CN113444340A

CN113444340A - Resin composition

Info

Publication number: CN113444340A
Application number: CN202110305965.1A
Authority: CN
Inventors: 川口纯奈; 荻野启志
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2020-03-24
Filing date: 2021-03-23
Publication date: 2021-09-28
Also published as: KR20210119324A; JP2021152108A; TW202142588A; JP7415717B2

Abstract

The present invention addresses the problem of providing a resin composition that can provide a cured product having excellent impact resistance. The solution of the present invention is a resin composition comprising (A) an epoxy resin, (B) a thiol compound, and (C) a magnetic powder, wherein the elastic modulus of a cured product of the resin composition at 25 ℃ is 500MPa or less, and the elongation at break at 25 ℃ of the cured product of the resin composition is 30% or more.

Description

Resin composition

Technical Field

The present invention relates to a resin composition containing a magnetic powder. The present invention also relates to a cured product obtained using the resin composition, an electronic component, a motor containing a neodymium magnet, and the like.

Background

In an electronic component having a magnetic circuit such as a permanent magnet and a yoke, the use of a general adhesive has a problem that a magnetic flux leakage in the electronic component using the adhesive causes a performance degradation of the electronic component such as a motor due to a magnetic loss.

To solve such problems, a technique is known in which a magnetic powder is added to an adhesive to make the adhesive magnetic, thereby suppressing magnetic leakage in an adhesive portion on a magnetic circuit and improving the performance of an electronic component such as a motor (patent document 1).

Generally, when used in a camera module or the like, an adhesive having low elasticity is preferable for providing impact resistance, but if the adhesive is filled with magnetic powder, a cured product of the adhesive becomes hard, and the elastic modulus tends to be high.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 1-289883.

Disclosure of Invention

Problems to be solved by the invention

Accordingly, an object of the present invention is to provide a resin composition containing a magnetic powder and capable of obtaining a cured product having excellent impact resistance.

Means for solving the problems

As a result of intensive studies to achieve the object of the present invention, the present inventors have found that the object of the present invention can be achieved by using a resin composition containing a thiol compound, and have completed the present invention.

That is, the present invention includes the following.

[1] A resin composition comprising (A) an epoxy resin, (B) a thiol compound, and (C) a magnetic powder,

the cured product of the resin composition has an elastic modulus at 25 ℃ of 500MPa or less, and

the elongation at break at 25 ℃ of the cured product of the resin composition is 30% or more.

[2] The resin composition according to the above [1], wherein the epoxy equivalent of the component (A) is 200g/eq to 1000g/eq.

[3] The resin composition according to the above [1] or [2], wherein the component (B) is a thiol compound having 2 or more functions.

[4] The resin composition according to any one of the above [1] to [3], wherein a ratio (mercapto group/epoxy group) of the total number of mercapto groups of the thiol compound (B) to the total number of epoxy groups of the epoxy resin (A) is 0.3 to 1.0.

[5] The resin composition according to any one of the above [1] to [4], wherein the content of the component (C) is 40% by mass to 75% by mass, with 100% by mass of nonvolatile components in the resin composition.

[6] The resin composition according to any one of the above [1] to [5], further comprising a latent curing accelerator.

[7] The resin composition according to any one of the above [1] to [6], wherein the component (A) comprises (A-1) an epoxy resin having a flexible skeleton.

[8] The resin composition according to any one of the above [1] to [7], wherein a reaction peak temperature based on differential scanning calorimetry is 100 ℃ or less.

[9] The resin composition according to any one of the above [1] to [8], which is used as an adhesive.

[10] The resin composition according to the above [9], which is used as an adhesive for adhering a neodymium magnet as an adherend.

[11] The resin composition according to any one of the above [1] to [8], which is used as a sealing material.

[12] A cured product of the resin composition according to any one of [1] to [11 ].

[13] A motor comprising a neodymium-containing magnet, comprising the cured product according to [12 ].

[14] An electronic component comprising the cured product according to [12 ].

[15] An electronic component comprising a motor containing a neodymium magnet, and the cured product according to [12 ].

Effects of the invention

The present invention can provide a resin composition which contains a magnetic powder and can give a cured product having excellent impact resistance.

Drawings

Fig. 1 is a DSC chart showing differential scanning calorimetry curves (DSC curves) before and after curing of the resin composition obtained in example 1.

Detailed Description

The present invention will be described in detail below with reference to preferred embodiments thereof. However, the present invention is not limited to the following embodiments and examples, and may be modified and implemented within the scope of the claims and their equivalents without departing from the invention.

< resin composition >

The resin composition of the present invention comprises (A) an epoxy resin, (B) a thiol compound, and (C) a magnetic powder. The cured product of the resin composition of the present invention has an elastic modulus at 25 ℃ of 500MPa or less. The resin composition of the present invention has a cured product having a breaking point elongation at 25 ℃ of 30% or more. The cured product of such a resin composition has excellent impact resistance.

The resin composition of the present invention may further contain (D) a stabilizer, (E) a dispersant, (F) a curing accelerator, (G) an organic filler, (H) other additives, and (I) an organic solvent, in addition to (a) the epoxy resin, (B) the thiol compound, and (C) the magnetic powder. Hereinafter, each component contained in the resin composition will be described in detail.

(A) epoxy resin

The resin composition of the present invention comprises (a) an epoxy resin. (A) The epoxy resin means a curable resin having an epoxy group.

(A) The epoxy equivalent of the epoxy resin is not particularly limited, but is preferably 50 g/eq.or more, more preferably 100 g/eq.or more, further preferably 150 g/eq.or more, further more preferably 180 g/eq.or more, and particularly preferably 200 g/eq.or more, from the viewpoint of suppressing the elastic modulus to be low and improving the elongation at break. (A) The upper limit of the epoxy equivalent of the epoxy resin is not particularly limited, and in the aspect of use as an adhesive or a sealing material, from the viewpoint of obtaining a resin composition which is easier to handle, it is preferably 5000 g/eq.or less, more preferably 2000 g/eq.or less, still more preferably 1000 g/eq.or less, still more preferably 700 g/eq.or less, and particularly preferably 500 g/eq.or less. The epoxy equivalent is the mass of the resin having 1 equivalent of epoxy group on average. The epoxy equivalent can be measured according to JIS K7236.

(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and further preferably 400 to 1,500. The weight average molecular weight of the resin can be measured by a Gel Permeation Chromatography (GPC) method as a value in terms of polystyrene.

The content of the epoxy resin (a) in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100 mass%, it is preferably 99 mass% or less, more preferably 90 mass% or less, further preferably 80 mass% or less, further more preferably 65 mass% or less, and particularly preferably 50 mass% or less. The lower limit of the content of the epoxy resin (a) in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100 mass%, it is preferably 1 mass% or more, more preferably 5 mass% or more, further preferably 10 mass% or more, further more preferably 20 mass% or more, and particularly preferably 30 mass% or more. In one embodiment, the content of the (a) epoxy resin can be set based on the content of the (B) thiol compound and the thiol equivalent.

< (A-1) epoxy resin containing flexible skeleton

In the present invention, (a) the epoxy resin preferably contains (a-1) an epoxy resin having a flexible skeleton, from the viewpoint of suppressing the elastic modulus to a lower level and further increasing the elongation at break. The flexible skeleton-containing epoxy resin (A-1) is a curable resin having a flexible skeleton and an epoxy group. The flexible skeleton herein may be, for example, a saturated chain skeleton containing 6 or more (preferably 8 or more) skeleton atoms selected from carbon atoms and oxygen atoms in the main chain. (A-1) the flexible skeleton-containing epoxy resin preferably has 1 to 5, more preferably 1 to 3, and particularly preferably 2 epoxy groups in 1 molecule. The flexible skeleton-containing epoxy resin (A-1) may further have a functional group such as a hydroxyl group or an amino group.

Examples of the (A-1) flexible skeleton-containing epoxy resin include (A-1-1) flexible skeleton-containing aromatic epoxy resins (having an aromatic ring), and (A-1-2) flexible skeleton-containing non-aromatic epoxy resins (having no aromatic ring). The flexible skeleton-containing epoxy resin (A-1) may be used alone in 1 kind, or may be used in combination in an arbitrary ratio in 2 or more kinds.

(A-1-1) the aromatic epoxy resin having a flexible skeleton is an epoxy resin having at least 1 aromatic group (for example, phenylene group or the like) and at least 1 saturated chain skeleton containing 6 or more (preferably 8 or more) skeleton atoms selected from carbon atoms and oxygen atoms in the main chain.

Examples of the aromatic epoxy resin having a flexible skeleton of (A-1-1) include, but are not particularly limited to, a modified bisphenol type epoxy resin having a flexible skeleton, a modified biphenyl type epoxy resin having a flexible skeleton, a modified novolak type epoxy resin having a flexible skeleton, and a modified phenol aralkyl type epoxy resin having a flexible skeleton.

The modified bisphenol type epoxy resin having a flexible skeleton has a bisphenol ether skeleton such as a bisphenol a ether structure, a bisphenol AP ether structure, a bisphenol B ether structure, a bisphenol BP ether structure, a bisphenol C ether structure, a bisphenol E ether structure, a bisphenol F ether structure, a bisphenol TMC ether structure, and the like.

(A-1-1) the aromatic epoxy resin having a flexible skeleton may be, for example, an epoxy resin represented by the formula (1):

[ CHEM 1]

[ wherein R each independently represents a single bond, -CR¹ ₂-, -O-, -CO-, -S-, -SO-, or-SO₂-，R¹Each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 6 carbon atoms) or an aryl group (preferably having 6 to 14 carbon atoms), or 2R's bonded to the same carbon atom¹Are bonded together to form a cycloalkane ring (preferably having 3 to 8 carbon atoms), R²Each independently represents an alkyl group (preferably having 1 to 6 carbon atoms) or an aryl group (preferably having 6 to 14 carbon atoms), X and Y each independently represents an alkylene group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 10 carbon atoms) optionally having a hydroxyl group, a each independently represents an integer of 0 or more, b each independently represents an integer of 2 or more, c represents an integer of 1 or more, d each independently represents an integer of 6 or moreAn integer of 0 to 3]。

Alkyl refers to a straight, branched, and/or cyclic 1 valent aliphatic saturated hydrocarbon group.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a sec-pentyl group, a tert-pentyl group, a cyclopentyl group, and a cyclohexyl group, and a methyl group is preferable. Aryl means a 1-valent aromatic hydrocarbon group. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group, and a phenyl group is preferable. The cycloalkane ring means a cyclic aliphatic saturated hydrocarbon ring. Examples of the cycloalkane ring include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a methylcyclohexane ring, a dimethylcyclohexane ring, and a trimethylcyclohexane ring. Alkylene means a straight or branched 2-valent aliphatic saturated hydrocarbon group. As the alkylene group optionally having a hydroxyl group, there may be mentioned, for example, -CH₂-CH₂-、-CH(CH₃)-、-CH₂-CH₂-CH₂-、-CH₂-CH(CH₃)-、-CH(CH₃)-CH₂-、-C(CH₃)₂-、-CH₂-CH₂-CH₂-CH₂-、-CH₂-CH₂-CH(CH₃)-、-CH₂-CH(CH₃)-CH₂-、-CH(CH₃)-CH₂-CH₂-、-CH₂-C(CH₃)₂-、-C(CH₃)₂-CH₂-、-CH₂-CH₂-CH₂-CH₂-CH₂-、-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-、-CH₂-CH(CH₃)-CH₂-CH(CH₃)-CH₂-CH(CH₃)-、-CH(CH₃)-CH₂-CH(CH₃)-CH₂-CH(CH₃)-CH₂-、-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-、-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-、-CH₂-CH(CH₃)-CH₂-CH(CH₃)-CH₂-CH(CH₃)-CH₂-CH(CH₃)-、-CH(CH₃)-CH₂-CH(CH₃)-CH₂-CH(CH₃)-CH₂-CH(CH₃)-CH₂-、-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-、-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂-CH₂An alkylene group having 2 to 10 carbon atoms; -CH₂-CH(OH)-、-CH(OH)-CH₂-、-CH₂-CH(OH)-CH₂-、-CH(CH₂OH)-CH₂-、-CH₂-CH(CH₂OH)-、-CH₂-CH(CH₂OH)-CH₂A hydroxyalkylene group having 2 to 10 carbon atoms.

In the formula (1), R is each independently preferably-CR¹-。R¹Each independently is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group. R²Each independently is preferably an alkyl group. a is independently an integer of 0 to 20 (0 or an integer of 1 to 20), and more preferably an integer of 0 to 10 (0 or an integer of 1 to 10). b is independently preferably an integer of 3 to 20, more preferably an integer of 3 to 10. c is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and further preferably an integer of 1 to 8. Each d is independently preferably 0 or 1, more preferably 0.

Specific examples of the (A-1-1) aromatic epoxy resin having a flexible skeleton include epoxy resins represented by the following formulae (1A) to (1G):

[ CHEM 2]

[ in the formula, R³、R⁴And R⁵Each independently represents a hydrogen atom or a methyl group, x represents an integer of 1 to 10, and y each independently represents an integer of 1 to 10]。

(A-1-2) the non-aromatic epoxy resin having a flexible skeleton is an epoxy resin having a saturated aliphatic chain containing a skeleton atom selected from carbon atoms and oxygen atoms as a basic skeleton. Examples of the aromatic epoxy resin having a flexible skeleton include alkane diol diglycidyl ethers such as ethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, and 1, 6-hexanediol diglycidyl ether; polyalkylene glycol diglycidyl ethers such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polytetramethylene glycol diglycidyl ether.

(A-1-2) the non-aromatic epoxy resin having a flexible skeleton may be, for example, an epoxy resin represented by the formula (2):

[ CHEM 3]

[ wherein Z independently represents an alkylene group optionally having a hydroxyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 10 carbon atoms), and e represents an integer of 1 or more ].

In the formula (2), each Z independently preferably represents an alkylene group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 10 carbon atoms). e is preferably an integer of 1 to 20.

Examples of commercially available products of the flexible skeleton-containing epoxy resin (A-1) include "EP-4000S" and "EP-4010S" (modified bisphenol epoxy resins) manufactured by ADEKA; "YL 7175-500", "YL 7175-1000", "YL 7410" and "YX 7105" (modified bisphenol type epoxy resins) manufactured by Mitsubishi chemical company; "EXA-4850", "EXA-4850-," EXA-4816 "," EXA-4822 "(modified bisphenol epoxy resins) manufactured by DIC corporation; "EG-280" manufactured by Osaka ガス chemical company; "EX-830" (modified bisphenol epoxy resin) manufactured by ナガセケムテックス; YX7400 (polytetramethylene glycol diglycidyl ether) manufactured by Mitsubishi chemical corporation, and the like.

The epoxy equivalent of the flexible skeleton-containing epoxy resin (A-1) is not particularly limited, but is preferably 50 g/eq.or more, more preferably 100 g/eq.or more, still more preferably 200 g/eq.or more, still more preferably 300 g/eq.or more, and particularly preferably 400 g/eq.or more. The lower limit of the epoxy equivalent of the flexible skeleton-containing epoxy resin (A-1) is not particularly limited, but is preferably 5000 g/eq.or less, more preferably 2000 g/eq.or less, still more preferably 1000 g/eq.or less, still more preferably 700 g/eq.or less, and particularly preferably 500 g/eq.or less. The epoxy equivalent is the mass of the resin having 1 equivalent of epoxy group on average. The epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the flexible skeleton-containing epoxy resin (A-1) is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured by a Gel Permeation Chromatography (GPC) method in terms of polystyrene.

The content of the flexible skeleton-containing epoxy resin (a-1) in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100 mass%, it is preferably 70 mass% or less, more preferably 60 mass% or less, still more preferably 55 mass% or less, still more preferably 50 mass% or less, and particularly preferably 45 mass% or less. The lower limit of the content of the flexible skeleton-containing epoxy resin (a-1) in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100 mass%, it is preferably 0.1 mass% or more, more preferably 1 mass% or more, further preferably 5 mass% or more, further more preferably 8 mass% or more, and particularly preferably 10 mass% or more.

< (A-2) other optional epoxy resin

The (A) epoxy resin in the present invention may contain (A-2) other optional epoxy resins in addition to (A-1) the flexible skeleton-containing epoxy resin.

Examples of the other optional epoxy resin (A-2) include a bismethylphenol type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol novolac type epoxy resin, a phenol novolac type epoxy resin, a t-butyl-catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, a cresol novolac type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, an alicyclic epoxy resin, a heterocyclic epoxy resin, an epoxy resin containing a spiro ring, Cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, naphthalene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenol phthalimide type epoxy resin, phenolphthalein type epoxy resin, and the like. (A-2) other optional epoxy resins may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The resin composition preferably contains, as the other optional epoxy resin (a-2), an epoxy resin having 2 or more epoxy groups in 1 molecule. The proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, based on 100% by mass of the other optional epoxy resin (a-2).

(A-2) other optional epoxy resins can be classified into an epoxy resin that is liquid at a temperature of 20 ℃ (hereinafter, sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20 ℃ (hereinafter, sometimes referred to as "solid epoxy resin"). The resin composition of the present invention may contain only a liquid epoxy resin, only a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin as the other optional epoxy resin (a-2).

The liquid epoxy resin is preferably a liquid epoxy resin having 2 or more epoxy groups in 1 molecule.

The liquid epoxy resin is preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, or an epoxy resin having a butadiene structure.

Specific examples of the liquid epoxy resin include "HP 4032", "HP 4032D" and "HP 4032 SS" (naphthalene type epoxy resin) manufactured by DIC corporation; 828US, 828EL, jER828EL, 825, エピコート 828EL (bisphenol a epoxy resin) manufactured by mitsubishi chemical corporation; "jER 807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 152" (phenol novolac type epoxy resin) manufactured by mitsubishi chemical corporation; "630", "630 LSD" and "604" (glycidyl amine type epoxy resins) manufactured by Mitsubishi chemical corporation; "ED-523T" (glycyl-type epoxy resin) manufactured by ADEKA corporation; "EP-3950L" and "EP-3980S" (glycidyl amine type epoxy resins) manufactured by ADEKA corporation; EP-4088S (dicyclopentadiene type epoxy resin) manufactured by ADEKA Co; "ZX 1059" (a blend of bisphenol A epoxy resin と and bisphenol F epoxy resin) manufactured by Nissian King Kogyo Co., Ltd.; "EX-721" (glycidyl ester type epoxy resin) manufactured by ナガセケムテックス Co; "セロキサイド 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by ダイセル; ダイセル, "PB-3600", Japanese Kozak "JP-100" and "JP-200" (epoxy resin having a butadiene structure); "ZX 1658" and "ZX 1658 GS" (liquid 1, 4-glycidylcyclohexane-type epoxy resins) manufactured by Nippon iron Japan chemical Co., Ltd. These can be used alone in 1 kind, also can be combined with more than 2 kinds.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.

The solid epoxy resin is preferably a bismethylphenol type epoxy resin, a naphthalene type 4-functional epoxy resin, a naphthol novolac type epoxy resin, a cresol novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a naphthalene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol a type epoxy resin, a bisphenol AF type epoxy resin, a phenol aralkyl type epoxy resin, a tetraphenylethane type epoxy resin, a phenol phthalimide type epoxy resin, or a phenolphthalein type epoxy resin.

Specific examples of the solid epoxy resin include "HP 4032H" (naphthalene type epoxy resin) manufactured by DIC corporation; "HP-4700" and "HP-4710" (naphthalene type 4-functional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200", "HP-7200 HH", "HP-7200H" and "HP-7200L" (dicyclopentadiene type epoxy resins) manufactured by DIC; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S" and "HP 6000" (naphthalene ether type epoxy resins) manufactured by DIC; EPPN-502H (trisphenol type epoxy resin) manufactured by Nippon chemical Co., Ltd.; "NC 7000L" (naphthol novolac type epoxy resin) manufactured by japan chemicals); "NC 3000H", "NC 3000L", "NC 3000 FH" and "NC 3100" (biphenyl type epoxy resin) manufactured by japan chemical company; ESN475V (naphthalene type epoxy resin) manufactured by Nichika & マテリアル; ESN485 (naphthol type epoxy resin) manufactured by Nichika & マテリアル; ESN375 (dihydroxynaphthalene-type epoxy resin) manufactured by Nichika & マテリアル; "YX 4000H", "YX 4000 HK" and "YL 7890" (bismethylphenol type epoxy resin) manufactured by Mitsubishi chemical company; "YL 6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical corporation; YX8800 (anthracene-based epoxy resin) available from Mitsubishi chemical corporation; "YX 7700" (phenol aralkyl type epoxy resin) manufactured by Mitsubishi chemical corporation; PG-100 and CG-500 manufactured by Osaka ガス chemical company; "YL 7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL 7800" (fluorene-based epoxy resin) manufactured by Mitsubishi chemical corporation; "jER 1010" (bisphenol a type epoxy resin) manufactured by mitsubishi chemical corporation; "jER 1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi chemical corporation; "WHR 991S" (phenol phthalimide type epoxy resin) manufactured by Nippon chemical Co., Ltd. These can be used alone in 1 kind, also can be combined with more than 2 kinds.

(A-2) the epoxy equivalent of the other optional epoxy resins is preferably 50 g/eq.about 5,000 g/eq.about, more preferably 60 g/eq.about 2,000 g/eq.about, further preferably 70 g/eq.about 1,000 g/eq.about, further more preferably 80 g/eq.about 500 g/eq.about. The epoxy equivalent is the mass of the resin having 1 equivalent of epoxy group on average. The epoxy equivalent can be measured according to JIS K7236.

The weight average molecular weight (Mw) of the optional epoxy resin (A-2) is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured by a Gel Permeation Chromatography (GPC) method in terms of polystyrene.

The content of the other optional epoxy resin (a-2) in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, further more preferably 20% by mass or less, and particularly preferably 15% by mass or less. The lower limit of the content of the optional epoxy resin (a-2) in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100 mass%, the content may be, for example, 0 mass% or more, 0.01 mass% or more, 0.1 mass% or more, 0.5 mass% or more, 1 mass% or more, 3 mass% or more, 5 mass% or more, or the like.

When the resin composition contains (A-2) another optional epoxy resin, the mass ratio ((A-2)/(A-1)) of the (A-2) other optional epoxy resin to the (A-1) flexible skeleton-containing epoxy resin in the resin composition may be preferably 2 or less, more preferably 1.5 or less, still more preferably 1 or less, and particularly preferably 0.7 or less.

< (B) a thiol compound

The resin composition of the present invention contains (B) a thiol compound. When the thiol compound (B) is used as the curing agent for the epoxy resin (a), the curing agent can be cured at a relatively low temperature, and the decrease in magnetic properties can be suppressed.

(B) The thiol compound is an organic compound having a mercapto group (-SH), and is preferably a thiol compound having 2 or more functions from the viewpoint of obtaining excellent epoxy curability, and more preferably a thiol compound having 3 or more functions from the viewpoint of further increasing the crosslinking density. (B) In the description of the thiol compound, the number of functional groups is shown based on the number of mercapto groups (-SH) contained in 1 molecule. In addition, such a thiol compound is preferably a primary and/or secondary thiol compound from the viewpoint of improving reactivity.

(B) The thiol compound includes not only a saturated hydrocarbon structure but also an unsaturated hydrocarbon structure. (B) The thiol compound also includes a substance containing a linear, branched, and/or cyclic structure (e.g., an isocyanuric acid structure, a glycoluril structure, a benzene ring structure, etc.). In one embodiment, from the viewpoint of further improving impact resistance, it is preferable to include a thiol compound not having a cyclic structure (including a linear and/or branched thiol compound not having a cyclic structure). (B) The thiol compound may be a non-aromatic thiol compound (not containing an aromatic ring) or an aromatic thiol compound (containing an aromatic ring), and in one embodiment, a non-aromatic thiol compound (not containing an aromatic ring) is preferable from the viewpoint of further improving impact resistance. (B) The thiol compound may have a functional group such as a hydroxyl group, a carboxyl group, or an amino group in addition to a thiol group, and is preferably not present in one embodiment.

Examples of the thiol compound (B) include hydrocarbon thiol compounds, ether structure-containing thiol compounds, thioether structure-containing thiol compounds, amine-containing thiol compounds, alcohol-containing thiol compounds, carboxylate structure-containing thiol compounds, isocyanurate structure-containing thiol compounds, carboxylate structure-containing thiol compounds, glycoluril structure-containing thiol compounds, and the like. (B) The thiol compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds at an arbitrary ratio.

The hydrocarbon thiol compound is a thiol compound having a hydrocarbon as a basic skeleton, and examples thereof include 2-functional hydrocarbon thiol compounds such as 1, 4-butanedithiol, 1, 6-hexanedithiol, 1, 8-octanedithiol, 1, 10-decanedithiol, 2-dimethylpropane-1, 3-dithiol, 1, 4-cyclohexanedithiol, 1, 2-cyclohexanedithiol, m-xylene- α, α '-dithiol, and p-xylene- α, α' -dithiol; 3-functional hydrocarbon thiol compounds such as 2-mercaptomethyl-1, 3-propanedithiol, 2-ethyl-2- (mercaptomethyl) -1, 3-propanedithiol, 2-mercaptomethyl-1, 4-butanedithiol, and 1,2, 3-propanetrithiol; and 4-functional hydrocarbon thiol compounds such as tetrakis (mercaptomethyl) methane and 2, 2-bis (mercaptomethyl) -1, 3-propanedithiol.

The ether structure-containing thiol compound is a thiol compound having an ether structure, and examples thereof include 3, 6-dioxa-1, 8-octanedithiol, 3,6, 9-trioxaundecane-1, 11-dithiol, 3, 4-dimethoxybutane-1, 2-dithiol, 2, 3-dimercaptopropylmethyl ether, bis (2-mercaptoethyl) ether, 2-functional ether structure-containing thiol compounds such as bis [4- (2-mercaptoethyloxy) phenyl ] methane, bis [4- (3-mercaptopropyloxy) phenyl ] methane, 2-bis [4- (2-mercaptoethyloxy) phenyl ] propane, and 2, 2-bis [4- (3-mercaptopropyloxy) phenyl ] propane; (2-mercaptoethyl) (2, 3-dimercaptopropyl) ether, trimethylolpropane tris (2-mercaptoethyl) ether, trimethylolethane tris (2-mercaptoethyl) ether, trimethylolpropane tris (3-mercaptopropyl) ether, trimethylolethane tris (3-mercaptopropyl) ether, trimethylolpropane tris (4-mercaptobutyl) ether, trimethylolethane tris (4-mercaptobutyl) ether, glycerol tris (3-mercaptopropyl) ether, glycerol tris (4-mercaptobutyl) ether, trimethylolpropane tris (2-mercaptopropyl) ether, trimethylolethane tris (2-mercaptopropyl) ether, trimethylolpropane tris (3-mercaptobutyl) ether, trimethylolethane tris (3-mercaptobutyl) ether, glycerol tris (2-mercaptopropyl) ether, 3-functional ether structure-containing thiol compounds such as glycerol tris (3-mercaptobutyl) ether; 4-functional ether structure-containing thiol compounds such as bis (2, 3-dimercaptopropyl) ether, pentaerythritol tetrakis (2-mercaptoethyl) ether, pentaerythritol tetrakis (3-mercaptopropyl) ether, pentaerythritol tetrakis (4-mercaptobutyl) ether, pentaerythritol tetrakis (2-mercaptopropyl) ether, and pentaerythritol tetrakis (3-mercaptobutyl) ether; and 5 or more functional and polyfunctional ether structure-containing thiol compounds such as dipentaerythritol hexa (3-mercaptopropyl) ether and dipentaerythritol hexa (2-mercaptopropyl) ether.

The thiol compound having a thioether structure is a thiol compound having a thioether structure, and examples thereof include 2-functional thiol compounds having a thioether structure, such as bis (2-mercaptoethyl) sulfide, 3, 6-dithia-1, 8-octanedithiol, 3,6, 9-trithiaundecane-1, 11-dithiol, and 1, 4-dithiane-2, 5-bis (methanethiol); 3-functional thiol compounds having a thioether structure, such as 4- (2-mercaptoethyl) -3, 6-dithia-1, 8-octanedithiol and 4-mercaptomethyl-3, 6-dithia-1, 8-octanedithiol; 4-functional sulfide structure-containing thiol compounds such as 1,2,6, 7-tetramercapto-4-thiaheptane, 4, 7-bis (mercaptomethyl) -3,6, 9-trithiaundecane-1, 11-dithiol, 5, 7-bis (mercaptomethyl) -3,6, 9-trithiaundecane-1, 11-dithiol, 2, 6-bis (mercaptomethyl) -3, 5-dithiaheptane-1, 7-dithiol, and 3, 5-bis (mercaptomethylthio) -2, 6-dithiaheptane-1, 7-dithiol; and 5 or more functional polyfunctional sulfide structure-containing thiol compounds such as 1,2,9, 10-tetramercapto-6-mercaptomethyl-4, 7-dithiadecane, 1,2,6,10, 11-pentamercapto-4, 8-dithiaundecane, 1,2,9,13, 14-pentamercapto-6-mercaptomethyl-4, 7, 11-trithiotetradecane, 1,2,6,10,14, 15-hexamercapto-4, 8, 12-trithiopentadecane.

The amine-containing thiol compound refers to a thiol compound having an amine structure (preferably a secondary amine structure or a tertiary amine structure) (and further optionally having an ether structure or a thioether structure), and examples thereof include 2-functional amine-containing thiol compounds such as bis [4- (3-phenoxy-2-mercaptopropylamino) phenyl ] methane, bis {4- [3- (4-methylphenoxy) -2-mercaptopropylamino ] phenyl } methane, and 1, 4-bis (3-phenoxy-2-mercaptopropylamino) benzene.

The alcohol-containing thiol compound refers to a thiol compound having a hydroxyl group (further optionally having an ether structure or a thioether structure), and examples thereof include 2-functional alcohol-containing thiol compounds such as 1, 3-dimercapto-2-propanol, 2, 3-dimercapto-1-propanol, and 2, 2-bis (mercaptomethyl) -1, 3-propanediol; and 3-functional alcohol-containing thiol compounds such as pentaerythritol tris (3-mercaptopropyl) ether and 3-mercapto-2, 2-bis (mercaptomethyl) -1-propanol.

The thiol compound having a carboxylate structure is a thiol compound having a carboxylate structure (further optionally having an ether structure or a thioether structure), and examples thereof include bis (2-mercaptoethyl) succinate, bis (2-mercaptoethyl) phthalate, bis (3-mercaptopropyl) phthalate, bis (4-mercaptobutyl) phthalate, ethylene glycol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (4-mercaptobutyrate), propylene glycol bis (3-mercaptopropionate), propylene glycol bis (4-mercaptobutyrate), diethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (4-mercaptobutyrate), tetraethylene glycol bis (3-mercaptopropionate), 1, 4-butanediol bis (mercaptoacetate), 1, 4-butanediol bis (3-mercaptopropionate), 1, 4-butanediol bis (4-mercaptobutyrate), 1, 8-octanediol bis (3-mercaptopropionate), 1, 8-octanediol bis (4-mercaptobutyrate), bis (1-mercaptoethyl) phthalate, bis (2-mercaptopropyl) phthalate, bis (3-mercaptobutyl) phthalate, ethylene glycol bis (2-mercaptopropionate), ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (2-mercaptopropionate), propylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (2-mercaptopropionate), diethylene glycol bis (3-mercaptobutyrate), tetraethylene glycol bis (2-mercaptopropionate), 1, 2-functional thiol compounds having a carboxylate structure, such as 4-butanediol bis (2-mercaptopropionate), 1, 4-butanediol bis (3-mercaptobutyrate), 1, 8-octanediol bis (2-mercaptopropionate), and 1, 8-octanediol bis (3-mercaptobutyrate); bis (2-mercaptoethyl) thiomalate, trimethylolpropane tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptopropionate), trimethylolpropane tris (4-mercaptobutyrate), trimethylolethane tris (4-mercaptobutyrate), glycerol tris (3-mercaptopropionate), 3-functional thiol compounds having a carboxylate structure, such as glycerol tris (4-mercaptobutyrate), trimethylolpropane tris (2-mercaptopropionate), trimethylolethane tris (2-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), glycerol tris (2-mercaptopropionate), and glycerol tris (3-mercaptobutyrate); 4-functional thiol compounds having a carboxylate structure, such as 2, 3-dimercaptosuccinic acid bis (2-mercaptoethyl) ester, pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (4-mercaptobutyrate), pentaerythritol tetrakis (2-mercaptopropionate), and pentaerythritol tetrakis (3-mercaptobutyrate); and 5 or more functional polyfunctional thiol compounds containing a carboxylic ester structure, such as dipentaerythritol hexa (3-mercaptopropionate) and dipentaerythritol hexa (2-mercaptopropionate).

The isocyanurate structure-containing thiol compound is a thiol compound having an isocyanuric acid (i.e., 1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione) structure (further optionally having an ether structure or a thioether structure), and examples thereof include 3-functional isocyanurate structure-containing thiol compounds such as tris (3-mercaptopropyl) isocyanurate, tris (2-mercaptoethyl) isocyanurate, and tris (4-mercaptobutyl) isocyanurate.

The thiol compound having an isocyanurate structure of a carboxylate structure is a thiol compound having a carboxylate structure and an isocyanuric acid structure (further optionally having an ether structure or a thioether structure), and examples thereof include 3-functional thiol compounds having an isocyanurate structure of a carboxylate structure such as tris [2- (3-mercaptopropionyloxy) ethyl ] isocyanurate, tris [2- (4-mercaptobutyryloxy) ethyl ] isocyanurate, tris [2- (2-mercaptopropionyloxy) ethyl ] isocyanurate and tris [2- (3-mercaptobutyryloxy) ethyl ] isocyanurate.

The thiol compound having a glycoluril structure is a thiol compound having a glycoluril structure (i.e., tetrahydroimidazo [4,5-d ] imidazole-2, 5(1H,3H) -dione) structure, and examples thereof include 2-functional thiol compounds having a glycoluril structure, such as 1, 3-bis (2-mercaptoethyl) glycoluril, 1, 3-bis (3-mercaptopropyl) glycoluril, 1, 4-bis (2-mercaptoethyl) glycoluril, 1, 4-bis (3-mercaptopropyl) glycoluril, 1, 6-bis (2-mercaptoethyl) glycoluril, and 1, 6-bis (3-mercaptopropyl) glycoluril; 3-functional thiol compounds containing a glycoluril structure, such as 1,3, 4-tris (2-mercaptoethyl) glycoluril and 1,3, 4-tris (3-mercaptopropyl) glycoluril; and 4-functional thiol compounds containing a glycoluril structure, such as 1,3,4, 6-tetrakis (2-mercaptoethyl) glycoluril and 1,3,4, 6-tetrakis (3-mercaptopropyl) glycoluril.

In one embodiment, the thiol compound (B) is preferably a thiol compound containing no carboxylic ester structure from the viewpoint of further improving hydrolysis resistance.

In one embodiment, the thiol compound (B) may be a solid thiol compound at 25 ℃ or a liquid thiol compound at 25 ℃, and when the resin composition is used as a sealant or an adhesive, a liquid thiol compound at 25 ℃ may be preferable.

(B) The molecular weight of the thiol compound is not particularly limited, but is preferably 200 or more, more preferably 250 or more, further preferably 300 or more, and particularly preferably 350 or more. (B) The upper limit of the molecular weight of the thiol compound is not particularly limited, but is preferably 1,500 or less, more preferably 1,000 or less, further preferably 800 or less, and particularly preferably 700 or less.

(B) The thiol equivalent of the thiol compound is not particularly limited, but is preferably 1000 g/eq.less, more preferably 500 g/eq.less, still more preferably 300 g/eq.less, yet more preferably 200 g/eq.less, and particularly preferably 150 g/eq.less. (B) The lower limit of the thiol equivalent of the thiol compound is not particularly limited, but is preferably 50 g/eq.or more, more preferably 70 g/eq.or more, still more preferably 90 g/eq.or more, still more preferably 100 g/eq.or more, and particularly preferably 110 g/eq.or more. The thiol equivalent is the mass of thiol compound of 1 equivalent of mercapto group on average.

The ratio (mercapto group/epoxy group) of the total number of mercapto groups of the thiol compound (B) to the total number of epoxy groups of the epoxy resin (a) in the resin composition is preferably 0.1 or more, more preferably 0.3 or more, further preferably 0.5 or more, and particularly preferably 0.8 or more. The upper limit of the ratio (mercapto group/epoxy group) of the total number of mercapto groups of the thiol compound (B) to the total number of epoxy groups of the epoxy resin (a) in the resin composition is preferably 2.0 or less, more preferably 1.5 or less, further preferably 1.2 or less, and particularly preferably 1.0 or less.

The content of the thiol compound (B) in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, further more preferably 25% by mass or less, and particularly preferably 20% by mass or less. The lower limit of the content of the thiol compound (B) in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100% by mass, it is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and particularly preferably 7% by mass or more. In one embodiment, the content of the (B) thiol compound may be set based on the content of the (a) epoxy resin and the epoxy equivalent.

The mass ratio of the thiol compound (B) to the epoxy resin (a) ((B) thiol compound/(a) epoxy resin) in the resin composition is not particularly limited, but is preferably 0.1 or more, more preferably 0.15 or more, further preferably 0.2 or more, and particularly preferably 0.25 or more. The upper limit of the mass ratio of the thiol compound (B) to the epoxy resin (a) ((B) thiol compound/(a) epoxy resin) in the resin composition is not particularly limited, and is preferably 1.5 or less, more preferably 1 or less, further preferably 0.7 or less, and particularly preferably 0.5 or less.

Magnetic powder (C)

The resin composition of the present invention contains (C) a magnetic powder. By containing (C) a magnetic powder in the resin composition of the present invention, the specific permeability of the cured product thereof can be improved.

(C) The magnetic powder may be either a soft magnetic powder or a hard magnetic powder, and from the viewpoint of remarkably obtaining the effect of the present invention, a soft magnetic powder is preferable.

Examples of the magnetic powder (C) include iron oxide powders such as Fe-Mn based ferrite, Fe-Mn-Zn based ferrite, Mg-Zn based ferrite, Mn-Mg based ferrite, Cu-Zn based ferrite, Mg-Mn-Sr based ferrite, Ni-Zn based ferrite, Ba-Mg based ferrite, Ba-Ni based ferrite, Ba-Co based ferrite, Ba-Ni-Co based ferrite, Y based ferrite, iron oxide powder (III), and ferroferric oxide; pure iron powder; an iron alloy-based metal powder such as an Fe-Si-based alloy powder, an Fe-Si-Al-based alloy powder, an Fe-Cr-Si-based alloy powder, an Fe-Ni-Cr-based alloy powder, an Fe-Cr-Al-based alloy powder, an Fe-Ni-Mo-Cu-based alloy powder, an Fe-Co-based alloy powder, or an Fe-Ni-Co-based alloy powder; amorphous alloys such as Co-based amorphous alloys, and the like. (C) The magnetic powder may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Among them, the (C) magnetic powder is preferably at least 1 selected from iron oxide powder and iron alloy-based metal powder. The iron oxide powder preferably contains a ferrite containing at least 1 kind selected from the group consisting of Ni, Cu, Mn, and Zn, and more preferably contains at least 1 kind selected from the group consisting of Fe — Mn-based ferrite and Fe — Mn — Zn-based ferrite. The iron alloy-based metal powder preferably contains at least 1 kind selected from Si, Cr, Al, Ni, and Co.

As the (C) magnetic powder, commercially available products may be used, or 2 or more kinds may be used in combination. Specific examples of commercially available magnetic powders that can be used include M series such as "M05S" and "M05 SWD" manufactured by パウダーテック; パウダーテック, "MZ 05"; "PST-S" manufactured by Shanyang Special Steel works, Inc.; エプソンアトミックス, "AW 2-08", "AW 2-08PF 20F", "AW 2-08PF 10F", "AW 2-08PF 3F", "Fe-3.5 Si-4.5CrPF 20F", "Fe-50 NiPF 20F", "Fe-80 Ni-4MoPF 20F"; "LD-M", "LD-MH", "KNI-106 GSM", "KNI-106 GS", "KNI-109 GSM", "KNI-109 GS", manufactured by JFE chemical company; "KNS-415", "BSF-547", "BSF-029", "BSN-125", "BSN-714", "BSN-828", "S-1281", "S-1641", "S-1651", "S-1470", "S-1511", "S-2430" manufactured by Kontan industries, Ltd.; "JR 09P 2" manufactured by Nippon Seikagaku industries Co., Ltd.; "Nanotek" manufactured by CIK ナノテック Inc.; "JEMK-S" and "JEMK-H" manufactured by キンセイマテック: and "Yttrium iron oxide" manufactured by ALDRICH Co.

(C) The magnetic powder is preferably spherical. The value (aspect ratio) obtained by dividing the length of the major axis of the magnetic powder by the length of the minor axis is preferably 2 or less, more preferably 1.5 or less, and still more preferably 1.2 or less. By using spherical magnetic powder, magnetic loss can be reduced, and a resin composition having a desired preferable viscosity can be obtained.

(C) The average particle diameter of the magnetic powder is preferably 0.01 μm or more, more preferably 0.5 μm or more, and further preferably 1 μm or more, from the viewpoint of improving the specific magnetic permeability. (C) The upper limit of the average particle diameter of the magnetic powder is preferably 10 μm or less, more preferably 9 μm or less, and still more preferably 8 μm or less.

(C) The average particle diameter of the magnetic powder can be measured by a laser diffraction scattering method based on Mie scattering theory. Specifically, the particle size distribution of the magnetic powder can be prepared on a volume basis by a laser diffraction scattering particle size distribution measuring apparatus, and the median diameter thereof is determined as an average particle size. The measurement sample may preferably be a substance in which magnetic powder is dispersed in water by ultrasound. As the laser diffraction scattering type particle size distribution measuring apparatus, "LA-500" manufactured by horiba, Inc., SALD-2200 manufactured by Shimadzu, Inc., and the like can be used.

In one embodiment, the (C) magnetic powder may be treated with a surface treatment agent from the viewpoint of adjusting the viscosity of the resin composition and further improving the moisture resistance and dispersibility. Examples of the surface treatment agent include vinyl silane coupling agents, (meth) acrylic acid coupling agents, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, alkoxysilanes, organosilicon nitrogen compounds, titanate coupling agents, and the like. The surface treatment agent may be used alone in 1 kind, or may be used in any combination of 2 or more kinds.

Examples of commercially available surface-treating agents include "KBM 1003" (vinyltriethoxysilane), "KBM 503" (3-methacryloxypropyltriethoxysilane), and "KBM 403" (3-glycidoxypropyltrimethoxysilane), manufactured by shin-Etsu chemical Co., Ltd., "KBM 803" (3-mercaptopropyltrimethoxysilane), and "KBE 903" (3-aminopropyltriethoxysilane), manufactured by shin-Etsu chemical Co., Ltd., "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane), and "SZ-31" (hexamethyldisilazane), and "KBM 103" (phenyltrimethoxysilane), manufactured by shin-Etsu chemical Co., Ltd., "KBM-4803" (epoxy-type silane coupling agent), KBM-7103 (3,3, 3-trifluoropropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, Ltd.

The degree of surface treatment with the surface treatment agent preferably falls within a predetermined range from the viewpoint of improving the dispersibility of the (C) magnetic powder. Specifically, (C) 100 parts by mass of the magnetic powder is preferably surface-treated with 0.01 to 5 parts by mass of a surface treatment agent, preferably 0.05 to 3 parts by mass, and preferably 0.1 to 2 parts by mass.

(C) The content (volume%) of the magnetic powder is preferably 0.1 volume% or more, more preferably 1 volume% or more, further preferably 5 volume% or more, further more preferably 10 volume% or more, and particularly preferably 14 volume% or more, when the nonvolatile component in the resin composition is taken as 100 volume%, from the viewpoint of improving the specific permeability and reducing the loss coefficient. (C) The upper limit of the content (volume%) of the magnetic powder is not particularly limited, and in one embodiment, from the viewpoint of functioning as a magnetic adhesive in a paste form, when the nonvolatile component in the resin composition is taken as 100 mass%, it is preferably 85 volume% or less, more preferably 70 volume% or less, further preferably 60 volume% or less, further more preferably 50 volume% or less, and particularly preferably 40 volume% or less.

(C) The content (mass%) of the magnetic powder is preferably 5 mass% or more, more preferably 20 mass% or more, further preferably 30 mass% or more, further more preferably 35 mass% or more, and particularly preferably 40 mass% or more, when the nonvolatile component in the resin composition is taken as 100 mass%, from the viewpoint of improving the specific permeability and reducing the loss coefficient. (C) The upper limit of the content (mass%) of the magnetic powder is not particularly limited, and in one embodiment, from the viewpoint of functioning as a magnetic adhesive in a paste form, when the nonvolatile component in the resin composition is taken as 100 mass%, it is preferably 90 mass% or less, more preferably 85 mass% or less, further preferably 80 mass% or less, further more preferably 77 mass% or less, and particularly preferably 75 mass% or less.

(D) stabilizer

The resin composition of the present invention sometimes contains (D) a stabilizer as an optional ingredient. (D) The stabilizer has a function of improving the storage stability of the resin composition (particularly, one-pack type resin composition).

Examples of the stabilizer (D) include borate compounds, titanate compounds, aluminate compounds, zirconate compounds, isocyanate compounds, carboxylic acids, and carboxylic acid anhydrides. (D) The stabilizer may be used alone in 1 kind, or may be used in combination in 2 or more kinds at an arbitrary ratio.

Examples of the borate ester compound include trialkyl borates such as trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, tripentyl borate, trihexyl borate, tricyclohexyl borate, tri (2-ethylhexyl) borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, and trioctadecyl borate; triallyl borates such as triallyl borate; triaryl borates such as triphenyl borate, tris (2-methylphenyl) borate, tris (3-methylphenyl) borate, tris (4-methylphenyl) borate, tris (2-ethylphenyl) borate, tris (3-ethylphenyl) borate, tris (4-ethylphenyl) borate, tris (3, 5-dimethylphenyl) borate, and tris (2, 4-dimethylphenyl) borate; triaryl alkyl borates such as trityl borate; and amino group-containing boric acid esters such as triethanolamine borate.

Examples of the titanate compound include tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraoctyl titanate, and the like.

Examples of the aluminate compound include triethyl aluminate, tripropyl aluminate, triisopropyl aluminate, tributyl aluminate, and trioctyl aluminate.

Examples of the zirconate compound include tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, and tetrabutyl zirconate.

Examples of the isocyanate compound include n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, 2-ethylphenyl isocyanate, 2, 6-dimethylphenyl isocyanate, toluene diisocyanate (e.g., 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate), 1, 5-naphthalene diisocyanate, diphenylmethane-4, 4' -diisocyanate, ditolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, bicycloheptane triisocyanate, and the like.

Examples of the carboxylic acid include saturated aliphatic monobasic acids such as formic acid, acetic acid, propionic acid, butyric acid, caproic acid, and caprylic acid; unsaturated aliphatic monobasic acids such as acrylic acid, methacrylic acid, and crotonic acid; monohydric hydroxy acids such as glycolic acid and lactic acid; aliphatic aldehyde acids such as glyoxylic acid and gluconic acid; aliphatic polybasic acids such as oxalic acid, malonic acid, succinic acid, and maleic acid; aromatic monobasic acids such as benzoic acid, p-toluic acid, phenylacetic acid, cinnamic acid, and mandelic acid; aromatic polybasic acids such as phthalic acid and trimesic acid; halogenated fatty acids such as monochloroacetic acid and dichloroacetic acid.

Examples of the carboxylic acid anhydride include aliphatic polybasic acid anhydrides such as succinic anhydride, dodecenylsuccinic anhydride, maleic anhydride, hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, aromatic polybasic acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride.

The content of the stabilizer (D) in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100 mass%, it is preferably 1 mass% or less, more preferably 0.5 mass% or less, and still more preferably 0.3 mass% or less. The lower limit of the content of the stabilizer (D) in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100 mass%, the content may be, for example, 0 mass% or more, 0.001 mass% or more, preferably 0.01 mass% or more, more preferably 0.05 mass% or more, and still more preferably 0.1 mass% or more.

(E) dispersant

The resin composition of the present invention sometimes contains (E) a dispersant as an optional ingredient.

Examples of the dispersant (E) include phosphate dispersants such as polyoxyethylene alkyl ether phosphoric acid; polyoxyalkylene-based dispersants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylamines, and polyoxyethylene alkylamides; acetylene-based dispersants such as acetylene glycol; silicone dispersants such as polyether-modified polydimethylsiloxane, polyether-modified siloxane, and polyester-modified polydimethylsiloxane; anionic dispersants such as sodium polyacrylate, sodium dodecylbenzenesulfonate, sodium laurate, ammonium polyoxyethylene alkyl ether sulfate, and carboxymethyl cellulose sodium salt; cationic dispersants such as amino group-containing polyacrylate resins and amino group-containing polystyrene resins. (E) The dispersant may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

As commercially available products of the phosphate-based dispersant, there are "RS-410", "RS-610" and "RS-710" of "フォスファノール" series manufactured by Toho chemical industry Co., Ltd.

Commercially available polyoxyalkylene dispersants include "AKM-0531", "AFB-1521", "SC-0505K", "SC-1015F" and "SC-0708A" manufactured by Nikkiso Co., Ltd., and "HKM-50A", which are "マリアリム" series.

Commercially available acetylene-based dispersants include "82", "104", "440", "465" and "485" of "サーフィノール" series manufactured by Air Products and Chemicals inc.

Examples of commercially available products of silicone dispersants include "BYK 347" and "BYK 348" manufactured by ビックケミー.

Commercially available products of anionic dispersants include "PN-411" and "PA-111" manufactured by Torricellia fortunei ファインテクノ Co., Ltd.; ライオン, "A-550", "PS-1900", and the like.

Examples of commercially available cationic dispersants include "161", "162", "164", "182", "2000" and "2001" manufactured by ビックケミー; "PB-821", "PB-822", "PB-824" manufactured by KAIKOSU ファインテクノ; "V-216" and "V-220" manufactured by アイエスピー & ジャパン Co; ルーブリゾール, "ソルスパース 13940", "ソルスパース 24000", "ソルスパース 32000", and the like.

The content of the dispersant (E) in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100 mass%, it is preferably 1 mass% or less, more preferably 0.7 mass% or less, and still more preferably 0.5 mass% or less. The lower limit of the content of the dispersant (E) in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100 mass%, the content may be, for example, 0 mass% or more, 0.001 mass% or more, 0.01 mass% or more, preferably 0.05 mass% or more, more preferably 0.1 mass% or more, and still more preferably 0.2 mass% or more.

(F) curing Accelerator

The resin composition of the present invention sometimes contains (F) a curing accelerator as an optional ingredient.

As the (F) curing accelerator, a latent curing accelerator is preferably used. The latent curing accelerator is an important component particularly in the case of a one-pack type resin composition, and has a function of accelerating the curing of the epoxy resin (a) during heating without contributing to the curing of the epoxy resin (a) at normal temperature (25 ℃). (F) The curing accelerator may be used alone in 1 kind, or may be used in combination in 2 or more kinds at an arbitrary ratio.

The latent curing accelerator may be a liquid latent curing accelerator or a solid dispersion type latent curing accelerator, and more preferably a solid dispersion type latent curing accelerator.

The liquid latent curing accelerator is a liquid that is soluble in an epoxy resin at room temperature (25 ℃), and functions as a curing accelerator for an epoxy resin when heated. Examples of the liquid latent curing accelerator include, but are not limited to, ionic liquids.

Examples of the cation constituting the ionic liquid include ammonium cations such as imidazolium ions, piperidinium ions, pyrrolidinium ions, pyrazolium ions, guanidinium ions, pyridinium ions, and hydrocarbon (alkyl groups, phenyl groups, combinations thereof, and the like) substituents thereof; phosphonium cations such as tetraalkylphosphonium ions; sulfonium cations such as trialkylsulfonium ions, and the like.

Examples of the anion constituting the ionic liquid include halide anions such as fluoride ion, chloride ion, bromide ion, and iodide ion: alkylsulfuric acid-based anions such as methanesulfonate ion: fluorine-containing compound-based anions such as trifluoromethanesulfonic acid ion, hexafluorophosphonic acid ion, trifluorotris (pentafluoroethyl) phosphonic acid ion, bis (trifluoromethanesulfonyl) imide ion, trifluoroacetic acid ion, tetrafluoroboric acid ion, and the like: phenol anions such as phenol ion, 2-methoxyphenol ion, and 2, 6-di-tert-butylphenol ion: acidic amino acid ions such as aspartic acid ion and glutamic acid ion: neutral amino acid ions such as glycine ion, alanine ion, and phenylalanine ion: n-acyl amino acid ions such as N-benzoylalanine ion, N-acetylphenylalanine ion, N-acetylglycine ion, and N-acetylglycine ion: carboxylic acid anions such as formate ion, lactate ion, tartrate ion, hippurate ion, N-methylhippurate ion, and benzoate ion.

The solid dispersion type latent curing accelerator is a solid that is insoluble in an epoxy resin at normal temperature (25 ℃), and is a compound that is solubilized in the epoxy resin by heating and functions as a curing accelerator for the epoxy resin.

Examples of the solid-dispersion type latent curing accelerator include, but are not limited to, imidazole compounds which are solid at room temperature (25 ℃) and solid-dispersion type amine adduct type latent curing accelerators.

Examples of the imidazole compound which is solid at ordinary temperature (25 ℃) include 2-heptadecylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2, 4-diamino-6- [2- (2-methyl-1-imidazolyl) ethyl ] -1,3, 5-triazine isocyanuric acid adduct, 2-methylimidazole, 2-methoxyimidazole, and mixtures thereof, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N- (2-methylimidazolyl-1-ethyl) urea, and the like, but are not limited thereto.

Suitable examples of the solid dispersion type amine adduct-based latent curing accelerator include at least 1 selected from the group consisting of an epoxy adduct of an amine compound, a urea adduct of an amine compound, and a compound obtained by addition reaction of a hydroxyl group of an epoxy adduct with an isocyanate compound.

Examples of the epoxy compound used as one of raw materials for producing an epoxy adduct of an amine compound include polyglycidyl ethers obtained by reacting epichlorohydrin with a polyhydric phenol such as bisphenol a, bisphenol F, catechol, or resorcinol, or a polyhydric alcohol such as glycerol or polyethylene glycol; glycidyl ether ester obtained by reacting a hydroxycarboxylic acid such as p-hydroxybenzoic acid or β -hydroxynaphthoic acid with epichlorohydrin; polyglycidyl esters obtained by reacting epichlorohydrin with polycarboxylic acids such as phthalic acid and terephthalic acid; glycidyl amine compounds obtained by reacting epichlorohydrin with 4,4' -diaminodiphenylmethane, m-aminophenol, or the like; and polyfunctional epoxy compounds such as epoxidized phenol novolak resins, epoxidized cresol novolak resins, and epoxidized polyolefins, and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate, but are not limited thereto.

The amine compound used as a raw material for producing the solid-dispersed amine adduct-based latent curing accelerator may be any compound having 1 or more active hydrogens capable of undergoing an addition reaction with an epoxy group in the molecule and having at least 1 functional group selected from the group consisting of primary, secondary and tertiary amino groups in the molecule. Examples of such amine compounds include aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4' -diamino-dicyclohexylmethane; aromatic amine compounds such as 4,4' -diaminodiphenylmethane and 2-methylaniline; and nitrogen-containing heterocyclic compounds such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2, 4-dimethylimidazoline, piperidine, piperazine, and the like, but are not limited thereto.

Among them, a compound having a tertiary amino group in the molecule is a raw material of a latent curing accelerator which gives excellent curing acceleration ability, and examples of such a compound include amine compounds such as dimethylaminopropylamine, diethylaminopropylamine, di-N-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine; primary or secondary amines having a tertiary amino group in the molecule, such as imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazole Alcohols having a tertiary amino group in the molecule, such as oxazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2- (dimethylaminomethyl) phenol, 2,4, 6-tris (dimethylaminomethyl) phenol, N-. beta. -hydroxyethylmorpholine, 2-dimethylaminoethylthiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N-dimethylaminobenzoic acid, N-dimethylglycine, nicotinic acid, isonicotinic acid, picoline, N-dimethylglycine hydrazide, N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide and isonicotinic acid hydrazide, phenols, thiols, acid esters, and water-soluble salts thereof, Carboxylic acids and hydrazides, and the like.

In the case of producing a latent curing accelerator by addition reaction of an epoxy compound and an amine compound, an active hydrogen compound having 2 or more active hydrogens in the molecule may be further reacted. Examples of such an active hydrogen compound include, but are not limited to, polyphenols such as bisphenol a, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, biphenyltriol, and phenol novolac resins, polyols such as trimethylolpropane, polycarboxylic acids such as adipic acid and phthalic acid, 1, 2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, thioglycolic acid, anthranilic acid, and lactic acid.

As the isocyanate compound used as a raw material for producing the solid-dispersed amine adduct-based latent curing accelerator, for example, monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluene diisocyanate, 1, 5-naphthalene diisocyanate, diphenylmethane-4, 4' -diisocyanate, isophorone diisocyanate, xylylene diisocyanate, p-phenylene diisocyanate, 1,3, 6-hexamethylene triisocyanate, and bicycloheptane triisocyanate; and a compound containing a terminal isocyanate group obtained by reacting the polyfunctional isocyanate compound with an active hydrogen compound. Examples of such a compound having a terminal isocyanate group include, but are not limited to, an adduct compound having a terminal isocyanate group obtained by a reaction between tolylene diisocyanate and trimethylolpropane, and an adduct compound having a terminal isocyanate group obtained by a reaction between tolylene diisocyanate and pentaerythritol.

Examples of the urea compound used as a raw material for producing the solid-dispersed amine adduct-based latent curing accelerator include, but are not limited to, urea and thiourea.

The solid dispersion type amine adduct-based latent curing accelerator can be easily obtained by, for example: the above-mentioned raw materials are appropriately mixed, reacted at a temperature of from room temperature to 200 ℃, cooled and solidified, and then pulverized, or reacted in a solvent such as methyl ethyl ketone, dioxane, tetrahydrofuran, etc., and desolvated, and then the solid content is pulverized.

Examples of commercially available solid dispersion type amine adduct-based latent curing accelerators include "アミキュア PN-FJ" (manufactured by KAPPIN ファインテクノ), "アミキュア PN-23" (manufactured by KAPPIN ファインテクノ), "アミキュア PN-H" (manufactured by KAPPIN ファインテクノ), "ハードナー X-3661S" (manufactured by エー, シー, アール), "ハードナー X-3670S" (manufactured by エー, シー, アール), "FXR-1081" (manufactured by T & K TOKA), "フジキュア FXR-1000" (manufactured by T & K TOKA), "フジキュア FXR-1030" (manufactured by T & K TOKA), "ノバキュア -3721" (manufactured by Asahi chemical Co., Ltd), "HX-3722" (manufactured by Asahi chemical Co., Ltd.), "Sida chemical Co., Ltd "ノバキュア HX-3742" (manufactured by Asahi Kasei corporation), and the like.

The content of the curing accelerator (F) in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100 mass%, it is preferably 20 mass% or less, more preferably 10 mass% or less, and still more preferably 7 mass% or less. The lower limit of the content of the (F) curing accelerator in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100 mass%, it may be, for example, 0 mass% or more, 0.01 mass% or more, 0.1 mass% or more, preferably 0.5 mass% or more, more preferably 1 mass% or more, and still more preferably 2 mass% or more.

(G) organic filling Material

The resin composition of the present invention sometimes further contains (G) an organic filler as an optional ingredient.

(G) The organic filler is present in the resin composition in the form of particles. As the (G) organic filler, rubber particles are preferably used from the viewpoint of remarkably obtaining the desired effect of the present invention. (G) The organic filler may be used alone in 1 kind, or may be used in combination in 2 or more kinds at an arbitrary ratio.

Examples of the rubber component contained in the rubber particles include silicone elastomers such as polydimethylsiloxane; olefinic thermoplastic elastomers such as polybutadiene, polyisoprene, polychloroprene, ethylene-vinyl acetate copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-isobutylene copolymers, acrylonitrile-butadiene copolymers, isoprene-isobutylene copolymers, isobutylene-butadiene copolymers, ethylene-propylene-diene terpolymers, and ethylene-propylene-butene terpolymers; and thermoplastic elastomers such as acrylic thermoplastic elastomers such as poly (propyl (meth) acrylate), poly (butyl (meth) acrylate), poly (cyclohexyl (meth) acrylate), and poly (octyl (meth) acrylate. Further, a silicone rubber such as polyorganosiloxane rubber may be mixed in the rubber component. The glass transition temperature of the rubber component contained in the rubber particles is, for example, 0 ℃ or lower, preferably-10 ℃ or lower, more preferably-20 ℃ or lower, and still more preferably-30 ℃ or lower.

(G) The organic filler is preferably a core-shell type rubber particle from the viewpoint of remarkably obtaining the desired effect of the present invention. The core-shell type rubber particle is a granular organic filler containing the core particle containing a rubber component and 1 or more shell portions covering the core particle as exemplified above. Further, the core-shell type particle is preferably a core-shell type graft copolymer rubber particle containing the core particle containing the rubber component as exemplified above and a shell portion obtained by graft copolymerization with a monomer component copolymerizable with the rubber component contained in the core particle. The core-shell type as referred to herein does not necessarily mean a material that can be clearly distinguished only between the core particle and the shell portion, and includes a material in which the boundary between the core particle and the shell portion is not clear, and the core particle may not be completely covered with the shell portion.

The rubber component is contained in the core-shell type rubber particles preferably at least 40 mass%, more preferably at least 50 mass%, and still more preferably at least 60 mass%. The upper limit of the content of the rubber component in the core-shell type rubber particle is not particularly limited, and is, for example, 95 mass% or less, preferably 90 mass% from the viewpoint of sufficiently covering the core particle with the shell portion.

Monomer components forming the shell portion of the core-shell type rubber particle include, for example, (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, glycidyl (meth) acrylate, and the like; (meth) acrylic acid; n-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; a maleimide; α, β -unsaturated carboxylic acids such as maleic acid and itaconic acid; aromatic vinyl compounds such as styrene, 4-vinyltoluene and α -methylstyrene; (meth) acrylonitrile, etc., among them, a (meth) acrylate is preferably contained, and methyl (meth) acrylate is more preferably contained.

Examples of commercially available core-shell rubber particles include "CHT" manufactured by チェイルインダストリーズ corporation; "B602" manufactured by UMGABS corporation; ダウ "パラロイド EXL-2602", "パラロイド EXL-2603", "パラロイド EXL-2655", "パラロイド EXL-2311", "パラロイド -EXL 2313", "パラロイド EXL-2315", "パラロイド KM-330", "パラロイド KM-336P", "パラロイド KCZ-201", "68692C-223A", "メタブレン E-901", "メタブレン S-2001", "メタブレン W-450A", "メタブレン SRK-200" manufactured by Mitsubishi レイヨン "," カネエース M-511 "," カネエース M-600 "," カネエース M-400 "," カネエース M-580 "manufactured by chemical Japan, "カネエース MR-01", and the like.

(G) The organic filler material may be (a) an epoxy resin dispersion. (G) The (a) epoxy resin dispersion of the organic filler may be (G) in the (a) epoxy resin in a state of primary particles. (G) The content of the organic filler (G) in the epoxy resin dispersion (A) of the organic filler is preferably 10 to 40 wt%.

A commercially available epoxy resin dispersion (A) as the organic filler (G), examples thereof include カネエース "MX 120", "MX 125", "MX 130" (containing 25% by weight of a rubbery core-shell polymer (the rubber particle core is a styrene-butadiene copolymer)), MX960 ", MX 965" (containing 25% by weight of a rubbery core-shell polymer comprising a silicone rubber (the rubber particle core is polydimethylsiloxane, etc.)), RKB-3040 "(containing 29% by weight of a rubbery core-shell polymer (the rubber particle core is a butadiene rubber)) and RKB-3040H" (containing 25% by weight of a rubbery core-shell polymer (the rubber particle core is a butadiene rubber)) which are commercially available as rubbery core-shell polymer-modified bisphenol A epoxy resins.

(G) The average particle diameter (average primary particle diameter) of the organic filler is not particularly limited, but is preferably 20nm or more, more preferably 30nm or more, and still more preferably 50nm or more. (G) The upper limit of the average particle diameter (average primary particle diameter) of the organic filler is not particularly limited, but is preferably 5,000nm or less, more preferably 2,000nm or less, and still more preferably 1,000nm or less. (G) The average particle diameter (average primary particle diameter) of the organic filler can be measured using a Zeta potential particle size distribution measuring instrument or the like.

The content of the organic filler (G) in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is taken as 100 mass%, it is preferably 20 mass% or less, more preferably 10 mass% or less, and still more preferably 5 mass% or less. The lower limit of the content of the organic filler (G) in the resin composition is not particularly limited, and may be, for example, 0 mass% or more, 0.01 mass% or more, 0.1 mass% or more, 1 mass% or more, or 1.5 mass% or more, assuming that the nonvolatile component in the resin composition is 100 mass%.

< (H) other additives

The resin composition of the present invention may further contain optional additives as a nonvolatile component. Examples of such additives include curing agents other than thiol compounds such as phenol-based curing agents, naphthol-based curing agents, acid anhydride-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, carbodiimide-based curing agents, imidazole-based curing agents, and the like; thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, and polyester resins; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, biphenyltriol and phenothiazine; leveling agents such as siloxane; thickeners such as bentonite and montmorillonite; defoaming agents such as silicone defoaming agents, acrylic defoaming agents, fluorine defoaming agents, and vinyl resin defoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improving agents such as urea silane; adhesion imparting agents such as silane coupling agents, triazole-based adhesion imparting agents, tetrazole-based adhesion imparting agents, and triazine-based adhesion imparting agents; antioxidants such as hindered phenol antioxidants and hindered amine antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphine oxide compounds, red phosphorus), nitrogen flame retardants (e.g., melamine sulfate), halogen flame retardants, and inorganic flame retardants (e.g., antimony trioxide). The additive may be used alone in 1 kind, or may be used in combination in 2 or more kinds at an arbitrary ratio. (H) The content of other additives can be appropriately set by those skilled in the art.

Organic solvent (I)

The resin composition of the present invention may further contain an optional organic solvent as a volatile component in addition to the nonvolatile component. As the organic solvent (I), any known one may be suitably used as long as it can dissolve at least a part of the nonvolatile components, and the kind thereof is not particularly limited. Examples of the organic solvent (I) include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ -butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1, 4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl glycol acetate, γ -butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (I) The organic solvent may be used alone in 1 kind, or may be used in combination in 2 or more kinds at an arbitrary ratio. (I) When the organic solvent is used, 1 kind may be used alone, or 2 or more kinds may be used in combination at an arbitrary ratio. (I) The smaller the amount of the organic solvent, the more preferable the amount is (for example, 3% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.1% by mass or less, 0.01% by mass or less, in the case where the nonvolatile component in the resin composition is 100% by mass), and the more preferable the amount is not (0% by mass)

< method for producing resin composition >

The resin composition of the present invention can be produced by, for example, adding and mixing (a) an epoxy resin, (B) a thiol compound, (C) a magnetic powder, if necessary, (D) a stabilizer, (E) a dispersant if necessary, (F) a curing accelerator if necessary, (G) an organic filler if necessary, (H) other additives if necessary, and (I) an organic solvent if necessary in an arbitrary preparation vessel in an arbitrary order and/or partially or entirely at the same time. In addition, the temperature may be appropriately set during the process of adding and mixing the components, and heating and/or cooling may be performed temporarily or constantly. In addition, the components may be stirred or shaken during the mixing process. In addition, in the case of adding and mixing or after, the resin composition can be uniformly dispersed by stirring or shaking using a stirring device such as a mixer or a shaking device. Further, the defoaming can be performed under low pressure conditions such as vacuum while stirring or shaking. The mixing temperature may be, for example, 10 to 40 ℃. The stirring speed during mixing may be, for example, 100 to 10000 rpm. The mixing time may be, for example, 10 seconds to 10 minutes.

< Property of resin composition >

The resin composition of the present invention comprises (a) an epoxy resin, (B) a thiol compound, and (C) a magnetic powder, and a cured product of the resin composition has an elastic modulus at 25 ℃ of 500MPa or less and an elongation at break of 30% or more, and therefore a cured product having excellent impact resistance can be obtained. The impact resistance can be evaluated by the method of test example 5 described below, for example.

The cured product of the resin composition of the present invention has an elastic modulus at 25 ℃ of 500MPa or less. In one embodiment, the elastic modulus at 25 ℃ of the cured product of the resin composition of the present invention may be preferably 450MPa or less, 400MPa or less, more preferably 350MPa or less, 300MPa or less, further preferably 250MPa or less, 200MPa or less, particularly preferably 150MPa or less, or 100MPa or less, from the viewpoint of further improving the impact resistance. The elastic modulus can be measured, for example, by the method of test example 1 described below. It is known that the elastic modulus can be controlled to a desired elastic modulus by changing the selection of the components to be blended and the content thereof.

The resin composition of the present invention has a cured product having a breaking point elongation at 25 ℃ of 30% or more. In one embodiment, the elongation at break point at 25 ℃ of the cured product of the resin composition of the present invention may be preferably 35% or more, 40% or more, more preferably 45% or more, 50% or more, further preferably 55% or more, 60% or more, and particularly preferably 65% or more, and 70% or more, from the viewpoint of further improving the impact resistance. The breaking point elongation can be measured by, for example, the method of test example 2 described below. It is known that the elongation at break point can be controlled to a desired elongation at break point by changing the selection of the components and the content thereof.

In one embodiment, the specific magnetic permeability (μ') at 23 ℃ (measurement frequency of 100MHz) of the cured product of the resin composition of the present invention may be preferably 1 or more, more preferably 1.3 or more, further preferably 1.6 or more, and particularly preferably 2 or more. The specific magnetic permeability can be measured by, for example, the method of test example 3 described below.

In one embodiment, the viscosity at 25 ℃ of the resin composition of the present invention is not particularly limited, and may be preferably 0.001Pa · s or more, more preferably 0.01Pa · s or more, further preferably 0.1Pa · s or more, further more preferably 1Pa · s or more, and particularly preferably 10Pa · s or more. The lower limit of the viscosity at 25 ℃ of the resin composition of the present invention is not particularly limited, and may be preferably 1000Pa · s or more, more preferably 500Pa · s or more, further preferably 100Pa · s or more, and particularly preferably 50Pa · s or more. The viscosity can be measured, for example, by the method of test example 4 described below.

The reaction peak temperature in the differential scanning calorimetry may be preferably 150 ℃ or lower, 140 ℃ or lower, more preferably 130 ℃ or lower, 120 ℃ or lower, further preferably 110 ℃ or lower, 100 ℃ or lower, particularly preferably 95 ℃ or lower, 90 ℃ or lower, 85 ℃ or lower, or 80 ℃ or lower. By setting the range as above, the resin composition can be cured at a relatively low temperature, and thus a decrease in magnetic force can be suppressed. The lower limit of the reaction peak temperature may be, for example, 50 ℃ or higher. Here, the reaction peak temperature in the differential scanning calorimetry measurement indicates the temperature of the peak position on the lowest temperature side of the obtained differential scanning calorimetry curve (DSC curve) when the differential scanning calorimetry measurement is performed at a temperature rise rate of 5 ℃/min in a temperature range of 25 ℃ to 300 ℃.

The curing temperature of the resin composition of the present invention may be set to a temperature at which the curing reaction can be sufficiently progressed, for example, by referring to the reaction initiation temperature or the reaction peak temperature of the resin composition by Differential Scanning Calorimetry (DSC). In one embodiment, the resin composition of the present invention can be cured at a relatively low temperature, and therefore the curing temperature of the resin composition of the present invention may be, for example, 180 ℃ or lower, preferably 150 ℃ or lower, 140 ℃ or lower, more preferably 130 ℃ or lower, 120 ℃ or lower, further preferably 110 ℃ or lower, 100 ℃ or lower, particularly preferably 95 ℃ or lower, or 90 ℃ or lower. In order to further suppress the decrease in magnetic force, the curing temperature is preferably lower. The lower limit of the curing temperature may be, for example, 50 ℃ or higher, 60 ℃ or higher, 70 ℃ or higher, or the like. In the above-mentioned curing temperature, the curing time may be set to, for example, 10 minutes or more, 20 minutes or more, or the like. The upper limit of the curing time may be set to 60 minutes or less.

< use of resin composition >

The resin composition of the present invention can be used for various electronic parts in various semiconductor devices (for example, various electric products (for example, computers, mobile phones, smartphones, tablet personal computer devices, wearable devices, digital cameras, medical instruments, televisions, and the like) and passenger tools (for example, motorcycles, automobiles, trains, ships, airplanes and the like), and can be suitably used as, for example, an adhesive, a potting agent, a sealant, a fiber-reinforcing resin, a coating agent, a paint, and the like, and particularly suitably used as an adhesive or a sealant.

In particular, the resin composition of the present invention can suppress magnetic loss of a magnet, and therefore can be suitably used for an electronic component on which a magnet is mounted, for example, in an application in which a magnet is bonded as an adherend (in particular, in an application in which a magnet is bonded to another member as an adherend); a use in which members other than magnets are bonded to each other (particularly a use in which constituent members other than magnets are bonded to each other as an adherend); and the use in the step of bonding an electronic component after mounting a magnet-containing component.

The magnet is not particularly limited, and may be a known permanent magnet such as a ferrite magnet, an alnico magnet, or a rare-earth magnet (particularly a neodymium magnet). It is known that a neodymium magnet has a strong tendency to contract when heated and expand when cooled, but the resin composition of the present invention can have an excellent adhesive force to the neodymium magnet in one embodiment, and therefore can be particularly suitably used as an adhesive for adhering a neodymium magnet as an adherend.

The electronic component on which the magnet is mounted may be, for example, a motor, particularly an electronic component including a motor including a neodymium-containing magnet. The resin composition of the present invention can be used as an adhesive for electronic parts of a motor having a neodymium-containing magnet mounted thereon, particularly as an adhesive for bonding a magnet and a case in a motor having a neodymium-containing magnet.

Since the resin composition of the present invention is finally cured for use, an electronic component using the resin composition of the present invention may contain a cured product of the resin composition of the present invention, and in a specific embodiment, a motor containing a neodymium magnet and a cured product of the resin composition of the present invention. The motor including a neodymium magnet using the resin composition of the present invention may include a cured product of the resin composition of the present invention.

Examples

The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples. In the following, the terms "part(s)" and "%" as used herein mean "part(s) by mass" and "% by mass", respectively, unless otherwise specified. The temperature condition in the case where no temperature is specified is room temperature (25 ℃ C.).

First, the resin compositions of examples 1 to 11 and comparative examples 1 to 4 were prepared by mixing the respective components in the formulation shown in table 1 below. The details are as follows.

< example 1 >

In a special plastic container, 60 parts of an epoxy resin having a flexible skeleton (EXA-4850-150, 450g/eq, manufactured by DIC Co., Ltd.), 60 parts of a dispersion of a butadiene rubber particle epoxy resin (RKB-3040H, manufactured by クレハトレーディング Co., Ltd.), a bisphenol A/F type epoxy resin (a rubber-like core-shell polymer (butadiene rubber) having a 25% dispersion), 40 parts of an epoxy equivalent of 223g/eq), 39 parts of a thiol compound having a carboxylate structure (TMTP, manufactured by Takara chemical Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), 140g/eq in thiol equivalent), 110 parts of a magnetic powder (M05 SWD, manufactured by パウダーテック Co., Ltd.), 0.8 part of a stabilizer (TEB, triethyl borate, manufactured by Tokyo chemical Co., Ltd.), 1.1 part of a dispersant (SC-1015F, manufactured by Nichigan oil Co., Ltd.), 1.1 part of, 14 parts of an amine-epoxy adduct-based curing accelerator ("PN-FJ", manufactured by kairokosu ファインテクノ).

Thereafter, the magnetic powder was thoroughly mixed at room temperature at 25 ℃ and 2000rpm (it was confirmed that the magnetic powder was sufficiently dispersed and mixed by a spatula for about 30 seconds to about 1 minute) using an AWATORI RENTARO (シンキー, ARE-310), and further defoamed for 2 minutes under vacuum (pressure set to 0) and 1000rpm using an automatic revolution type agitation defoaming machine "HM-200W" manufactured by Co., Ltd, to obtain a resin composition.

< example 2 >

A resin composition was obtained in the same manner as in example 1 except that 60 parts of the flexible skeleton-containing epoxy resin ("EXA-4850-150" manufactured by DIC) was replaced with 60 parts of the flexible skeleton-containing epoxy resin ("YX-7400" manufactured by Mitsubishi chemical corporation and having an epoxy equivalent of 440g/eq), the amount of the thiol compound having a carboxylate structure ("TMTP" manufactured by Takechemistry industries) was changed from 39 parts to 40 parts, and the amount of the magnetic powder ("M05 SWD" manufactured by パウダーテック) was changed from 110 parts to 120 parts.

< example 3 >

A resin composition was obtained in the same manner as in example 1 except that the amount of the epoxy resin having a flexible skeleton ("EXA-4850-3040H", manufactured by DIC) was changed from 60 parts to 100 parts, the amount of the thiol compound having a carboxylate structure ("TMTP", manufactured by Takechemial Co., Ltd.) was changed from 39 parts to 28 parts, and the amount of the magnetic powder ("M05 SWD", manufactured by パウダーテック) was changed from 110 parts to 105 parts, without using 40 parts of the dispersion of the butadiene rubber particle epoxy resin ("RKB-3040H", manufactured by クレハトレーディング Co., Ltd.).

< example 4 >

A resin composition was obtained in the same manner as in example 1, except that 110 parts of a magnetic powder (エプソンアトミックス of "AW 2-08PF 3F") was used instead of 110 parts of a magnetic powder (M05 SWD "manufactured by パウダーテック).

< example 5 >

A resin composition was obtained in the same manner as in example 1, except that the amount of the magnetic powder (M05 SWD manufactured by パウダーテック) used was changed from 110 parts to 155 parts.

< example 6 >

A resin composition was obtained in the same manner as in example 1, except that the amount of the magnetic powder (M05 SWD manufactured by パウダーテック) used was changed from 110 parts to 268 parts.

< example 7 >

A resin composition was obtained in the same manner as in example 1, except that the amount of the magnetic powder (M05 SWD manufactured by パウダーテック) used was changed from 110 parts to 416 parts.

< example 8 >

A resin composition was obtained in the same manner as in example 1, except that 38 parts of an isocyanurate structure-containing thiol compound ("TMPIC" manufactured by kaffir ファインテクノ, tris (3-mercaptopropyl) isocyanurate, thiol equivalent 117g/eq) were used instead of 39 parts of a carboxylate structure-containing thiol compound ("TMTP" manufactured by lakeman chemical industries).

< example 9 >

A resin composition was obtained in the same manner as in example 1 except that 33 parts of a thiol compound having a carboxylate structure (PE-1, pentaerythritol tetrakis (3-mercaptobutyrate), thiol equivalent 136g/eq, manufactured by Showa Denko K.K.) was used in place of 39 parts of the thiol compound having a carboxylate structure (TMTP, manufactured by chemical industries, Ltd.).

< example 10 >

A resin composition was obtained in the same manner as in example 1, except that 1.1 parts of a dispersant (PB-821, manufactured by KAIKOUZEN ファインテクノ Co., Ltd.) was used in place of 1.1 parts of the dispersant (SC-1015F, manufactured by Nichikoku Co., Ltd.).

< example 11 >

A resin composition was obtained in the same manner as in example 1, except that 1.1 parts of a dispersant (SC-1015F, manufactured by Nichiyu oil Co., Ltd.) was not used.

< comparative example 1 >

A resin composition was obtained in the same manner as in example 1 except that 15 parts of polyamine (FXR-1081, manufactured by T & K TOKA) was used instead of 39 parts of the thiol compound having a carboxylate structure (TMTP, manufactured by chemical industries, Ltd.) and the amount of the magnetic powder (M05 SWD, manufactured by パウダーテック) was changed from 110 parts to 90 parts.

< comparative example 2 >

A resin composition was obtained in the same manner as in example 1 except that 39 parts of a thiol compound having a carboxylate structure (TMTP manufactured by daiko chemical industries, inc.), 39 parts of an allyl-containing phenol (MEH-8000H, 141g/eq in hydroxyl equivalent) were used, the amount of the magnetic powder (M05 SWD manufactured by パウダーテック) was changed from 110 parts to 111 parts, 0.8 part of a stabilizer (TEB, triethyl borate manufactured by tokyo chemical industries, inc.), 1.1 parts of a dispersant (SC-1015F manufactured by nikko corporation), 14 parts of an amine-epoxy adduct-based curing accelerator (PN-FJ manufactured by kayaku ファインテクノ), and 0.4 parts of a phosphorus-based curing accelerator (TBP-DA, tetrabutylphosphonium caprate manufactured by beixing chemical industries, inc.).

< comparative example 3 >

A resin composition was obtained in the same manner as in example 1 except that 35 parts of phenol novolac cyanate ester ("PT-30" manufactured by Ronza corporation, equivalent to functional group of シアネート) was used instead of 39 parts of thiol compound ("TMTP" manufactured by starch chemical industry corporation), the amount of magnetic powder ("M05 SWD" manufactured by パウダーテック) was changed from 110 parts to 105 parts, 0.8 part of stabilizer ("TEB" manufactured by tokyo chemical corporation, triethyl borate) and 1.1 part of dispersant ("SC-1015F" manufactured by nippon oil corporation were not used, and 0.4 part of metal-based curing accelerator ("PN-FJ" manufactured by ファインテクノ corporation was used instead of 14 parts of amine epoxy adduct-based curing accelerator ("PN-FJ") and 0.4 part of manganese (III) (tris (2, 4-pentanedionato) manganese (III)) was used instead of thiol compound having a carboxylate structure (manufactured by tokyo chemical industry corporation).

< comparative example 4 >

A resin composition was obtained in the same manner as in example 1, except that 39 parts of a thiol compound having a carboxylate structure (TMTP manufactured by lakeko chemical industries, inc.), instead of using 79 parts of the magnetic powder (M05 SWD manufactured by パウダーテック, inc.), 0.8 part of a stabilizer (TEB, triethyl borate manufactured by tokyo chemical industries, inc.), 1.1 part of a dispersant (SC-1015F manufactured by solar oil, inc.), and 2 parts of a phosphorus-based curing accelerator (TBP-DA, tetrabutylphosphonium decanoate, manufactured by beixingheng chemical industries, inc.) were used instead of 14 parts of an amine epoxy adduct-based curing accelerator (PN-FJ manufactured by kayaku ファインテクノ, inc.).

< test example 1: measurement of elastic modulus

Each of the resin compositions obtained in examples and comparative examples was coated on a release PET film (NS-80A: manufactured by Toho レ Co.) by bar coating, and each was heated (setting the curing temperature to a reaction peak temperature of. + -. 30 ℃ and curing time of 30 minutes or more (the same applies hereinafter) for examples 1 to 11, namely 30 minutes at 80 ℃, 30 minutes at 100 ℃, 60 minutes at 180 ℃ for comparative example 1, 120 minutes at 200 ℃ for comparative example 3, and 60 minutes at 150 ℃) to obtain a cured product. The resulting cured product having a thickness of 100 μm was punched out with a dumbbell (trade name: スーパーダンベルカッター (model: SDMK-5889-01), manufactured by ダンベル) to prepare a test piece for tensile strength measurement. The PET film was peeled from the test piece. A tensile test was carried out at a temperature of 25 ℃ and a humidity of 50% at a tensile rate of 5 mm/min using an テンシロン universal tester (RTM-500, オリエンテック Co.) to measure the modulus of elasticity (MPa).

In each example, DSC (differential scanning calorimetry) measurements were performed before and after curing, and it was confirmed that no peak (peak near 60 ℃ to 90 ℃) of a differential scanning calorimetry curve (DSC curve) at a curing reaction temperature existing before curing was found in a cured product after curing. DSC was measured by using a differential scanning calorimeter (DSC7000X, manufactured by Hitachi ハイテク Co., Ltd.) and raising the temperature from 25 ℃ to 300 ℃ at 5 ℃/min. In any of examples 1 to 11, the peak temperature of the reaction was 90 ℃ or lower. Fig. 1 is a DSC chart showing differential scanning calorimetry curves (DSC curves) before and after curing of the resin composition obtained in example 1. In fig. 1, the solid line indicates before curing, and the dotted line indicates after curing.

< test example 2: determination of elongation at Break Point >

Each of the resin compositions obtained in examples and comparative examples was coated on a release PET film (NS-80A: manufactured by Toho レ Co.) by bar coating, and each was heated (30 minutes at 80 ℃ in examples 1 to 11, 30 minutes at 100 ℃ in comparative example 1, 60 minutes at 180 ℃ in comparative example 2, 120 minutes at 200 ℃ in comparative example 3, and 60 minutes at 150 ℃ in comparative example 4) to obtain a cured product. The resulting cured product having a thickness of 100 μm was punched out with a dumbbell (trade name: スーパーダンベルカッター (model: SDMK-5889-01), manufactured by ダンベル) to prepare a test piece for tensile strength measurement. The PET film was peeled from the test piece. A tensile test was carried out at a temperature of 25 ℃ and a humidity of 50% at a tensile rate of 5 mm/min by using an テンシロン universal tester (RTM-500, オリエンテック Co., Ltd.), and the elongation at break (%) was measured.

< test example 3: measurement of specific magnetic permeability

Each of the resin compositions obtained in examples and comparative examples was coated on a release PET film (NS-80A: manufactured by Toho レ Co.) by bar coating, and each was heated (30 minutes at 80 ℃ in examples 1 to 11, 30 minutes at 100 ℃ in comparative example 1, 60 minutes at 180 ℃ in comparative example 2, 120 minutes at 200 ℃ in comparative example 3, and 60 minutes at 150 ℃ in comparative example 4) to obtain a cured product. The PET film was peeled from the test piece. The resulting cured product having a thickness of 400 μm was cut into test pieces having a width of 10mm and a length of 30mm to prepare test pieces for measurement. The evaluation sample was measured for specific magnetic permeability (. mu.) at room temperature of 23 ℃ by short-circuiting a measurement frequency in the range of 0.1MHz to 500MHz by using アジレントテクノロジーズ (manufactured by Agilent Technologies, Inc. "HP 8362B") and a short-circuiting stripline method. The specific permeability shown in table 1 below is the specific permeability (μ') when the measurement frequency was 100 MHz.

< test example 4: measurement of viscosity >

The temperature of each of the resin compositions obtained in examples and comparative examples was maintained at 25 ℃ (± 2 ℃), and the viscosity (Pa · s) was measured using an E-type viscometer ("RE-85U", manufactured by eastern mechanical industries, 3 ° × R9.7 ロータ) under measurement conditions of a measurement sample of 0.22ml and a rotation speed of 20 rpm.

< test example 5: evaluation of impact resistance >

A fluorine rubber sheet (manufactured by アズワン Co.) having a thickness of 4mm and cut into 60mm X100 mm was further cut into half, and a rectangle of 10mm X80 mm was cut out from the center of one of the sheets. A release agent DAIFREE (manufactured by GA-9700, ダイキン, Ltd.) was sprayed on the inner surface of the scooped-out mold and heated at a curing temperature for 30 minutes.

After the heated fluororubber sheets were taken out from the thermostatic bath and cooled, two sheets of the fluororubber sheets were stacked, the periphery was fixed by a jig, and the resin compositions obtained in examples and comparative examples were poured into rectangular recesses so that the surfaces thereof became flat, and were heated individually (30 minutes at 80 ℃ in examples 1 to 11, 30 minutes at 100 ℃ in comparative example 1, 60 minutes at 180 ℃ in comparative examples 2 and 3, and 60 minutes at 200 ℃ in comparative example 4) to be cured.

The solidified material was taken out from the thermostatic bath and cooled, and then taken out from the mold to obtain a test piece of 10 mm. times.80 mm. times.4 mm. The test piece was inserted into a fixing portion of an アイゾット impact tester (manufactured by オリエンテック corporation) by 30mm, and the test piece was subjected to hammer impact at a position of 45mm from the fixing portion to confirm whether the test piece was broken or not. The gap between the test piece and the impact test piece fixing portion is not bonded. In addition, no cut (notch) was made in the test piece.

The result of the impact resistance test (N =3) was evaluated as "o" when each of the test pieces was not broken and as "x" when the test pieces were broken, and as final evaluations, 3 of the 3 test pieces were regarded as "excellent" when all of the test pieces were non-broken, 2 test pieces were regarded as "good", 1 test piece was regarded as "Δ", and 3 test pieces were regarded as "x".

The nonvolatile components and the amounts of the nonvolatile components of the resin compositions of examples and comparative examples, and the measurement results and evaluation results of the test examples are shown in table 1 below.

[ TABLE 1]

。

< investigation of evaluation results >

It is found that the resin compositions of examples 1 to 11 give cured products having excellent impact resistance as compared with the resin compositions of comparative examples 1 to 4. Specifically, in examples 1 to 11 using the thiol compound, the elastic modulus was suppressed to be low, and the elongation at the break point was high, and it was found that the impact resistance was excellent. In addition, in comparative examples 1 to 3 using other curing agents and comparative example 4 as a homopolymerization system of epoxy resin, it was confirmed that the elastic modulus and the elongation at break were deteriorated and not effective for impact resistance.

Claims

1. A resin composition comprising (A) an epoxy resin, (B) a thiol compound, and (C) a magnetic powder,

2. The resin composition according to claim 1, wherein the epoxy equivalent of the component (a) is 200g/eq to 1000g/eq.

3. The resin composition according to claim 1, wherein the component (B) is a thiol compound having 2 or more functions.

4. The resin composition according to claim 1, wherein the ratio (mercapto group/epoxy group) of the total number of mercapto groups of the thiol compound (B) to the total number of epoxy groups of the epoxy resin (A) is 0.3 to 1.0.

5. The resin composition according to claim 1, wherein the content of the component (C) is 40 to 75% by mass, with the nonvolatile component in the resin composition being taken as 100% by mass.

6. The resin composition of claim 1, further comprising a latent cure accelerator.

7. The resin composition according to claim 1, wherein the component (A) comprises (A-1) an epoxy resin having a flexible skeleton.

8. The resin composition according to claim 1, wherein a reaction peak temperature based on differential scanning calorimetry is 100 ℃ or lower.

9. The resin composition according to claim 1, which is used as an adhesive.

10. The resin composition according to claim 9, which is used as an adhesive for adhering a neodymium magnet as an adherend.

11. The resin composition according to claim 1, which is used as a sealing material.

12. A cured product of the resin composition according to any one of claims 1 to 11.

13. A neodymium magnet-containing motor comprising the cured product according to claim 12.

14. An electronic component comprising the cured product according to claim 12.

15. An electronic component comprising a motor containing a neodymium magnet and the cured product according to claim 12.