Thermosetting resin compositions, adhesives, cured products, and joints

Abstract

To provide a thermosetting resin composition which is excellent in adhesion, low elasticity and impact reliability of a cured product, and has low viscosity.SOLUTION: A thermosetting resin composition contains an epoxy resin (A), a curing agent (B), a first elastomer (C) containing at least one of polyrotaxane and a block copolymer, and a second elastomer (D) containing a siloxane oligomer. The ratio of the epoxy resin (A) is 13 mass% or more and 55 mass% or less. The ratio of the curing agent (B) is 20 mass% or more and 55 mass% or less. The ratio of the first elastomer (C) is 10 mass% or more and 20 mass% or less. The ratio of the second elastomer (D) is more than 5 mass% and 25 mass% or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to thermosetting resin compositions, adhesives, cured products, and joints, and more particularly to thermosetting resin compositions useful as adhesives and sealing materials, adhesives made from this thermosetting resin composition, cured products of this thermosetting resin composition, and joints containing this cured product. [Background technology]

[0002] Thermosetting resin compositions used in adhesives and sealing materials are required to have low viscosity so that the cured product obtained by thermosetting has excellent adhesion to the adherend and excellent coatability. As such a thermosetting resin composition, Patent Document 1 discloses a curing agent composition containing calix(n+m+1)arene and an epoxy resin curing agent with a boiling point of 100°C or higher. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2002-284861 [Overview of the project] [Problems that the invention aims to solve]

[0004] When such thermosetting resin compositions are used for bonding or sealing electronic components, it is preferable that the cured product of the composition has low elasticity in order to suppress delamination and cracking due to excessive stress. In addition, since the joint obtained by bonding with this composition is required to be resistant to damage when dropped, the cured product of the composition is also required to have high impact resistance reliability. However, it is not easy to achieve low elasticity and high impact resistance reliability of the cured product simultaneously while maintaining low viscosity in the conventional compositions.

[0005] An object of the present disclosure is to provide a thermosetting resin composition that is excellent in adhesion, low elasticity, and impact resistance reliability of a cured product, has a low viscosity, an adhesive comprising the thermosetting resin composition, a cured product of the thermosetting resin composition, and a joined body including the cured product.

Means for Solving the Problems

[0006] The thermosetting resin composition according to one aspect of the present disclosure includes an epoxy resin (A), a curing agent (B), and a first elastomer (C) including at least one of polyrotaxane and a block copolymer. A component different from the polyrotaxane and block copolymer contained in the first elastomer (C), containing a siloxane oligomer ingredients ( and (D). The proportion of the epoxy resin (A) is 13% by mass or more and 55% by mass or less. The proportion of the curing agent (B) is 20% by mass or more and 55% by mass or less. The proportion of the first elastomer (C) is 10% by mass or more and 20% by mass or less. The Noted components ( proportion of (D) is more than 5% by mass and 25% by mass or less.

[0007] The adhesive according to one aspect of the present disclosure is composed of the thermosetting resin composition.

[0008] The cured product according to one aspect of the present disclosure is a cured product of the thermosetting resin composition.

[0009] The joined body according to one aspect of the present disclosure includes a first member, a second member, and a joining layer that is interposed between the first member and the second member and joins the first member and the second member. The joining layer includes the cured product.

Effects of the Invention

[0010] According to the present disclosure, it is possible to provide a thermosetting resin composition that is excellent in adhesion, low elasticity, and impact resistance reliability of a cured product, has a low viscosity, an adhesive comprising the thermosetting resin composition, a cured product of the thermosetting resin composition, and a joined body including the cured product.

Modes for Carrying Out the Invention

[0011] 1. Overview The thermosetting resin composition according to this embodiment (hereinafter, also referred to as composition (X)) includes an epoxy resin (A), a curing agent (B), a first elastomer (C) containing at least one of polyrotaxane and a block copolymer, and a siloxane oligomer. ingredients ( It contains (D). The proportion of the epoxy resin (A) is 13% by mass or more and 55% by mass or less. The proportion of the curing agent (B) is 20% by mass or more and 55% by mass or less. The proportion of the first elastomer (C) is 10% by mass or more and 20% by mass or less. component( The proportion of (D) is more than 5% by mass and 25% by mass or less.

[0012] As a result of intensive studies to solve the above problems, the inventors added an elastomer in addition to the epoxy resin (A) and the curing agent (B) in the thermosetting resin composition. As this elastomer, a first elastomer (C) containing at least one of polyrotaxane and a block copolymer, and a siloxane oligomer. ingredients ( It was found that by selecting and using (D) in combination and further setting the mass ratio of the components (A) to (D) to the above range with respect to the entire composition (X), it is possible to obtain excellent adhesion, low elasticity and impact resistance reliability of the cured product while maintaining a low viscosity, and the present disclosure was completed.

[0013] The composition (X) according to this embodiment is excellent in the adhesion, low elasticity and impact resistance reliability of the cured product and has a low viscosity. Regarding the reason for achieving the above effects by the composition (X) having the above configuration, it is not necessarily clear, but it can be speculated as follows. That is, as the elastomer, a first elastomer (C) that tends to have a relatively high viscosity by containing at least one of polyrotaxane and a block copolymer, and a relatively low viscosity by containing a siloxane oligomer. Ingredients ( By using (D) in combination and setting the proportions of the components (A) to (D) to the above ranges respectively, the composition (X) can maintain a low viscosity and make the phase separation structure formed by curing into a smaller sea-island structure. As a result, it is considered that the cured product can improve both low elasticity and impact resistance reliability while maintaining adhesion.

[0014] 2.Details <Thermosetting resin composition> The composition (X) according to this embodiment contains the components (A) to (D) described above. In addition to these, composition (X) also contains second The elastomer (E) may also contain a flexible epoxy resin. Furthermore, other components may be included, to the extent that they do not impair the effects of the present disclosure. Each component will be described below.

[0015] [Epoxy resin (A)] The epoxy resin (A) is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule.

[0016] Specific examples of epoxy resin (A) include, for example, bisphenol-type epoxy resins such as biphenyl-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol S-type epoxy resin; hydrogenated bisphenol-type epoxy resins such as hydrogenated bisphenol A-type epoxy resin, hydrogenated bisphenol F-type epoxy resin, and hydrogenated bisphenol S-type epoxy resin; naphthalene ring-containing epoxy resin, anthracene ring-containing epoxy resin, alicyclic epoxy resin, dicyclopentadiene-type epoxy resin, phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, triphenylmethane-type epoxy resin, brome-containing epoxy resin, aliphatic epoxy resin, aliphatic polyether-type epoxy resin, triglycidyl isocyanurate, glycidyl group-containing silicone resin, and glycidylamine-type epoxy resin. Composition (X) may contain one or more of these selected as epoxy resin (A).

[0017] The epoxy resin (A) is preferably liquid at 25°C. In this case, the viscosity of composition (X) can be lowered, thereby improving its applicability. Furthermore, the epoxy resin (A) and components (B) to (D) can be mixed more easily, allowing for the preparation of a more uniform composition (X).

[0018] The epoxy resin (A) preferably contains a bisphenol-type epoxy resin, and more preferably contains at least one of a bisphenol A-type epoxy resin and a bisphenol F-type epoxy resin.

[0019] [Hardening agent (B)] The hardening agent (B) is a component that reacts with the epoxy resin (A) to harden it.

[0020] Examples of curing agents (B) include visible curing agents (B1) and latent curing agents (B2).

[0021] (Manifested curing agent (B1)) The "manifested curing agent" has the activity to cure epoxy resin (A) when mixed with epoxy resin (A) at room temperature. Composition (X) can further improve its curability by containing the manifested curing agent (B1) as the curing agent (B).

[0022] Examples of the visible curing agent (B1) include amine curing agents, acid anhydride curing agents, phenol resin curing agents, and thiol curing agents. Composition (X) may contain one or more of the visible curing agents (B1).

[0023] Amine curing agents are curing agents having at least two amino groups. Examples of amino groups include -NH2, monosubstituted NH2, disubstituted NH2, trisubstituted NH2, and so on.

[0024] Examples of amine curing agents include polyamine-based curing agents, modified polyamine-based curing agents, polyamide-polyamine-based curing agents, and modified polyamide-polyamine-based curing agents.

[0025] Examples of polyamine-based curing agents include aliphatic polyamines, alicyclic polyamines, and aromatic polyamines.

[0026] Examples of aliphatic polyamines include diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, and 2-methylpentamethylenediamine.

[0027] Examples of alicyclic polyamines include alicyclic polyamines such as isophoronediamine, 1,3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, and 1,2-diaminocyclohexane; and piperazine-type polyamines such as N-aminoethylpiperazine and 1,4-bis(2-amino-2-methylpropyl)piperazine.

[0028] Examples of aromatic polyamines include diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, trimethylenebis(4-aminobenzoate), and polytetramethyleneoxide-di-p-aminobenzoate.

[0029] Examples of modified polyamine-based curing agents include modified products obtained by epoxide addition, Michael addition, Mannich addition, thiourea addition, acrylonitrile addition, ketone blockade, etc., of polyamines.

[0030] Examples of polyamide-polyamine-based curing agents include condensates of dimer acid and polyamine.

[0031] Examples of modified polyamide-polyamine curing agents include addition products of polyamide-polyamines with epoxy compounds, etc.

[0032] Examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecinyl succinic anhydride, nadic anhydride, and trimellitic anhydride.

[0033] Examples of phenol resin curing agents include phenol novolac resins, cresol novolac resins, naphthol novolac resins, bisphenol novolac resins, biphenyl novolac resins, dicyclopentadiene-phenol addition type resins, phenol aralkyl resins, naphthol aralkyl resins, triphenolmethane type resins, tetraphenolethane type resins, and aminotriazine-modified phenol resins.

[0034] Examples of thiol curing agents include pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), and trimethylolpropanetris (3-mercaptopropionate).

[0035] The visible curing agent (B1) preferably contains an amine curing agent, and more preferably a polyamine curing agent. In this case, the curability of composition (X) can be further improved.

[0036] (Latent curing agent (B2)) A "latent curing agent" is a substance that does not exhibit curing activity towards epoxy resin (A) at room temperature, but becomes activated by heating, etc., through melting, decomposition, or transformation reactions, thereby promoting the curing of epoxy resin (A). Composition (X) can further improve storage stability by containing a latent curing agent (B2) as the curing agent (B).

[0037] Examples of latent curing agents (B2) include microencapsulated curing agents, solid dispersion curing agents, reactive group blocking curing agents, dissolution curing agents, and ionic curing agents.

[0038] Examples of microencapsulated curing agents include those having a structure in which the surface of a core containing the curing agent is covered with a shell containing an inorganic oxide, synthetic resin, etc. Examples of commercially available microencapsulated curing agents include Asahi Kasei's Novacure HX-3721, 3722, 3741, 3742, 3748, 3613, 3088, 3921HP, 3941HP, and HXA9322HP.

[0039] Examples of solid-disperse curing agents include dicyandiamide and its derivatives, hydrazide compounds, imidazole and its derivatives.

[0040] Examples of dicyandiamide derivatives include addition compounds of dicyandiamide with epoxy resins, vinyl compounds, acrylic compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.

[0041] Examples of hydrazide compounds include 9,9-bis(hydrazinocarbonylalkyl)fluorenes such as 9,9-bis(hydrazinocarbonylmethyl)fluorene, and adipic acid dihydrazides.

[0042] Examples of imidazole derivatives include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole.

[0043] Examples of reaction group-blocking curing agents include reaction products of amine compounds and epoxy compounds (amine-epoxy adduct systems), and reaction products of amine compounds and isocyanate compounds or urea compounds (urea-type adduct systems).

[0044] Examples of dissolving curing agents include molecular sieve-encapsulated curing agents.

[0045] Examples of ionic curing agents include ionic compounds containing ammonium cations and organic acid anions.

[0046] The latent curing agent (B2) preferably includes a microencapsulated curing agent from the viewpoint of further improving the storage stability of composition (X).

[0047] The curing agent (B) preferably contains an apparent curing agent (B1) and a latent curing agent (B2). In this case, the curability and storage stability of composition (X) can be further improved.

[0048] When composition (X) contains a visible curing agent (B1) and a latent curing agent (B2) as the curing agent (B), the mass ratio of the latent curing agent (B2) to the visible curing agent (B1) ((B2) / (B1)) is preferably 0.1 or more and 10 or less, more preferably 1 or more and 7 or less, even more preferably 2 or more and 6 or less, and particularly preferably 3 or more and 5 or less. By setting the mass ratio of (B2) / (B1) within the above range, the curability and storage stability of composition (X) can be further improved.

[0049] [First Elastomer (C)] The first elastomer (C) comprises at least one of a polyrotaxane (C1) and a block copolymer (C2). The first elastomer (C) may or may not react with the epoxy resin (A).

[0050] The statement that the first elastomer (C) "reacts with epoxy resin (A)" means that the functional groups of the compounds constituting the first elastomer (C) can react with the epoxy groups of the epoxy resin (A). Examples of reactions with epoxy groups include the addition of functional groups to epoxy groups and the reaction of epoxy groups with epoxy groups by the action of a curing catalyst. Examples of functional groups that react with epoxy groups (hereinafter also referred to as epoxy reactive groups) include hydroxyl groups, amino groups, carboxyl groups, acid anhydride groups, sulfanyl groups, and epoxy groups. Examples of hydroxyl groups include alcoholic hydroxyl groups and phenolic hydroxyl groups. Examples of amino groups include -NH2, monosubstituted NH2, disubstituted NH2, and trisubstituted NH2. The epoxy reactive groups preferably include at least one group selected from the group consisting of hydroxyl groups, amino groups, and epoxy groups, more preferably include at least one group selected from the group consisting of hydroxyl groups and epoxy groups, and even more preferably include at least one group selected from the group consisting of alcoholic hydroxyl groups and epoxy groups.

[0051] (Polyrotaxane (C1)) A "polyrotaxane" is a molecule having a chain portion, two or more cyclic molecules through which part of the chain portion is traversed, and blocking groups located at both ends of the chain portion.

[0052] The chain portion of polyrotaxane (C1) is, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyisoprene, polyisobutylene, polybutadiene, or poly(meth)acrylic acid ester. , It is formed from polymers such as polyethylene and polypropylene. The weight-average molecular weight of this polymer is preferably 1,000 to 500,000, more preferably 4,000 to 100,000, and even more preferably 7,000 to 30,000.

[0053] Examples of the cyclic molecule of the polyrotaxane (C1) include cyclic polymers or cyclic oligomers such as cyclic polyethers, cyclic polyesters, cyclic polyetheramines, cyclic polyamines; cyclodextrins such as α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, and the like.

[0054] Examples of the block group of the polyrotaxane (C1) include bulky groups, ionic groups, and the like. Examples of the bulky group include an adamantyl group, a dinitrophenyl group, a trityl group, a fluorenyl group, a pyrenyl group, an anthryl group, and the like. Examples of the ionic group include a carboxyl group and the like.

[0055] Examples of the polyrotaxane (C1) include molecules represented by the following formula (1) and the like.

[0056] [[ID=第13]]

Chemical formula

[0057] In formula (1), G and G 2 each independently represent the terminal atom of the chain portion. That is, the line connecting G 1 and G 2 represents the chain portion. Z 1 and Z 2 are each independently a group containing a block group. L represents a cyclic molecule. p represents the number of cyclic molecules L that the polyrotaxane has, and is an integer of 2 or more and 1000 or less. The plurality of Ls may be the same or different. Q 1 and Q[[ID=第35]] 2 are each independently a single bond or a divalent linking group. X 1 and X[[ID=第39]] 2 are each independently a hydrogen atom or an epoxy reactive group.

[0058] The polyrotaxane (C1) preferably has epoxy reactive groups in its chemical structure, and more preferably has epoxy reactive groups in a cyclic molecule. In this case, the bonding of the polyrotaxane (C1) and the epoxy resin (A) can further improve the low elasticity and impact resistance reliability of the cured product of composition (X). The epoxy reactive group preferably includes at least one group selected from the group consisting of hydroxyl groups, amino groups, and epoxy groups, more preferably includes a hydroxyl group, and even more preferably includes an alcoholic hydroxyl group.

[0059] X in equation (1) 1 and / or X 2 When is an epoxy reactive group, this molecule has an epoxy reactive group in the cyclic molecule L, and the epoxy reactive group is introduced by substituting some or all of the hydrogen atoms of the hydroxyl group of the cyclic molecule L with a group containing the epoxy reactive group (-QX). The number of epoxy reactive groups introduced is, for example, an integer from 1 to 20, preferably from 1 to 8, more preferably from 2 to 5, and even more preferably 2.

[0060] G 1 -G 2 The chain portion represented is preferably formed from polyalkylene glycol, and more preferably from polyethylene glycol.

[0061] G 1 and G 2 The terminal atom represented is usually an oxygen atom or a carbon atom.

[0062] Z 1 and Z 2 The block group represented by preferably contains a polycyclic group, more preferably a polycyclic alicyclic hydrocarbon group, and even more preferably an adamantyl group.

[0063] p is preferably between 10 and 800, and more preferably between 100 and 500.

[0064] Q 1 and Q 2 Examples of divalent linking groups represented by this symbol include a chain-like group consisting of a carbon atom and an oxygen atom, and an oxygen atom. 1 and Q 2 It is preferable that it contains polylactone chains, and more preferably that it contains polycaprolactone chains.

[0065] The cyclic molecule represented by L preferably contains cyclodextrin, and more preferably contains α-cyclodextrin.

[0066] The weight-average molecular weight of polyrotaxane (C1) is preferably 5,000 to 3,000,000, more preferably 10,000 to 2,000,000, and even more preferably 100,000 to 1,000,000.

[0067] Examples of commercially available polyrotaxane (C1) products include ASM's Cellum Superpolymer SH1300P, SH2400P, SB1300P, and SC1300P.

[0068] (Block copolymer (C2)) A "block copolymer" is a copolymer having two or more blocks of continuous monomer units. The block copolymer (C2) may or may not have epoxy reactive groups, but it is preferable that it does not have epoxy reactive groups. By not having epoxy reactive groups, the block copolymer (C2) can be compatible with the epoxy resin (A), and the low elasticity and impact resistance reliability of the cured product of composition (X) can be further improved.

[0069] The number of blocks constituting the block copolymer (C2) is preferably 2 to 10, more preferably 2 to 5, and even more preferably 2 or 3.

[0070] Examples of monomer units that make up the block copolymer (C2) include (meth)acrylic units, styrene units, olefin units, (meth)acrylonitrile units, and butadiene units. rank Examples include: "(Meta)acrylic" means either acrylic or methacrylic, or both.

[0071] Examples of monomers that give (meth)acrylic units include propyl (meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and iso-propyl (meth)acrylate; butyl (meth)acrylate such as n-butyl (meth)acrylate, iso-butyl (meth)acrylate, sec-butyl (meth)acrylate, and tert-butyl (meth)acrylate; octyl (meth)acrylate such as pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; alkyl (meth)acrylate such as decyl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, and hexadecyl (meth)acrylate; and hydroxyalkyl (meth)acrylate such as hydroxyethyl (meth)acrylate.

[0072] Examples of monomers that provide styrene units include styrene, o-,m-,p-methylstyrene, o-,m-,p-chlorostyrene, and α-methylstyrene.

[0073] Examples of monomers that provide olefin units include ethylene, propylene, butylene, hexylene, and cyclohexene.

[0074] Examples of monomers that give (meth)acrylonitrile units include (meth)acrylonitrile and cis,trans-crotononitrile.

[0075] Examples of monomers that yield butadiene units include butadiene, isoprene, and 1,3-cyclohexadiene.

[0077] The block copolymer (C2) preferably contains a block copolymer having two types of blocks, more preferably contains at least one of an AB-type diblock copolymer and an ABA-type triblock copolymer, even more preferably contains an ABA-type triblock copolymer, and particularly preferably contains an ABA-type triblock copolymer of methyl methacrylate block-butyl acrylate block-methyl methacrylate block.

[0078] Examples of commercially available block copolymers (C2) include Clarity LA2140, LA2330, LA3320, and LK9243 manufactured by Kuraray Co., Ltd.

[0079] [ component( D)] component( D) contains a siloxane oligomer (D1). A "siloxane oligomer" is a low polymer formed from a siloxane monomer having an -Si-O- bond, preferably a compound having 2 to 500 siloxane (-Si-O-) units, more preferably a compound having 2 to 100 units, and even more preferably a compound having 2 to 20 units.

[0080] Examples of siloxane oligomers (D1) include compounds represented by the following formula (2).

[0081] [ka]

[0082] In formula (2), E 1 and E 2 A is a hydrogen atom or an epoxy reactive group. 1 and A 2 Each of these is independently a single bond or a divalent linking group. 1 ~R 6Each of these is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, either substituted or unsubstituted. n is an integer between 0 and 500. If n is 2 or greater, there are multiple R 3 They may be the same or different, and multiple R 4 They may be the same or different.

[0083] A 1 and A 2 Examples of divalent linking groups represented by include divalent organic groups with 1 to 20 carbon atoms, including ether groups. 1 and A 2 It is preferable that it contains an alkylene oxyalkylene group or an oxyalkylene oxyalkylene group, and more preferably a propylene oxymethylene group or an oxypropylene oxymethylene group.

[0084] R 1 ~R 6 Examples of monovalent hydrocarbon groups represented by include linear hydrocarbon groups such as alkyl groups like methyl and ethyl groups; alicyclic hydrocarbon groups such as cycloalkyl groups like cyclohexyl and cyclohexylmethyl groups; and aromatic hydrocarbon groups such as aryl groups like phenyl and aralkyl groups like benzyl groups. Examples of substituents on hydrocarbon groups include hydroxyl groups and halogen atoms. 1 ~R 6 It is preferable that it contains an alkyl group or an aryl group, and more preferably a methyl group, an ethyl group, or a phenyl group.

[0085] n is preferably an integer between 0 and 100, more preferably between 0 and 50, and even more preferably 0.

[0086] The siloxane oligomer (D1) may or may not have epoxy reactive groups, but it is preferable that it has epoxy reactive groups. The siloxane oligomer (D1) preferably contains a siloxane oligomer having epoxy groups at both ends, side chains, or both ends and side chains, and more preferably contains a siloxane oligomer having epoxy groups at both ends. In this case, the bonding of the siloxane oligomer (D1) and the epoxy resin (A) can further improve the low elasticity and impact resistance reliability of the cured product of composition (X).

[0087] Examples of commercially available siloxane oligomers (D1) include TSL9906 and CostOSil MP200 from Momentive, X22-163 from Shin-Etsu Chemical Co., Ltd., and DOWSIL EP2601 from DOW.

[0088] [ second Elastomer (E) second The elastomer (E) contains a flexible epoxy resin (E1). The "flexible epoxy resin" is an epoxy resin having a flexible chain structure within its molecule. The flexible epoxy resin (E1) is not included in the epoxy resin (A). The flexible epoxy resin (E1) has epoxy groups as epoxy reaction groups. The flexible epoxy resin (E1) preferably has epoxy groups at at least one end of its molecule, and more preferably at both ends.

[0089] Examples of flexible chain-like structures include linear aliphatic carbon skeletons such as polyalkylene ether chains and polymethylene chains, and polyester chains.

[0090] Examples of commercially available flexible epoxy resins (E1) include YX7105 from Mitsubishi Chemical Corporation, EXA-4850S-150 from DIC Corporation, and EP-4000S from ADEKA Corporation.

[0091] [Other ingredients] Composition (X) may contain other components such as fillers such as silica, functional fillers such as conductive fillers, thixotropic agents, stabilizers, pigments such as carbon black, dyes, flame retardants, flame retardant aids, ultraviolet absorbers, antistatic agents, diluents, coupling agents, and curing accelerators, as long as the sum of the proportions of the components constituting composition (X) is within the range of 100% by mass or less. Composition (X) may contain one or more of these other components. The proportion of these other components is, for example, 0.01 parts by mass or more and 2 parts by mass or less of the total composition (X).

[0092] [Percentage of each component] The proportion of epoxy resin (A) is 13% by mass or more and 55% by mass or less of the total composition (X). If the proportion of epoxy resin (A) is less than 13% by mass, the adhesion of the cured product will decrease. If the proportion of epoxy resin (A) exceeds 55% by mass, the cured product will not be sufficiently low-elastic and the impact resistance reliability will decrease. The lower limit of the proportion of epoxy resin (A) is preferably 17% by mass or more, more preferably 20% by mass or more, and even more preferably 23% by mass or more. The upper limit of the proportion of epoxy resin (A) is preferably 44% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.

[0093] The proportion of the curing agent (B) is 20% by mass or more and 55% by mass or less of the total composition (X). If the proportion of the curing agent (B) is less than 20% by mass, the adhesion of the cured product will decrease. If the proportion of the curing agent (B) exceeds 55% by mass, the cured product will not be sufficiently low-elastic and the impact resistance reliability will decrease. The lower limit of the proportion of the curing agent (B) is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 33% by mass or more. The upper limit of the proportion of the curing agent (B) is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 42% by mass or less.

[0094] The proportion of the first elastomer (C) is 10% by mass or more and 20% by mass or less of the total composition (X). If the proportion of the first elastomer (C) is less than 10% by mass, it is difficult to achieve sufficient low elasticity of the cured product. If the proportion of the first elastomer (C) exceeds 20% by mass, the viscosity of the composition tends to increase significantly. The lower limit of the proportion of the first elastomer (C) is preferably 11% by mass or more, more preferably 13% by mass or more, and even more preferably 14% by mass or more. The upper limit of the proportion of the first elastomer (C) is preferably 19% by mass or less, more preferably 17% by mass or less, and even more preferably 16% by mass or less.

[0095] component( The proportion of D) is greater than 5% by mass and less than or equal to 25% by mass of the entire composition (X). component( If the proportion of D) is 5% by mass or less, the proportion of the first elastomer (C) must be relatively increased in order to ensure the total amount of elastomer, and as a result, the sufficient effect of lowering the viscosity of the composition cannot be obtained. Conversely, if the proportion of the first elastomer (C) is also reduced in order to suppress the increase in viscosity, the total amount of elastomer decreases, and the impact resistance reliability of the cured product tends to decline. component( If the proportion of D) exceeds 25% by mass, the proportion of the first elastomer (C) will be relatively reduced in order to suppress the total amount of elastomer, and as a result, the impact resistance reliability of the cured product will decrease. component( The lower limit of the proportion of D) is preferably 6% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, and particularly preferably 13% by mass or more. component( The upper limit of the proportion of D) is preferably 23% by mass or less, more preferably 20% by mass or less, and even more preferably 18% by mass or less.

[0096] For the first elastomer (C) ingredients (The mass ratio ((D) / (C)) of D) is preferably 0.5 or more and 3 or less, more preferably 0.8 or more and 2.2 or less, and even more preferably 1 or more and 2 or less.

[0097] The proportion of the curing agent (B) is preferably 30 parts by mass or more and 600 parts by mass or less, more preferably 50 parts by mass or more and 500 parts by mass or less, and even more preferably 70 parts by mass or more and 350 parts by mass or less, per 100 parts by mass of epoxy resin (A).

[0098] The proportion of the first elastomer (C) is preferably 5 parts by mass or more and 200 parts by mass or less, more preferably 10 parts by mass or more and 150 parts by mass or less, and even more preferably 20 parts by mass or more and 120 parts by mass or less, per 100 parts by mass of epoxy resin (A).

[0099] component( The proportion of D) is preferably 5 parts by mass or more and 400 parts by mass or less, more preferably 10 parts by mass or more and 300 parts by mass or less, and even more preferably 30 parts by mass or more and 250 parts by mass or less, per 100 parts by mass of epoxy resin (A).

[0100] Composition (X) second If it contains elastomer (E), second The proportion of elastomer (E) is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and particularly preferably 13% by mass or more, relative to the total composition (X). second By setting the proportion of elastomer (E) within the aforementioned range, the impact resistance reliability of the cured product can be further improved. second The proportion of elastomer (E) is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 18% by mass or less. second By setting the proportion of elastomer (E) within the aforementioned range, the adhesion of the cured product can be further improved.

[0101] Composition (X) second If it contains elastomer (E), second The proportion of elastomer (E) is preferably 1 to 500 parts by mass, more preferably 5 to 400 parts by mass, and even more preferably 10 to 250 parts by mass, per 100 parts by mass of epoxy resin (A).

[0102] The composition (X) of this embodiment has low viscosity, is suitable for application to an object, and can produce a cured product with low elasticity. The viscosity of composition (X) is not particularly limited as long as it is low enough to obtain suitable application properties, but it can be adjusted so that, when measured using an E-type rotational viscometer at 25°C and 1 rpm, it is, for example, less than 30 Pa·s, preferably 25 Pa·s or less. Furthermore, the elastic modulus of the cured product of composition (X) can be made low elastic, for example less than 1.5 GPa, preferably 1 GPa or less. The composition (X) of this embodiment can be suitably used as an adhesive, and can also be suitably used as a material for forming sealants, structural materials, etc.

[0103] <Adhesive> The adhesive according to this embodiment consists of composition (X). Since the adhesive of this embodiment consists of the above-described composition (X), it has low viscosity while exhibiting excellent adhesion, low elasticity, and impact resistance of the cured product. Therefore, the adhesive of this embodiment has excellent applicability, and the bonded body obtained by bonding with this adhesive has suppressed peeling and cracking, and improved drop impact reliability.

[0104] <Cured product> The cured product according to this embodiment is a cured product of composition (X). The cured product of this embodiment is obtained, for example, by heating and curing composition (X). The heating temperature is, for example, 50°C to 200°C, preferably 60°C to 120°C, and more preferably 70°C to 90°C. The heating time is, for example, 1 minute to 10 hours, preferably 10 minutes to 5 hours, and more preferably 30 minutes to 3 hours.

[0105] As described above, the cured product of this embodiment has excellent adhesion, low elasticity, and impact resistance, and can therefore be suitably used as a sealing material in, for example, cameras, camera modules, sensors, sensor modules, modules with displays, modules with dry cell batteries and coin batteries, etc.

[0106] <zygote> The joint according to this embodiment (hereinafter also referred to as joint (Y)) comprises a first member (hereinafter also referred to as member (1)), a second member (hereinafter also referred to as member (2)), and a bonding layer (hereinafter also referred to as bonding layer (h)). The bonding layer (h) is interposed between member (1) and member (2) to bond member (1) and member (2). The bonding layer (h) contains a cured product of composition (X).

[0107] As described above, the bonded body (Y) is manufactured using a composition (X) that has excellent adhesion, low elasticity, and impact resistance of the cured material, as well as low viscosity. Therefore, it can be manufactured simply and reliably, and peeling and cracking are suppressed, while drop impact reliability is improved.

[0108] The joint (Y) consists of member (1), member (2), and a bonding layer (h) interposed between them and formed by curing composition (X). The number of members to be bonded is not limited to 2, but may be 3 or more. Also, the number of members comprising the joint (Y) is not limited to 2, but may be 3 or more.

[0109] The components (1) and (2) are not particularly limited, but examples include substrates and electronic devices in electronic equipment. The bonded body (Y) is not particularly limited as long as it is made by bonding multiple components together with composition (X), but examples include various electronic devices and electrical equipment.

[0110] The aforementioned joint (Y) can be manufactured, for example, by interposing a composition (X) between member (1) and member (2) and heating the composition (X) to create a joint layer (h).

[0111] In the manufacturing of the joint (Y), first, a composition (X) is interposed between member (1) and member (2). The method of interposition is not particularly limited, but examples include a method in which the members are brought into close contact and then the composition (X) is applied to the contacted area, or a method in which the composition (X) is applied to each member and then the applied areas are brought into close contact.

[0112] Next, the composition (X) interposed between member (1) and member (2) is heated. This causes the composition (X) to heat-cur, creating a bonding layer (h). With the creation of the bonding layer (h), members (1) and (2) of the joined body (Y) are bonded more firmly, and the joined body (Y) is created. [Examples]

[0113] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples.

[0114] <Preparation of thermosetting resin composition> A thermosetting resin composition was prepared by mixing the raw materials shown in Table 1. Details of the raw materials shown in Table 1 are as follows.

[0115] - Epoxy resin (A) • Epoxy resin (A-1): Liquid bisphenol F type epoxy resin (YDF8170 manufactured by Nippon Steel Chemical & Material Co., Ltd.) • Epoxy resin (A-2): Liquid bisphenol A type epoxy resin (YD8125 manufactured by Nippon Steel Chemical & Material Co., Ltd.) - Hardener (B) (Manifested curing agent (B1)) • Obvious curing agent (B1-1): Amine curing agent (polyamine-based, "EH5030S" manufactured by ADEKA) (Latent curing agent (B2)) • Latent curing agent (B2-1): Microencapsulated curing agent ("NovaCure HXA9322HP" manufactured by Asahi Kasei Corporation) -First Elastomer (C) • Polyrotaxane (C1-1): SH1300P manufactured by ASM - component( D) • Siloxane oligomer (D-1): "CostOsil" manufactured by Momentive MP200 - second Elastomer (E) • Flexible epoxy resin (E-1): "YX7105" manufactured by Mitsubishi Chemical Corporation

[0116] <Rating> [Adhesion] Three mg of an adhesive consisting of a thermosetting resin composition was applied to four locations on a 3 cm square liquid crystal polymer (LCP) substrate. A 3 cm x 5 mm aluminum rivet was then placed on the adhesive portion to prepare a test specimen. The resulting test specimen was heat-cured in an 80°C dryer for 60 minutes. The shear strength of the heat-cured specimen was measured using a desktop bond tester (series 4000, Dage Precision Industry). Adhesion was evaluated according to the following criteria. ○: The shear strength was 15 MPa or higher. △: Shear strength was between 10 MPa and 15 MPa. ×: The shear strength was 10 MPa or less.

[0117] [Low elasticity and impact resistance reliability] A thermosetting resin composition was cured by heating at 80°C for 90 minutes to prepare test specimens with a width of 5 mm, a length of 10 mm, and a thickness of 0.5 mm. Tensile tests were performed on the obtained test specimens using an Autograph (AGS-X manufactured by Shimadzu Corporation) under the following conditions: 25°C, load cell 5000 N, tensile speed 5 mm / min, calculation range for elastic modulus: strain 0.25% to 0.5%, calculation range for fracture strain: sensitivity 0.1, and grip distance: 40 mm. The elastic modulus and fracture strain of the cured material were measured. (Low elasticity) The low elasticity of the cured product was evaluated according to the following criteria. ○: The modulus of elasticity was 1 GPa or less. △: The modulus of elasticity was greater than 1 GPa but less than 1.5 GPa. ×: The modulus of elasticity was 1.5 GPa or higher. (Shock resistance reliability) Regarding the impact resistance reliability of the cured material, the fracture strain value was measured as an indicator of resistance to fracture and evaluated according to the following criteria. ○: The fracture strain was 5% or more. △: The fracture strain was greater than 2% but less than 5%. ×: The fracture strain was 2% or less.

[0118] [Low viscosity] The viscosity of the thermosetting resin composition was measured using an E-type rotational viscometer (RE-215U, manufactured by Toki Sangyo Co., Ltd.) at 25°C and 1 rpm. The low viscosity of the composition was evaluated according to the following criteria. ○: The viscosity was 25 Pa·s or less. △: Viscosity was greater than 25 Pa·s and less than 30 Pa·s. ×: The viscosity was 30 Pa·s or higher.

[0119] [Table 1]

[0120] The results in Table 1 show that the thermosetting resin compositions of Examples 1 to 13, in which the proportions of all components (A) to (D) were within the specified range, exhibited excellent adhesion, low elasticity, impact reliability (breaking strain), and low viscosity. On the other hand, the thermosetting resin compositions of Comparative Examples 1 to 4, in which at least one of the proportions of components (A) to (D) was outside the specified range, exhibited poor performance in at least one of the aforementioned properties.

Claims

1. The material contains an epoxy resin (A), a curing agent (B), a first elastomer (C) comprising at least one of polyrotaxane and block copolymer, and a component (D) which is different from the polyrotaxane and block copolymer contained in the first elastomer (C) and comprises a siloxane oligomer. The proportion of the epoxy resin (A) is 13% by mass or more and 55% by mass or less. The proportion of the curing agent (B) is 20% by mass or more and 55% by mass or less. The proportion of the first elastomer (C) is 10% by mass or more and 20% by mass or less. A thermosetting resin composition in which the proportion of component (D) is greater than 5% by mass and less than or equal to 25% by mass.

2. The thermosetting resin composition according to claim 1, further comprising a flexible epoxy resin as a second elastomer (E).

3. The thermosetting resin composition according to claim 1, wherein the curing agent (B) comprises an apparent curing agent (B1) and a latent curing agent (B2).

4. The thermosetting resin composition according to claim 1, wherein the viscosity measured using an E-type rotational viscometer at 25°C and 1 rpm is less than 30 Pa·s, and the elastic modulus of the cured product is less than 1.5 GPa.

5. An adhesive comprising the thermosetting resin composition according to any one of claims 1 to 4.

6. A cured product of a thermosetting resin composition according to any one of claims 1 to 4.

7. The device comprises a first member, a second member, and a bonding layer interposed between the first member and the second member to join the first member and the second member. The bonding layer comprises a bonded body containing the cured product described in claim 6.

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