) and polyolefin polyol (a4). Among these, it is preferable that the polyol (A) contains polyether polyol (a1).

Examples of the polyether polyol (a1) include aliphatic polyether polyols and aromatic polyether polyols.
Examples of the aliphatic polyether polyol include diols obtained by addition polymerization of 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, and preferred are propylene glycol, 1,4-butanediol (tetramethylene glycol), and glycerin.
Examples of 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. When two or more of them are used in combination, the bonding mode of the AOs may be any of block addition, random addition, and a combination of these.

Specific examples of the aliphatic polyether polyol include polyoxyethylene polyols (polyethylene glycol, etc.), polyoxypropylene polyols (polypropylene glycol, etc.), polyoxyethylene/oxypropylene polyols, polytetramethylene glycol, and polyoxypropylene glyceryl ether.
These are also available on 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 NOF Corporation], and the like.

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

As the polyether polyol (a1), an aliphatic polyether polyol is preferable from the viewpoint of excellent moldability.
The number average molecular weight (Mn) of the polyether polyol (a1) is preferably from 100 to 3,000, and more preferably from 200 to 2,000, from the viewpoint of excellent moldability.

In this specification, the number average molecular weight (Mn) can be measured by gel permeation chromatography (hereinafter abbreviated as GPC) under the following conditions.
Device body: 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% by weight
Injection volume: 200 μl
Standard material: TSK STANDARD POLYETHYLENE OXIDE manufactured by Tosoh Corporation
Data processing software: GPC-8020 model II (Tosoh Corporation)

Examples of the polyester polyol (a2) include condensates of polyols (such as the above-mentioned 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, nonadecanedioic acid, and eicosane diacid, etc.]; alicyclic polycarboxylic acids having 5 to 20 carbon atoms [cyclopropane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, cyclohexene dicarboxylic 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-stilbene dicarboxylic acid, naphthalene dicarboxylic acid, 4,4-biphenyl dicarboxylic acid, orthophthalic acid, diphenyl ether dicarboxylic acid, etc.], and the like, can be mentioned. These are commercially available as Kuraray Polyol P-2010 [manufactured by Kuraray Co., Ltd.], etc.

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.

Aliphatic polyols include trivalent or higher alcohols among aliphatic polyols having 3 to 20 carbon atoms, such as glycerin and pentaerythritol, with glycerin being preferred.

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

AO adducts of alicyclic polyols include compounds in which AO is added to the above-mentioned alicyclic polyols. As AO, the same ones as those exemplified in the description of polyether polyol (a1) can be used, and the same are preferred.

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

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

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

From the viewpoint of excellent moldability, the number average molecular weight of polyol (A) is preferably 100 to 3000, and more preferably 200 to 2000.

Examples of polyisocyanates (B) include linear aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and isocyanurates of these polyisocyanates.

The chain aliphatic polyisocyanate may be, for example, a chain aliphatic polyisocyanate having 4 to 20 carbon atoms, and preferably includes ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate. It is also available on the market as A201H [manufactured by Asahi Kasei Corporation, a dimer of hexamethylene diisocyanate], etc.

Examples of alicyclic polyisocyanates include alicyclic polyisocyanates having 6 to 17 carbon atoms, and preferably 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 available on the market as Desmodur I [manufactured by Sumika Covestro Urethane Co., Ltd.], etc.

Examples of aromatic polyisocyanates include aromatic polyisocyanates having 8 to 22 carbon atoms, and preferably 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).

Examples of the isocyanurate of polyisocyanate include trimers of polyisocyanates (such as the above-mentioned 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.

From the viewpoint of excellent moldability, it is preferable that the polyisocyanate (B) contains at least one selected from the group consisting of chain aliphatic polyisocyanates, alicyclic polyisocyanates, isocyanurates of chain aliphatic polyisocyanates, and isocyanurates of alicyclic polyisocyanates.
The polyisocyanate (B) may be used alone or in combination of two or more kinds.

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, based on the weight of the curable urethane resin composition.

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.

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

［一般式（１）中、Ｒ^１は、水素原子、炭素数２～２０のアルキル基、又は、炭素数２～２０のアルケニル基であり、前記アルキル基、又は、アルケニル基の水素原子の一部がハロゲン原子で置換されていてもよい。Ａ^１Ｏは炭素数２～３のアルキレンオキシ基であり、ｎ１はＡ^１Ｏの平均付加モル数を表し、０～１５の数であり、Ｒ^２は、水素原子又は－（Ａ^２Ｏ）_ｎ２Ｒ^３（Ｒ^３は、炭素数２～２０のアルキル基、又は、炭素数２～２０のアルケニル基であり、前記アルキル基、又は、アルケニル基の水素原子の一部がハロゲン原子で置換されていてもよい。Ａ^２Ｏは炭素数２～３のアルキレンオキシ基であり、ｎ２はＡ^２Ｏの平均付加モル数を表し、０～１５の数である）である。］
で表される。

[In the 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 a part of the hydrogen atoms of the alkyl group or the alkenyl group may be substituted with a halogen atom. ^{A 1} O is an alkyleneoxy group having 2 to 3 carbon atoms, n1 represents the average number of moles of A ¹ O added and is a number from 0 to 15, and R ² is a hydrogen atom or -(A ² O) _n2 R ³ (R ³ is an alkyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, and a part of the hydrogen atoms of the alkyl group or the alkenyl group may be substituted with a halogen atom. ^{A 2} O is an alkyleneoxy group having 2 to 3 carbon atoms, and n2 represents the average number of moles of A ² O added and is a number from 0 to 15).]
It is expressed as:

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, each of which 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.
The halogen atom is preferably a fluorine atom.

^R1 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, R1 is preferably an alkyl group having 12 to 18 carbon atoms.

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

R ² is a hydrogen atom or -(A ² O) _n2 R ³ (R ³ 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 alkenyl group may be substituted with halogen atoms. ^{A 2} O is an alkyleneoxy group having 2 to 3 carbon atoms, and n2 represents the average number of moles of A ² O added and is a number from 0 to 15).
^Examples of R3 include the same as those of ^R1 , and the preferred examples are also the same.
Examples of A ² O include the same as those of A ¹ O, and the preferred examples are also the same.
When ^R2 is a hydrogen atom, the compound of general formula (1) is a monoester, and when ^R2 is -( ^A2O ) _n2R3 , the compound of general formula (1) is a ^diester . When ^R2 is -( ^A2O ) _n2R3 , ^R1 and ^R3 may be the same or different. ⁿ¹ and n2 may be the same or different.

As the phosphoric acid ester (C) represented by the general formula (1), a mixture of two or more types having different ^R1 may be used, or a mixture of a monoester ( ^R2 is H) ^and a diester ( ^R2 is -( ^A2O ) _n2R3 ) may be used. The phosphoric acid ester (C) represented by the general formula (1) is generally obtained as a mixture of a monoester and a diester (mono-di mixture). In addition, a salt of the phosphoric acid ester represented by the general formula (1) (metal salts such as sodium, potassium, and magnesium, and ammonium salts) may also be used.

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 the general formula (1) can be obtained by phosphate esterification using polyether and phosphorus oxide. Also available on the market are Clopol P-10A [manufactured by Sanyo Chemical Industries, Ltd.], Disparlon DA-375 [manufactured by Kusumoto Chemical Industries, Ltd.], Plysurf A208N [manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], Phosphanol 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], Phosphanol RS-710 [manufactured by Toho Chemical Industry Co., Ltd., (C12-15) Palace-9 phosphate, R ¹ , R ³ : C12-15 alkyl group, A ¹ O, A ^{2 O} : ethyleneoxy group, n1, n2: 2, mono-di mixture], 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- and 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- and 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 ² O: 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 kinds.

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

The material of the soft magnetic ferrite particles (D) may be a spinel type soft magnetic ferrite, and examples of the soft magnetic ferrite include NiCuZn ferrite, MnZn ferrite, NiZn ferrite, MnMgZn ferrite, MgZn ferrite, MgZnCu ferrite, LiZn ferrite, LiZnCu ferrite, etc. In addition, Co, Si, etc. may be further added as elements constituting the soft magnetic ferrite for modification.

The magnetic material that constitutes the magnetic particles may be appropriately selected according to the desired magnetization characteristics (relative magnetic permeability) and volume electrical resistivity.

The soft magnetic ferrite can be obtained from the market as BSN-125 (NiCuZn-based ferrite), BSN-714 (NiZn-based ferrite), BSN-828 (NiCuZn-based ferrite), BSF-547 (MnZn-based ferrite), BSF-029 (MnZn-based ferrite), KSN-415 (MnZn-based ferrite), FRX-843 (MnMgZn-based ferrite) [all manufactured by Toda Kogyo Co., Ltd.], and the like.
The soft magnetic ferrite particles (D) may be used alone or in combination of two or more kinds.

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, from the viewpoint of high filling ability in resin, spherical particles are preferred, and those with adjusted particle size distribution are more preferred.

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 volume-based particle size distribution is 50%] of the soft magnetic ferrite particles (D) is preferably 1 to 200 μm, more preferably 2 to 150 μm, from the viewpoints 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.

The soft magnetic ferrite particles (D) are preferably soft magnetic ferrite powder.
The soft magnetic ferrite powder can be obtained, for example, by calcining 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 a precipitate obtained by precipitating each element in an aqueous solution, in 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.

The content of the soft magnetic ferrite particles (D) is preferably 40 to 74 volume % based on the volume of the curable urethane resin composition, and more preferably 45 to 65 volume %. If the content of the soft magnetic ferrite particles (D) is 40 volume % or more, the magnetic permeability tends to be high, and if it is 74 volume % or less, the moldability of the cured product is easily ensured.

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) to the extent that 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 (such as ultraviolet absorbers described in JP 2018-076537 A) used in urethane resins as other components.

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.

Examples of the polyoxyalkylene type nonionic surfactant (E1) include AO adducts (preferably 1 to 30 moles of addition) 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.
As the aliphatic alcohol constituting the polyoxyalkylene type nonionic surfactant (E1), n-, i-, sec- or t-butanol, octanol, dodecanol, etc. are preferred; as the alkylphenol, phenol, methylphenol, nonylphenol, etc. are preferred; as the aliphatic amine, laurylamine, methylstearylamine, etc. are preferred; and as the aliphatic amide, stearic acid amide, etc. are preferred.

Examples of ester-type nonionic surfactants (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.

The anionic surfactant (E3) includes carboxylate, sulfate and sulfonate types.
Examples of the carboxylate type include alkali metal salts of the above 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 aliphatic alcohols having 4 to 30 carbon atoms or AO adducts of aliphatic alcohols, and examples of the sulfonate type include alkali metal sulfonates of alkylphenols. They are also available on the market as polyether carboxylic acids [Kao Akipo RLM-100, manufactured by Kao Corporation], etc.

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

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 ester], epoxy plasticizers such as epoxidized soybean oil, trimellitate plasticizers, pyromellitate plasticizers, polyester plasticizers, sulfonate ester plasticizers, etc. It is also available commercially as diisononyl phthalate [DINP, manufactured by Aekyung Petrochemical Co., Ltd.], polyethylene glycol benzoate ester [EB-300, manufactured by Sanyo Chemical Industries, Ltd.], etc.

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.]. They are also available on the market as inorganic bismuth catalysts [manufactured by Nitto Kasei Co., Ltd., Neostan U-600], etc.

Examples of the filler (H) include zeolite 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), etc. By using a thermally conductive filler, the cured product of the curable urethane resin composition (i.e., the urethane resin) can be made suitable for use as a heat dissipation member.
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 & 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.], or the like.
Fillers other than those mentioned above can also be used, and by changing the type of filler, it is possible to obtain urethane resin compositions and urethane resins having various functions according to 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 highly flame-retardant urethane resin can be obtained; by including ammonium polyphosphate and/or halide having flame retardant action, a highly light-shielding urethane resin can be obtained; by including titanium black, 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.

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

The dispersing agent (J) includes sorbitan fatty acid esters, fatty acids having 12 to 24 carbon atoms, sucrose fatty acid esters, and glycerin fatty acid esters.
Examples of sorbitan fatty acid esters include mono- to triesters of sorbitan and fatty acids having 8 to 22 carbon atoms. Specific examples thereof include sorbitan palmitate [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 [IONET S-80 manufactured by Sanyo Chemical Industries, Ltd., etc.], and polyoxyethylene sorbitan fatty acid esters [IONET T-60V manufactured by Sanyo Chemical Industries, Ltd., etc.].
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 stearate esters [DK Ester F-50 (HLB=6), F-70 (HLB=8), and F-110 (HLB=11), manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and Ryoto Sugar Ester S-770 (HLB=about 7), S-970 (HLB=about 9), S-1170 (HLB=about 11), and S-1170F (HLB=about 11), manufactured by Mitsubishi Chemical Corporation].
Examples of glycerol fatty acid esters include mono- to triesters of glycerol or polyglycerol polymers (degree of polymerization 2 to 20) and fatty acids having 8 to 22 carbon atoms. Specific examples of such esters include diglycerol monolaurate [Poem DL-100 (HLB=9.4) manufactured by Riken Vitamin Co., Ltd., etc.], diglycerol monomyristate [Poem DM-100 (HLB=8.7) manufactured by Riken Vitamin Co., Ltd., etc.], diglycerol mono Examples of such glycerol stearate include Poem DS-100A (HLB=7.7) manufactured by Riken Vitamin Co., Ltd., and the like; diglycerol monooleate, Poem DO-100V (HLB=7.3), Rikemal DO-100 (HLB=7.4), manufactured by Riken Vitamin Co., Ltd., and the like; and decaglycerol stearate, Poem J-0081HV (HLB=12), Poem J-0381V (HLB=12), manufactured by Riken Vitamin Co., Ltd., and the like.

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

When the curable urethane resin composition of the first embodiment contains a plasticizer (F), the amount of the plasticizer (F) per 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.

When the curable urethane resin composition of the first embodiment contains a urethane catalyst (G), the amount of the urethane catalyst (G) 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 0.001 to 8 parts by weight, and particularly preferably 0.005 to 8 parts by weight.

When the curable urethane resin composition of the first embodiment 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).

When the curable urethane resin composition of the first embodiment 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.

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

The curable urethane resin composition of the first embodiment can be easily produced as a cured product by a known method of urethane reaction on any substrate or in a mold having a shape appropriate for the purpose.

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

A second embodiment is one in which 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 first magnetic particles (D1), and the second agent contains polyisocyanate (B) and second magnetic particles (D2).
The second aspect will now be described.

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

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).

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

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

The content of the phosphate ester (C) in the first agent is preferably 0.1 to 4 parts by weight per 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 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.

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 are also preferred. The first magnetic particles (D1) and the second magnetic particles (D2) may be the same or different. The first magnetic particles (D1) and the second magnetic particles (D2) being different also includes the case where the first magnetic particles (D1) and the second magnetic particles (D2) are each composed of two or more types of fillers and only the compounding ratio is different.

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

The second agent may further contain a phosphate ester (C). When the second agent contains a 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).

The total weight ratio of polyol (A) and 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 agents).

In the curable urethane resin composition of the second embodiment, 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 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 resin properties after curing can be made good.

The first and second agents 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.) within the scope that does not affect the effects of the present invention.

When the first agent and/or the second agent contains a surfactant (E), it is preferable that the surfactant (E) is contained in a total amount of 0.001 to 30 parts by weight, 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.

When the first agent and/or the second agent contains a plasticizer (F), the total weight of the plasticizer (F) per 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.

When the first agent and/or the second agent contains a urethane catalyst (G), the total weight of the urethane catalyst (G) 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 0.001 to 8 parts by weight, and particularly preferably 0.005 to 8 parts by weight.

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).

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.

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

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 necessary (surfactant (E), plasticizer (F), urethanization catalyst (G), filler (H), antioxidant (I), dispersant (J), etc.) using a known mixing device (such as a mixing tank equipped with a stirrer). Each component may be mixed all at once, or any two or more components may be mixed in advance and the remaining components (which may be a mixture) may be mixed.

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 necessary (surfactant (E), plasticizer (F), urethanization catalyst (G), filler (H), antioxidant (I), dispersant (J), etc.) using a known mixing device (such as a mixing tank equipped with a stirrer). Each component may be mixed all at once, or any two or more components may be mixed in advance and the remaining components (which may be a mixture) may be mixed.

The curable urethane resin composition of the second aspect can be easily produced by mixing the first agent and the second agent and carrying out a urethanization reaction on any substrate or in a mold having a shape according to the purpose by a known method, thereby producing a cured urethane resin.
The first and second parts 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-liquid mixing and supplying device.

[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.

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

The following items are disclosed in this specification:

［一般式（１）中、Ｒ^１は、水素原子、炭素数２～２０のアルキル基、又は、炭素数２～２０のアルケニル基であり、前記アルキル基、又は、アルケニル基の水素原子の一部がハロゲン原子で置換されていてもよい。Ａ^１Ｏは炭素数２～３のアルキレンオキシ基であり、ｎ１はＡ^１Ｏの平均付加モル数を表し、０～１５の数であり、Ｒ^２は、水素原子又は－（Ａ^２Ｏ）_ｎ２Ｒ^３（Ｒ^３は、炭素数２～２０のアルキル基、又は、炭素数２～２０のアルケニル基であり、前記アルキル基、又は、アルケニル基の水素原子の一部がハロゲン原子で置換されていてもよい。Ａ^２Ｏは炭素数２～３のアルキレンオキシ基であり、ｎ２はＡ^２Ｏの平均付加モル数を表し、０～１５の数である）である。］
で表されるリン酸エステル（Ｃ）と、軟磁性フェライト粒子（Ｄ）とを含有する硬化性ウレタン樹脂組成物である。 The present disclosure (1) is
Polyol (A), polyisocyanate (B), and a compound represented by the following general formula (1):

[In the 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 a part of the hydrogen atoms of the alkyl group or the alkenyl group may be substituted with a halogen atom. ^{A 1} O is an alkyleneoxy group having 2 to 3 carbon atoms, n1 represents the average number of moles of A ¹ O added and is a number from 0 to 15, and R ² is a hydrogen atom or -(A ² O) _n2 R ³ (R ³ is an alkyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, and a part of the hydrogen atoms of the alkyl group or the alkenyl group may be substituted with a halogen atom. ^{A 2} O is an alkyleneoxy group having 2 to 3 carbon atoms, and n2 represents the average number of moles of A ² O added and is a number from 0 to 15).]
and soft magnetic ferrite particles (D).

The present disclosure (2) is a 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.

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

The present disclosure (4) is a curable urethane resin composition according to any one of the present disclosures (1) to (3), in which 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).

The present disclosure (5) is a curable urethane resin composition according to any one of the present disclosures (1) to (4), which is made up of a first agent and a second agent, the soft magnetic ferrite particles (D) being made up of 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).

The present disclosure (6) is a 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.

The present disclosure (7) is a 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).

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.

The present disclosure (9) is a curable urethane resin composition according to any one of the present disclosures (5) to (8), in which 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).

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

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

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

In Table 1, NCO means an isocyanate group. The NCO content of the polyisocyanate indicates the isocyanate group content (% by weight) measured in accordance with JIS K 1603-1:2007.
The phosphate ester (C) is a mixture of a monoester ( ^R2 in the general formula (1) is a hydrogen atom) and a diester.

<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 a curable urethane resin composition.
Using the obtained curable urethane resin composition, a urethane resin sheet was produced by the following production method.
Each composition was poured into a molding die (length 1 cm × width 1 cm × depth 0.2 cm) so as to fill it, pressed with a press, and allowed to stand at 25° C. for 24 hours to react, thereby obtaining a urethane resin sheet.
The compositions of Comparative Examples 1 and 2 could not be molded, and urethane resin sheets could not be obtained.
The molded products (Examples 1 to 10) were evaluated for complex relative magnetic permeability, staining/powdering resistance, flexibility, and thermal conductivity by the following methods. The results are shown in Table 2. For Comparative Examples 1 and 2, as described above, no urethane resin sheet was obtained and evaluation was not possible, so they are indicated as "unmoldable" in Table 2.

<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 the first and second agents. The first and second agents were then mixed until uniform, to obtain a curable urethane resin composition.
The viscosity of the first and second agents 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. Note that, in Comparative Examples 4 to 6, those for which it was difficult to measure the viscosity are indicated as "measurable" in Tables 5 and 8.
A urethane resin sheet was produced by the same production method as in Example 1 using the obtained curable urethane resin composition.
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 permeability, staining/powdering resistance, flexibility, and thermal conductivity by 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 was obtained and evaluation was not possible, so they are indicated as "unmoldable" in Tables 5 and 8.

[Evaluation method]
<Complex relative permeability>
The 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 obtained. The real part μ' is shown in Tables 2 to 8.

<Staining and powder fall-off>
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 180° direction from the sheet surface at a peeling speed of 50 mm/sec, and the staining and powder falling off of the adhesive surface were evaluated according to the following criteria to confirm the moldability of the molded product.
5: No contamination or powder fall-off is observed on the adhesive surface.
4: Some contamination is observed on the adhesive surface, but no powder fall-off is observed.
3: Contamination and powder fall are observed on some parts of the adhesive surface.
2: Contamination and powder fall are observed on the entire adhesive surface.
1: Significant contamination and powder fall-off are observed over the entire adhesive surface.

<Flexibility>
The urethane resin sheet was wrapped around a round bar having an outer diameter of 11 mm, and the flexibility of the molded product was confirmed by evaluating the sheet for cracks and tears according to the following criteria.
5: No cracks or tears are observed in the resin sheet.
4: Cracks are observed in some parts of the resin sheet, but no tears are observed.
3: Part of the resin sheet is cracked.
2: Cracking is observed throughout the resin sheet.
1: The resin sheet was very brittle and the test was not possible.

<Thermal Conductivity>
The urethane resin sheet was allowed to stand at 25°C for 2 hours, and then the thermal conductivity (unit: W/m·K) was measured by a laser flash method using a thermal conductivity meter "Xenon Flash Analyzer LFA447 NanoFlash" (manufactured by Netzsch Japan Co., Ltd.).
A higher thermal conductivity indicates better heat dissipation.

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 excellent moldability and flexibility.

Claims (11)

Polyol (A), polyisocyanate (B), and a compound represented by the following general formula (1):

[In the 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 a part of the hydrogen atoms of the alkyl group or the alkenyl group may be substituted with a halogen atom. ^{A 1} O is an alkyleneoxy group having 2 to 3 carbon atoms, n1 represents the average number of moles of A ¹ O added and is a number from 0 to 15, and R ² is a hydrogen atom or -(A ² O) _n2 R ³ (R ³ is an alkyl group having 2 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms, and a part of the hydrogen atoms of the alkyl group or the alkenyl group may be substituted with a halogen atom. ^{A 2} O is an alkyleneoxy group having 2 to 3 carbon atoms, and n2 represents the average number of moles of A ² O added and is a number from 0 to 15).]
and soft magnetic ferrite particles (D). 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. The curable urethane resin composition according to claim 1 or 2, wherein the polyol (A) contains a polyether polyol (a1). The curable urethane resin composition according to claim 1 or 2, in which 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). Consists of a first agent and a second agent,
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 a polyol (A), a phosphoric acid ester (C), and first magnetic particles (D1),
The curable urethane resin composition according to claim 1 or 2, wherein the second agent contains a polyisocyanate (B) and second magnetic particles (D2). 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. 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). 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. The second agent further contains a phosphoric acid ester (C),
6. The curable urethane resin composition according to claim 5, wherein 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). The curable urethane resin composition according to claim 5, in which the isocyanate index of the second agent relative to the first agent is 0.8 to 1.2. A urethane resin which is a cured product of the curable urethane resin composition according to claim 1 or 2.