JPWO2017187783A1 - Thermosetting resin composition, cured product, molding material, and molded article - Google Patents

Abstract

This invention provides the thermosetting resin composition which can obtain the hardened | cured material which is excellent in toughness and adhesiveness, without significantly reducing mechanical strength and heat resistance. Moreover, this invention provides the hardened | cured material, molding material, and molded object which use this thermosetting resin composition.
The present invention relates to a polyrotaxane comprising a compound having a maleimide group, a cyclic molecule, a linear molecule penetrating through the opening of the cyclic molecule, and a blocking group that blocks both ends of the linear molecule. Is a thermosetting resin composition.

Description

The present invention relates to a thermosetting resin composition. Moreover, this invention relates to the hardened | cured material, molding material, and molded object which use this thermosetting resin composition.

Conventionally, epoxy resins have been widely used as sealing materials for electronic devices because of their advantages such as low warpage, low stress, high thermal conductivity, and high insulation. However, due to high performance of devices and severe use conditions, it has become difficult for conventional epoxy resins to satisfy requirements regarding heat resistance and the like. In particular, in the field of power devices, which have been attracting attention due to the recent trend of energy saving, development of silicon carbide elements and gallium nitride elements has been promoted, and operation of these elements at a temperature of 200 ° C. or higher is required. Yes. Therefore, a new sealing material that can cope with the operation guarantee at a temperature of 200 ° C. or higher has been demanded, and maleimide resin has attracted attention as a sealing material that replaces the epoxy resin.

The maleimide resin has high heat resistance and excellent dimensional stability, but generally has a drawback that the obtained cured product is brittle. As a method for improving this defect, a method of improving the molecular structure of maleimide resin (Patent Document 1) and a method of adding rubber or thermoplastic resin (Patent Documents 2 and 3) are disclosed.

JP-A-5-295111 Japanese Patent Laid-Open No. 7-149952 JP-A-6-41332

However, in the method for improving the molecular structure in the maleimide resin as disclosed in Patent Document 1, the molecular structure affects the heat resistance of the cured product, and it is difficult to achieve both high heat resistance and toughness. I found out that Moreover, in the method of adding rubber or thermoplastic resin to maleimide resin as disclosed in Patent Documents 2 and 3, it is necessary to add a large amount of rubber or thermoplastic resin to obtain the required toughness. As a result, it has been found that there is a problem that the mechanical strength and heat resistance are lowered.
An object of this invention is to provide the thermosetting resin composition which can obtain the hardened | cured material which is excellent in toughness and adhesiveness, without significantly reducing mechanical strength and heat resistance. Moreover, this invention aims at providing the hardened | cured material, molding material, and molded object which use this thermosetting resin composition.

The present invention relates to a polyrotaxane comprising a compound having a maleimide group, a cyclic molecule, a linear molecule penetrating through the opening of the cyclic molecule, and a blocking group that blocks both ends of the linear molecule. Is a thermosetting resin composition.
The present invention is described in detail below.

The present inventors have found that a cured product having excellent mechanical strength, heat resistance, and toughness can be obtained by using a compound having a maleimide group and a polyrotaxane in combination, and the present invention has been completed. It was.

The thermosetting resin composition of the present invention contains a compound having a maleimide group (hereinafter also referred to as “maleimide compound”).
For example, in a polyimide compound obtained by condensing tetracarboxylic dianhydride and diamine, molecules grow linearly. This polyimide compound has high strength and is mainly excellent in adhesion to metals. For example, it is used for flexible copper-clad laminates, but voids (bubbles) are easily generated due to by-product of water and alcohol during curing. There is a problem that. On the other hand, the maleimide compound used in the thermosetting resin composition of the present invention has the advantage that there is no by-product and no voids are generated because curing proceeds by an addition reaction. Further, the maleimide compound is excellent in strength, and in the curing reaction, the molecule grows in a three-dimensional network structure. Therefore, in addition to the metal, the maleimide compound has excellent adhesion to a wide range of materials such as glass and organic materials. It is used in glass-based copper-clad laminates and organic-based copper-clad laminates. The thermosetting resin composition of the present invention can impart high toughness to a cured product while maintaining the excellent characteristics of the maleimide compound described above by using such a maleimide compound and a polyrotaxane in combination. Further expansion of applications can be expected.

The maleimide compound preferably has two or more maleimide groups in one molecule. By having two or more maleimide groups in one molecule, a three-dimensional network structure can be easily formed, and a cured product having higher heat resistance can be obtained.
The maleimide compound is preferably a maleimide compound having an aromatic ring.

Examples of the compound having two or more maleimide groups in one molecule include compounds represented by the following formula (1).

In formula (1), Z is a divalent or higher residue, and n is an integer of 2 or higher.

In the formula (1), examples of the divalent or higher-valent residue represented by Z include, for example, a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 9 carbon atoms, a phenylene group, a naphthalene group, and benzenetriyl. Groups, substituted or unsubstituted aromatic hydrocarbon groups such as a benzenetetrayl group, and groups containing these aliphatic hydrocarbon groups and aromatic hydrocarbon groups.

Among the compounds represented by the formula (1), a compound represented by the following formula (2) and a compound represented by the following formula (3) are preferable from the viewpoint of heat resistance of the cured product. Moreover, the compound which has a structure represented by following formula (4) from a heat resistant viewpoint of hardened | cured material other than the compound represented by said Formula (1) is preferable.

In formula (2), Y represents a bond, a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, —N═N—, —N═C═N—, —C (═O) —, —SO. _2- , -S (= O)-, -O-, -S-, a divalent substituted or unsubstituted cyclic aliphatic hydrocarbon group, or a divalent substituted or unsubstituted aromatic hydrocarbon group R ¹ and R ² are each independently a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a halogen group, o and p are each independently an integer of 0 to 4. When o is 2 or more, the plurality of R ¹ may be the same or different, and when p is 2 or more, the plurality of R ² may be the same. And may be different.

In Formula (3), R ³ is a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a halogen group, and q is 0 to 0. It is an integer of 4. When q is 2 or more, the plurality of R ³ may be the same or different.

In Formula (4), R ⁴ is a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a halogen group, and r is 0 to 0. It is an integer of 3, and m is 2 or more. When r is 2 or more, the plurality of R ⁴ may be the same or different.

An aromatic hydrocarbon group in Y of Formula (2), R ¹ and R ² in Formula ( ² ), R ^{3 in} Formula (3), and a hydrocarbon group or an alkoxy group in R ⁴ of Formula (4) When it is substituted, examples of the substituent include a halogen group, a hydroxy group, an alkyl group having 10 or less carbon atoms, an alkoxy group having 10 or less carbon atoms, an acyloxy group, an acyl group, and a heterocyclic group.

Specific examples of the maleimide compound include 4,4′-bismaleimide biphenyl, bis (4-maleimidophenyl) methane, bis (3-maleimidophenyl) methane, bis (4-maleimidocyclohexyl) methane, and bis ( 3-maleimidocyclohexyl) methane, bis (3-methyl-4-maleimidophenyl) methane, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-4-maleimidophenyl) methane, bis ( 3,5-diethyl-4-maleimidophenyl) methane, bis (3-propyl-4-maleimidophenyl) methane, bis (3,5-dipropyl-4-maleimidophenyl) methane, bis (3-butyl-4-maleimide) Phenyl) methane, bis (3,5-dibutyl-4-maleimidophenyl) Methane, bis (3-ethyl-4-maleimido-5-methylphenyl) methane, 1,6′-bismaleimide- (2,2,4-trimethyl) hexane, 1,1,1,3,3,3- Hexafluoro-2,2-bis [4- (4-maleimidophenyloxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-maleimidophenyl) propane, 2,2-bis (4-maleimidophenyl) propane, 2,2-bis [4- (4-maleimidophenyloxy) phenyl] propane, bis (4-maleimidophenyl) ether, bis (3-maleimidophenyl) ether, Bis (4-maleimidophenyl) ketone, bis (4-maleimidophenyl) sulfone, bis (3-maleimidophenyl) sulfone, bis [4- (4-maleic Midphenyloxy) phenyl] sulfone, bis (4-maleimidophenyl) sulfide, bis (3-maleimidophenyl) sulfide, bis (4-maleimidophenyl) sulfoxide, bis (3-maleimidophenyl) sulfoxide, bis (4-maleimidophenyl) ) Diphenylsilane, 1,4-bis (4-maleimidophenyl) cyclohexane, 4-methyl-1,3-phenylenebismaleimide, 1,3-phenylenebismaleimide, 1,4-phenylenebismaleimide, 1,2-phenylene Examples thereof include bismaleimide, naphthalene-1,5-dimaleimide, 4-chloro-1,3-phenylenebismaleimide, novolac type polymaleimide, and zylock type polymaleimide. These maleimide compounds may be used alone or in combination of two or more.
The maleimide group of the compound having two or more maleimide groups in one molecule is preferably present at a position where the molecule has line symmetry from the viewpoint of heat resistance of the cured product.

The maleimide compound may have an alkenyl group and / or an amino group in addition to the maleimide group.
Examples of the maleimide compound having an alkenyl group include N-allylmaleimide, N-methacrylmaleimide, N-ethylmalemidyl methacrylate, N-ethylmalemidyl acrylate, and the like.
Examples of maleimide compounds having an amino group include N-aminomethylmaleimide, N- (2-aminoethyl) maleimide, N- (4-aminophenyl) maleimide and the like.

The minimum with preferable content of the said maleimide compound in the whole thermosetting resin composition of this invention is 30 mass%, a preferable upper limit is 95 mass%, a more preferable minimum is 50 mass%, and a more preferable upper limit is 85 mass%. It is.

The thermosetting resin composition of the present invention comprises a polyrotaxane comprising a cyclic molecule, a linear molecule penetrating through the opening of the cyclic molecule, and a blocking group that blocks both ends of the linear molecule. contains.

The cyclic molecule is a compound that can be included so that a linear molecule penetrates like a skewer in an opening and can move on the linear molecule.
As a method for including the linear molecule by the cyclic molecule, a conventionally known method (for example, a method described in JP-A-2005-154675) can be used.
In the present specification, “cyclic” of the cyclic molecule means substantially cyclic, and may be a complete ring-closed structure as long as it can move on the linear molecule. For example, a spiral structure may be used.

Examples of the cyclic molecule include cyclic polymers such as cyclic polyether, cyclic polyester, and cyclic polyetheramine, pillar arenes, cyclophanes, ring-expanded porphyrins, and cyclodextrins.
Examples of the cyclic polymer include crown ether and derivatives thereof, calixarene and derivatives thereof, cyclophane and derivatives thereof, cryptand and derivatives thereof, and the like.
The cyclic molecule is appropriately selected depending on the type of linear molecule to be used. However, since it is easily available and many types of blocking groups can be selected, α-cyclodextrin, β-cyclodextrin, γ-cyclo Cyclodextrins such as dextrin are preferred. For example, as will be described later, when polyethylene glycol is selected as the linear molecule, α-cyclodextrin is preferred from the viewpoint of the stability of the resulting clathrate.

When a cyclodextrin is used as the cyclic molecule, a part of the hydroxyl group of the cyclodextrin is modified with a modifying group that improves compatibility with the maleimide compound (hereinafter also referred to as “solubility imparting group”). It is preferable.

Examples of the solubility-imparting group include an acetyl group, an alkyl group having 1 to 18 carbon atoms, a trityl group, a trimethylsilyl group, a phenyl group, a polyester chain, an oxyethylene chain, and a polyacrylate chain. These modifying groups may be introduced alone or two or more of them may be introduced. When introducing two or more kinds of modifying groups, for example, when introducing an oxyethylene chain and a polyester chain, the hydroxyl group of the cyclodextrins is first modified with an oxyethylene chain, and the introduced hydroxyl group at the end of the oxyethylene chain is changed. As a starting point, a method of introducing a polyester chain or the like can be used. Specifically, after adding a hydroxypropyl group to a hydroxyl group present in cyclodextrin itself, ring-opening polymerization of ε-caprolactone through the hydroxyl group of the hydroxypropyl group to introduce a polycaprolactone (polyester) chain Can do.

From the viewpoint of compatibility with the maleimide compound, the introduction rate of the solubility-imparting group is preferably 10 mol%, preferably the upper limit with respect to the total hydroxyl groups of the cyclodextrins when cyclodextrins are used as the cyclic molecules. Is 90 mol%, a more preferred lower limit is 30 mol%, and a more preferred upper limit is 70 mol%.

The polyrotaxane contained in the thermosetting resin composition of the present invention may have a substituent that can directly participate in the thermosetting reaction (hereinafter also referred to as “curing reactive substituent”). When the polyrotaxane has a curing reactive substituent, the curing reactive substituent may be directly introduced into a cyclic molecule, for example, a hydroxyl group of cyclodextrins, or the terminal reactive site of the solubility-imparting group, For example, after a hydroxypropyl group is added to the hydroxyl group of cyclodextrins, a polycaprolactone (polyester) chain is introduced by ring-opening polymerization of ε-caprolactone via the hydroxyl group of the hydroxypropyl group. It may be introduced into the terminal hydroxyl group of the caprolactone chain. When the polyrotaxane has a curing reactive substituent, compatibility is improved. Moreover, since polyrotaxane also causes a curing reaction, polyrotaxane is dispersed at the molecular level (nm order), and a transparent cured product is obtained. On the other hand, when the polyrotaxane does not have a curing reactive substituent, the polyrotaxane is dispersed on the order of μm, and an opaque cured product is obtained. That is, when used for applications requiring transparency, such as optical electronic materials, the polyrotaxane preferably has a curing reactive substituent.

Examples of the curing reactive substituent include (meth) acryloyl group, vinyl group, allyl group and the like.
In the present specification, the “(meth) acryloyl” means at least one of “acryloyl” and “methacryloyl”.

The curing reactive substituent is a compound having a reactive group such as a hydroxyl group in the cyclic molecule before introducing the curing reactive substituent, a functional group capable of reacting with the reactive group, and a curing reactive substituent. It can introduce | transduce by making it react.

As a compound having a functional group capable of reacting with the reactive group and a curing reactive substituent, when a (meth) acryloyl group is introduced, for example, (meth) acryloyl chloride, (meth) acrylic anhydride, 2 -(Meth) acryloyloxyethyl isocyanate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, α-methacryloyloxy-γ-butyrolactone, β-methacryloyloxy-γ-butyrolactone, and the like.
When introducing a vinyl group, for example, p-vinylbenzoic acid, p-vinylbenzoic acid chloride, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, vinyl chloroacetate and the like can be mentioned.
When introducing an allyl group, for example, p-allylbenzoic acid, p-allylbenzoic acid chloride, allyl isocyanate, allyl isothiocyanate and the like can be mentioned.
Among these, from the viewpoint of easy availability and high reactivity, (meth) acryloyl chloride, 2- (meth) acryloyloxyethyl isocyanate, glycidyl (meth) acrylate, 3-isopropenyl isocyanate, α, α -Dimethylbenzyl, vinyl chloroacetate and allyl isocyanate are preferred.
In the present specification, the “(meth) acrylate” means at least one of “acrylate” and “methacrylate”.

When the cyclodextrin is used as a cyclic molecule, the introduction rate of the curing reactive substituent is preferably a lower limit of 5 mol% and a preferable upper limit of 80 mol% with respect to the total hydroxyl groups of the cyclodextrins. When the introduction rate of the curing reactive substituent is within this range, the cured product is particularly excellent in transparency. A more preferable lower limit of the introduction ratio of the curing reactive substituent is 10 mol%, and a more preferable upper limit is 50 mol%.

When the inclusion ratio of the amount of inclusion of the cyclic molecule as a percentage with respect to the amount (maximum inclusion amount) that can be included at the maximum when the cyclic molecule includes the linear molecule is included, The preferable lower limit of the contact ratio is 0.1%, the preferable upper limit is 60%, the more preferable lower limit is 1%, the more preferable upper limit is 50%, the still more preferable lower limit is 5%, and the further preferable upper limit is 40%. .
The maximum inclusion amount can be determined by the length of the linear molecule and the thickness of the cyclic molecule. For example, the maximum amount of inclusion when the linear molecule is polyethylene glycol and the cyclic molecule is α-cyclodextrin is experimentally determined (see Macromolecules 1993, 26, 5698-5703).

The linear molecule can be clasped into the opening of a cyclic molecule, for example, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinyl methyl ether, polytetrahydrofuran. , Polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), casein, gelatin, starch, cellulose resin (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc.), polyolefin resin (polyethylene, polypropylene, polyisobutylene, and Copolymers of these with other olefinic monomers), polyester resins, polyvinyl chloride resins (vinyl chloride-vinyl acetate) Copolymer), polystyrene resin (polystyrene, acrylonitrile-styrene copolymer, etc.), acrylic resin (poly (meth) acrylic acid, polymethyl methacrylate, (meth) acrylic acid ester copolymer, acrylonitrile-methyl acrylate) Polymer), polycarbonate resin, polyurethane resin, polyvinyl acetal resin (polyvinyl butyral resin, etc.), polyamide resin (nylon (registered trademark), etc.), polyimide resin, polydiene resin (polyisoprene, polybutadiene, etc.), polysiloxane resin (poly Dimethylsiloxane), polysulfone resin, polyimine resin (polyethyleneimine, etc.), polyamine resin, polyacetic anhydride resin, polyurea resin, polysulfide resin, polyphosphazene resin, polyketone resin, polyketone resin, Phenylene resins, polyhaloolefins resin and copolymers thereof, derivatives, modified products and the like. Among these, polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol, and polyvinyl methyl ether are preferable, polyethylene glycol, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, Polyethylene and polypropylene are more preferred, and polyethylene glycol is even more preferred.
In the present specification, the “(meth) acryl” means at least one of “acryl” and “methacryl”.

The preferable lower limit of the weight average molecular weight of the linear molecule is 3000, and the preferable upper limit is 300,000. When the weight average molecular weight of the linear molecule is within this range, the effect of improving the toughness of the cured product obtained without deteriorating the compatibility between the polyrotaxane and the maleimide compound is obtained. The more preferable lower limit of the weight average molecular weight of the linear molecule is 5000, the more preferable upper limit is 100,000, the still more preferable lower limit is 10,000, and the still more preferable upper limit is 50,000.
In addition, the mass average molecular weight of the said linear molecule is a value calculated | required by polyethyleneglycol conversion, measuring with gel permeation chromatography (GPC). Examples of the column for measuring the mass average molecular weight in terms of polyethylene glycol by GPC include TSKgel SuperAWM-H (manufactured by Tosoh Corporation).
Further, the mass average molecular weight other than the linear molecule is a value determined by polystyrene conversion after measurement by GPC unless otherwise specified. Examples of the column for measuring the mass average molecular weight in terms of polystyrene by GPC include TSKgel SuperHM-M (manufactured by Tosoh Corporation).

In the polyrotaxane used in the present invention, the linear molecule is preferably polyethylene glycol, and the cyclic molecule is preferably a molecule derived from α-cyclodextrin.

The blocking groups are arranged at both ends of the linear molecule included in the cyclic molecule and have a role of preventing the cyclic molecule from leaving. As a method for blocking both ends of a linear molecule with a blocking group, a conventionally known method (for example, a method described in JP-A-2005-154675) can be used.

Examples of the blocking group include dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, silsesquioxanes, pyrenes, anthracenes, and the like having a mass average molecular weight of 1,000 to 1,000,000. Examples include a main chain or a side chain of a polymer.
Of these, dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, silsesquioxanes, and pyrenes are preferable, and adamantane groups and trityl groups are more preferable.
Examples of the polymer having a mass average molecular weight of 1,000 to 1,000,000 include polyamide, polyimide, polyurethane, polydimethylsiloxane, and polyacrylic acid ester.
Two or more of these blocking groups may be mixed in the polyrotaxane.

The content of the polyrotaxane is such that a preferable lower limit is 1 part by mass and a preferable upper limit is 20 parts by mass with respect to 100 parts by mass of the maleimide compound. When the content of the polyrotaxane is within this range, the obtained cured product is particularly excellent in toughness and mechanical strength. The minimum with more preferable content of the said polyrotaxane is 3 mass parts, and a more preferable upper limit is 10 mass parts.
Moreover, the minimum with preferable content of the said polyrotaxane in the whole thermosetting resin composition of this invention is 0.5 mass%, and a preferable upper limit is 10 mass%. When the content of the polyrotaxane is within this range, the obtained cured product is particularly excellent in toughness and mechanical strength. The minimum with more preferable content of the said polyrotaxane is 2 mass%, and a more preferable upper limit is 5 mass%.

The thermosetting resin composition of the present invention further has, as a curing agent, an aromatic compound having two or more alkenyl groups in one molecule other than the maleimide compound, and two or more amino groups in one molecule. It is preferable to contain a compound and at least one compound selected from the group consisting of aromatic compounds each having one alkenyl group and one amino group in one molecule. These compounds have a role of promoting the formation of a three-dimensional network structure and further improving the heat resistance of the resulting cured product.

Examples of the aromatic compound having two or more alkenyl groups in one molecule include compounds represented by the following formula (5).

In Formula (5), R ⁵ is a substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms, s is an integer of 1 to 4, and X is a monovalent atom or atomic group, or a divalent or higher residual group. A group, l is an integer of 1 or more, and when X does not include an alkenyl group, at least one of s and l is 2 or more, and when X is a monovalent atom or atomic group, l Is 1. When there are a plurality of R ⁵ , each R ⁵ may be the same or different.

In said Formula (5), as a monovalent atom or atomic group represented by X, a halogen atom, a C1-C6 substituted or unsubstituted alkyl group, etc. are mentioned, for example.
In the formula (5), examples of the divalent or higher residue represented by X include a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, —N═N—, —N═C═N—. , —C (═O) —, —SO ₂ —, —S (═O) —, —O—, —S—, divalent substituted or unsubstituted cyclic aliphatic hydrocarbon group, divalent substitution Or an unsubstituted aromatic hydrocarbon group etc. are mentioned.

Among the compounds represented by the formula (5), a compound represented by the following formula (6) is preferable from the viewpoint of heat resistance of the cured product.

In formula (6), W represents a bond, a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, —N═N—, —N═C═N—, —C (═O) —, —SO. _2- , -S (= O)-, -O-, -S-, a divalent substituted or unsubstituted cyclic aliphatic hydrocarbon group, or a divalent substituted or unsubstituted aromatic hydrocarbon group R ⁶ and R ⁷ are each independently a substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms, t and u are each independently an integer of 0 to 4, and t + u is 2 That's it. When t or u is 2 or more, the plurality of R ⁶ or R ⁷ may be the same or different.

Specific examples of the aromatic compound having two or more alkenyl groups in one molecule include 2,2′-diallylbisphenol A, 2,2′-diallylbisphenol F, and 2,2-bis [4. -Hydroxy-3,5-di (2-propenylphenyl)] propane, bis [4-hydroxy-3- (2-propenyl) phenyl] sulfoxide, bis [4-hydroxy-3- (2-propenyl) phenyl] sulfide Bis [4-hydroxy-3- (2-propenyl) phenyl] ether, bis [4-hydroxy-3- (2-propenyl) phenyl] sulfone, 1,1-bis [4-hydroxy-3- (2- Propenyl) phenyl] ethylbenzene, 1,1-bis [4-hydroxy-3- (2-propenyl) phenyl] cyclohexane, 1,1,1,3 3,3-hexafluoro-2,2-bis- [4-hydroxy-3- (2-propenyl) phenyl] propane, bis [4-hydroxy-3- (2-propenyl) phenyl] ketone, 9,9- Bis [4-hydroxy-3- (2-propenyl) phenyl] fluorene, 3,3-bis [4-hydroxy-3- (2-propenyl) phenyl] phthalide, 2,2-bis [4-hydroxy-3- Methyl-5- (2-propenyl) phenyl] propane, 2,2-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] propane, bis [4-hydroxy-3- (2-methyl) -2-propenyl) phenyl] methane and the like.

The compound having two or more amino groups in one molecule is preferably a compound represented by the following formula (7) from the viewpoint of heat resistance of the cured product.

In formula (7), V is a divalent substituted or unsubstituted aromatic hydrocarbon group or a divalent substituted or unsubstituted alicyclic hydrocarbon group.

Specific examples of the compound having two or more amino groups in one molecule include metaphenylene diamine, paraphenylene diamine, 2,2-bis (4-aminophenyl) propane, and 4,4′-diamino. Diphenylmethane, bis (4-aminophenyl) diphenylsilane, bis (4-aminophenyl) methylphosphine oxide, bis (3-aminophenyl) methylphosphine oxide, bis (4-aminophenyl) phenylphosphine oxide, metaxylylenediamine, P-xylylenediamine, 1,1-bis (p-aminophenyl) phthalane, 6,6′-diamino-2,2′-dipyridyl, 4,4′-diaminobenzophenone, 4,4′-diaminoazobenzene, bis ( 4-aminophenyl) phenylmethane, 1,1-bis ( -Aminophenyl) cyclohexane, 1,1-bis (4-amino-3-methylphenyl) cyclohexane, 2,5-bis (m-aminophenyl) -1,3,4-oxadiazol, 4,4'- Diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ether, 2,6-diaminopyridine, 1,5-diaminonaphthalene, 3,3′-dimethyl-4,4′- Diaminobiphenyl, 3,3′-dimethoxybenzidine, 2,5-diamino-1,3,4-oxadiazol, 2,4-bis (β-amino-tert-butyl) toluene, bis (p-β-amino) -Tert-butylphenyl) ether, bis (p-β-methyl-α-aminophenyl) benzene, bis-p- (1,1-dimethyl-5-aminopen) Til) benzene, 1-isopropyl-2,4-m-phenyldiamine, 4,4｀-methylenebiscyclohexanediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1, Examples include 3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, isophorone diamine, norbornene diamine, and the like.

From the viewpoint of the heat resistance of the cured product, the alkenyl group of the aromatic compound having two or more alkenyl groups in one molecule and the amino group of the compound having two or more amino groups in one molecule are: It is preferable that the molecule exists at a position where the molecule has line symmetry.

Examples of the aromatic compound having one alkenyl group and one amino group in one molecule include 2-allylaniline, 2-allyl-5-methoxyaniline, 4-allylaniline, 4-isopropenylaniline, Examples include 2-methyl-4-isopropenyl aniline, 3-methyl-4-isopropenyl aniline, 3-chloro-4-isopropenyl aniline, 4-isobutenyl aniline, and the like.

When the thermosetting resin composition of the present invention contains the curing agent, the preferred lower limit of the maleimide compound / curing agent (molar ratio) is preferably 0.5, as the content ratio of the maleimide compound and the curing agent. The upper limit is 5. When the maleimide compound / curing agent (molar ratio) is within this range, the resulting cured product is particularly excellent in heat resistance and flexibility. The more preferable lower limit of the maleimide compound / curing agent (molar ratio) is 1, and the more preferable upper limit is 3.
Moreover, the minimum with preferable content of the said hardening | curing agent in the whole thermosetting resin composition of this invention is 4.5 mass%, a preferable upper limit is 60 mass%, A more preferable minimum is 10 mass%, A more preferable upper limit Is 45% by weight.

The thermosetting resin composition of the present invention is, as necessary, other resins, curing accelerators, reinforcing fiber materials, antioxidants, pigments (dyes), ultraviolet absorptions, as long as the object of the present invention is not impaired. You may contain various additives, such as an agent, a flame retardant, and a coupling agent.

Examples of the other resin include rubber components such as natural rubber, butadiene rubber, nitrile rubber, and carboxy-modified nitrile rubber, polyolefin, acid-modified polyolefin, polyester, polyether, polyethersulfone, polyetheretherketone, and polyether. Examples thereof include thermoplastic resins such as imide, polysulfone, polyphenylene sulfide, and nylon.

Examples of the curing accelerator include N, N-dimethylcyclohexylamine, N-methyldicyclohexylamine, dimethylaminomethylphenol, benzyldimethylamine, trisdimethylaminomethylphenol, 1,8-diazabicyclo [5,4,0]. Amines such as undecene-7, imidazoles such as 2-methylimidazole, 2-phenylimidazole, heptadecylimidazole, 2-heptadecylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and trimethylphosphine , Triethylphosphine, tributylphosphine, triphenylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, methyldiphenylphosphine, dibutylphenylphosphine Phosphines such as tricyclohexylphosphine, 1,2-bis (diphenylphosphine) ethane, bis (diphenylphosphine) methane, metal compounds such as tin octylate, tin chloride, aluminum chloride, tetrabutylphosphonium bromide, tetraphenylphosphonium Quaternary phosphonium salts such as bromide, methyltriphenylphosphonium bromide, boron compounds such as boron trifluoride-diethyl ether complex, boron trichloride-amine complex, benzoyl peroxide, di-tert-butyl peroxide, dichloride Examples thereof include organic peroxides such as mill peroxide and azo compounds such as azobisisobutyronitrile and dimethyl-2,2-azobis (2-methylpyropionate).

Examples of the reinforcing fiber material include plant fibers such as paper, cotton, hemp, banana fiber, bamboo fiber and bagasse fiber, animal fibers such as silk and wool, glass fiber, ceramic fiber, carbon fiber, and silicon carbide fiber. And synthetic polymer fibers such as aramid fibers, polyester fibers, and nylon fibers. Examples of the form of these reinforcing fiber materials include nonwoven fabric, woven fabric, filament, strand, chopped strand, yarn, roving and the like.

Examples of the antioxidant include 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-p-ethylphenol, stearyl-β- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol) 4,4'-thiobis (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2 -{Β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10- Tetraoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, bis [ 3,3′-bis- (4′-hydroxy-3′-tert-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-tert-butyl-4′- Hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol, dilauryl-3,3′-thiodipropionate, dimyristyl- , 3'-thiodipropionate, distearyll-3,3'-thiodipropionate, riphenyl phosphite, diphenylisodecyl phosphite, phenyldiisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite Tris (2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbis (2,4-di-tert-butylphenyl) phosphite, Cyclic neopentanetetraylbis (2,4-di-tert-butyl-4-methylphenyl) phosphite, bis [2-tert-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl ] Hydrogen Sphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa -10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like.

Examples of the pigment (dye) include titanium oxide, zinc oxide, molybdenum red, cadmium yellow, cadmium red, bitumen, ultramarine blue, bengara, and carbon black.

Examples of the ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxy Benzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfo Benzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5 '-G-tert Butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-) tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole, 2-{(2'-hydroxy-3', 3 " , 4 ", 5", 6 "-tetrahydrophthalimidomethyl) -5'-methylphenyl} benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2 , 6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [{3,5-bis (1, - dimethylethyl) -4-hydrido hydroxyphenyl} methyl] butyl malonate, and the like.

Examples of the flame retardant include brominated epoxy resins such as brominated bisphenol A type epoxy resin and brominated phenol novolak type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetra Bromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene, 2, Brominated flame retardants such as 4,6-tris (tribromophenoxy) -1,3,5-triazine, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di 2,6 carboxymethyl Les sulfonyl phosphate, resorcinol bis (diphenyl phosphate), and phosphorus-based flame retardant of red phosphorus, aluminum hydroxide, and metal hydroxides such as magnesium hydroxide. Further, a flame retardant aid such as antimony trioxide and antimony pentoxide may be used in combination.

Examples of the coupling agent include 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (phenylamino) propyltrimethoxysilane, and 3- (2-aminoethyl). Aminopropylmethyldimethoxysilane, N-6- (aminohexyl) 3-aminopropyltrimethoxysilane, N- (3- (trimethoxysilyl) propyl) -1,3-benzenedimethanamine, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltri (β-methoxyethoxy) silane, γ-mercaptopropyltrimethoxysilane, 3- Examples include mercaptopropylmethyldimethoxysilane, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropylisostearoyl diacryl titanate, acetoalkoxyaluminum diisopropylate, and the like.

The thermosetting resin composition of the present invention is obtained by uniformly dissolving the maleimide compound, the polyrotaxane, and additives such as a curing agent and a curing accelerator used as necessary in an organic solvent, and then adding the organic solvent. And a method of uniformly kneading using a melt mixing apparatus such as a roll or a kneader.

A cured product obtained by curing the thermosetting resin composition of the present invention is also one aspect of the present invention.
The thermosetting resin composition of the present invention varies depending on the type of material used and the blending ratio, but usually, the curing reaction hardly proceeds at the melt mixing temperature or solution mixing temperature when producing the thermosetting resin composition. The resulting thermosetting resin composition can be cured by further heating.
The curability when curing the thermosetting resin composition of the present invention varies depending on the presence or absence of a curing accelerator, the heating temperature, the way of heating, and the like, and the curing reaction is controlled by adjusting these conditions. be able to.

The curing temperature for curing the thermosetting resin composition of the present invention is usually 80 to 350 ° C, preferably 120 to 300 ° C, and more preferably 150 to 250 ° C. The curing time when curing the thermosetting resin composition of the present invention is usually 6 to 24 hours, and preferably 6 to 12 hours.

A molding material obtained by blending a filler with the thermosetting resin composition of the present invention is also one aspect of the present invention. By blending the filler, functions such as high conductivity, high thermal conductivity, insulation, and low hygroscopicity can be improved, and a thermosetting resin composition suitable for the application can be obtained.
As the filler, inorganic fillers or organic fillers having various shapes can be used. Specifically, for example, metal particles such as aluminum powder, iron powder, copper powder, fumed silica, calcined silica, precipitated silica, ground silica, fused silica, clay, mica, talc, iron oxide, zinc oxide, titanium oxide, Inorganic particles such as barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, aluminum hydroxide, alumina, glass, etc., wood powder, pulp powder, various textile pulverized products, pulverized products of thermosetting resin cured products, etc. Organic particles etc. are mentioned.

The minimum with preferable content of the said filler in the whole molding material of this invention is 1 mass%, and a preferable upper limit is 90 mass%. When the content of the filler is within this range, the effect of improving functions such as high conductivity without deteriorating workability becomes excellent. The minimum with more preferable content of the said filler is 5 mass%, and a more preferable upper limit is 80 mass%.

Examples of the method for producing the molding material of the present invention include a method of melt-kneading the thermosetting resin composition of the present invention and the filler.

A molded body obtained by curing the molding material of the present invention is also one aspect of the present invention.
A conventionally known method can be used as a method for obtaining the molded product of the present invention by curing the molding material of the present invention. Specifically, for example, injection molding method, melt casting method, compression molding method, transfer molding method, prepreg lamination press molding method, prepreg autoclave molding method, matched die molding method, hand lay-up molding method, SMC (Sheet Molding Compound) Examples thereof include a press molding method, a BMC (Bulk Molding Compound) molding method, a resin infusion molding method, a filament winding molding method, a pultrusion molding method, and a pin winding molding method.

Further, the thermosetting resin composition of the present invention can be formed into a prepreg by dissolving in a solvent and impregnating and drying the reinforcing fiber material as a varnish, a hand lay-up method, a spray-up method, or the like. it can.

The thermosetting resin composition of the present invention can be used for electrical / electronic materials such as semiconductor encapsulating materials and printed circuit boards, automobile parts such as balance shaft gears, clutch facings, brake linings, disk pads, railway vehicles, aircraft, It can be used for structural materials, parts, interior / exterior materials, floor materials, wall materials, panels, etc. used in ships and the like. It can also be used for interior / exterior materials, ceiling materials, wall materials, heat insulation panels, refrigeration / freezer warehouse panels, etc. used in buildings. Furthermore, it can be applied to various pipe heat insulation materials for tanks and plants. In addition, it can also be applied to resin concrete, sports applications such as golf shafts and fishing rods, paints, and adhesives. Especially, since the hardened | cured material obtained using the thermosetting resin composition of this invention has high fracture toughness and high heat resistance, it is suitable for the sealing material for semiconductors.

ADVANTAGE OF THE INVENTION According to this invention, the thermosetting resin composition which can obtain the hardened | cured material which is excellent in toughness and adhesiveness, without significantly reducing mechanical strength and heat resistance can be provided. Moreover, according to this invention, the hardened | cured material, molding material, and molded object which use this thermosetting resin composition can be provided.

It is a graph which shows the relationship between the storage elastic modulus E 'and temperature in the hardened | cured material obtained in Example 1, Example 2, and the comparative example 1. FIG. 6 is a graph showing the relationship between the loss elastic modulus E ″ and temperature in the cured products obtained in Example 1, Example 2, and Comparative Example 1. 6 is a graph showing the relationship between the loss tangent tan δ and the temperature in the cured products obtained in Example 1, Example 2, and Comparative Example 1.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. Hereinafter, the polyrotaxane used in the production examples was prepared with reference to the method described in JP2011-241401A.

(Production Example 1)
(Production of polyrotaxane)
As a linear molecule, polyethylene glycol (mass average molecular weight 35000), as a cyclic molecule, after introducing a hydroxypropyl group, α-cyclodextrin grafted with ε-caprolactone (hydroxypropyl group introduction rate 51 mol%), A polymerization inhibitor was added to 300 g of a 35 mass% xylene solution of a polyrotaxane having an adamantaneamine group as a blocking group (inclusion rate of cyclic molecules 25%, mass average molecular weight 470000, hydroxyl value 74 mg KOH / g, hereinafter also referred to as “PR”). Then, 50 mg of dibutylhydroxytoluene was added and stirred at 25 ° C. for 30 minutes to completely dissolve dibutylhydroxytoluene. Next, 11.8 g of 2-methacryloyloxyethyl isocyanate was added and stirred at 25 ° C. for 30 minutes, and then the temperature was raised to 60 ° C. and allowed to react for 4 hours. The obtained reaction solution was cooled to 25 ° C., added to a large amount of methanol, stirred, and a precipitate was taken out by a centrifugal separation method. The obtained precipitate was dissolved in a large amount of acetone, added to a large amount of methanol, stirred to reprecipitate, and the precipitate was taken out by a centrifugal separation method. The obtained precipitate was dried to obtain 108.9 g of a polyrotaxane (hereinafter, also referred to as “MPR”) having a methacryloyloxyethylcarbamoyl group which is a curing reactive substituent in the cyclic molecule. When the introduction rate of the curing reactive substituent was determined for the obtained MPR, it was 50 mol%.

(Production Example 2)
(Production of caprolactone-grafted cyclic product)
30 g of hydroxypropylated β-cyclodextrin having a hydroxypropyl group introduced as a cyclic molecule (hydroxypropyl group introduction rate 25.9 mol%) was dried at 120 ° C. for 1 hour under normal pressure using a hot air dryer. . To 27 g of dried hydroxypropylated β-cyclodextrin (weight loss on drying 1% by weight), 122 g of ε-caprolactone and 0.858 g of tin 2-ethylhexanoate as a catalyst were added and polymerized at 120 ° C. for 7 hours. Then, 149 g of a caprolactone-grafted cyclic product (hereinafter also referred to as “PCL-PO-β-CD”) grafted with ε-caprolactone was obtained.

Example 1
6.6 g of PR was dissolved in 3 times the amount of acetone, and this was added to 100 g of 2,2′-diallylbisphenol A heated to 90 ° C. Acetone was removed by vacuum degassing at 110 ° C. for 60 minutes. Next, 116.2 g of bis (4-maleimidophenyl) methane was added, heated and melted at 170 ° C., and vacuum degassed at 120 ° C. for 15 minutes to obtain a thermosetting resin composition. The obtained thermosetting resin composition was cast into an aluminum plate mold using a Teflon (registered trademark) plate having a thickness of 3 mm as a spacer, and in order, 2 hours at 160 ° C., 2 hours at 180 ° C., 2 at 200 ° C. The cured product was obtained by heating at 230 ° C. for 2 hours and at 250 ° C. for 2 hours.

(Example 2)
A thermosetting resin composition and a cured product were obtained in the same manner as in Example 1 except that the amount of PR was 11.0 g.

(Example 3)
A thermosetting resin composition and a cured product were obtained in the same manner as in Example 1 except that MPR 6.5 g was used instead of PR 6.6 g.

Example 4
A thermosetting resin composition and a cured product were obtained in the same manner as in Example 3 except that the blending amount of MPR was 10.9 g.

(Example 5)
A thermosetting resin composition and a cured product were obtained in the same manner as in Example 1 except that 183 g of 4-methyl-1,3-phenylenebismaleimide was used instead of 116.2 g of bis (4-maleimidophenyl) methane. Got.

(Example 6)
A thermosetting resin composition and a cured product were obtained in the same manner as in Example 5 except that 6.5 g of MPR was used instead of PR 6.6 g.

(Example 7)
PR5.8 g was dissolved in 3 times the amount of acetone, and this was heated to 170 ° C. 100 g of bis (4-maleimidophenyl) methane, 4-methyl-1,3-phenylenebismaleimide 50 g, 1,6-bismaleimide- To a mixture of 16.7 g of (2,2,4-trimethyl) hexane, vacuum deaeration was performed at 130 ° C. for 20 minutes to remove acetone. 25 g of metaphenylenediamine melted by heating was added thereto to obtain a thermosetting resin composition. The obtained thermosetting resin composition was cast into an aluminum plate mold using a Teflon (registered trademark) plate having a thickness of 3 mm as a spacer, and in order, 2 hours at 160 ° C., 2 hours at 180 ° C., 2 at 200 ° C. The cured product was obtained by heating at 230 ° C. for 2 hours and at 250 ° C. for 2 hours.

(Example 8)
A thermosetting resin composition and a cured product were obtained in the same manner as in Example 7 except that MPR 5.8 g was used instead of PR 5.8 g.

(Comparative Example 1)
A thermosetting resin composition and a cured product were obtained in the same manner as in Example 1 except that PR was not used.

(Comparative Example 2)
A thermosetting resin composition and a cured product were obtained in the same manner as in Example 5 except that PR was not used.

(Comparative Example 3)
A thermosetting resin composition and a cured product were obtained in the same manner as in Example 7 except that PR was not used.

(Comparative Example 4)
A thermosetting resin composition and a cured product were obtained in the same manner as in Example 1 except that 6.6 g of PCL-PO-β-CD was used instead of PR.

(Comparative Example 5)
A thermosetting resin composition and a cured product were obtained in the same manner as in Example 1 except that 11.0 g of PCL-PO-β-CD was used instead of PR.

(Comparative Example 6)
A thermosetting resin composition and a cured product were obtained in the same manner as in Comparative Example 4 except that 183 g of 4-methyl-1,3-phenylene bismaleimide was used instead of 116.2 g of bis (4-maleimidophenyl) methane. Got.

(Comparative Example 7)
A thermosetting resin composition and a cured product were obtained in the same manner as in Example 7 except that PCL-PO-β-CD 5.8 g was used instead of PR 5.8 g.

<Evaluation>
The following evaluation was performed about each hardened | cured material obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.

(Fracture toughness)
About each hardened | cured material obtained by the Example and the comparative example, using the material universal testing machine (Minebea company make, "Technograph AL-50kNB"), according to ASTM D5045, according to ASTM D5045, the distance between fulcrums of 40 mm, We performed fracture toughness test at a loading rate 1 mm / min condition, was calculated critical stress intensity factor K _IC.

(Bending strength and flexural modulus)
About each hardened | cured material obtained by the Example and the comparative example, using a material universal testing machine (Minebea company make, "Technograph AL-50kNB"), according to JISK-7203, the distance between fulcrum Bending strength and bending elastic modulus were measured under the conditions of 48 mm and a load speed of 1.5 mm / min.

(Linear expansion coefficient)
About each hardened | cured material obtained by the Example and the comparative example, the temperature increase rate of 5 degree-C / min according to JISK-7197 using a thermomechanical characteristic measuring apparatus (The Hitachi High-Tech Science company make, "TG-DTA220"). The linear expansion coefficient was measured under the condition of a load of 5N.

(Dynamic viscoelasticity measurement)
About each hardened | cured material obtained by the Example and the comparative example, using a viscoelasticity measuring apparatus (The product made by UBM, "Rheogel-4000FZ"), frequency 1Hz, temperature increase rate 2 degree-C / min, -100 to 350 degreeC. The storage elastic modulus E ′, loss elastic modulus E ″, and loss tangent tan δ were measured in the temperature range of ° C. The measurement was performed in a bending mode, and the peak temperature of the loss tangent was defined as the glass transition temperature.
1 to 3 are graphs showing the relationship between storage elastic modulus E ′ and temperature, loss elastic modulus E ″, in the cured products obtained in Example 1, Example 2, and Comparative Example 1, respectively. It is a graph which shows the relationship between temperature, and the graph which shows the relationship between loss tangent tan-delta and temperature.

(Pyrolysis temperature)
About each hardened | cured material obtained by the Example and the comparative example, 25-600 degreeC with the temperature increase rate of 10 degree-C / min using the differential thermothermal weight simultaneous measuring apparatus (The Hitachi High-Tech Science company make, "TG-DTA220"). It heated in air atmosphere to 0 degreeC, and measured 5% weight loss temperature as thermal decomposition temperature.

(Tensile shear adhesive strength)
About the thermosetting resin composition prepared by the method similar to an Example and a comparative example, the tensile shear bond strength was measured.
Oxygen-free copper (JIS C1020P) was used as a test piece. Pretreatment of the test piece was performed by degreasing with acetone, polishing with No. 240 polishing paper, washing with running cold water, then warm water, and drying. The prepared thermosetting resin composition was applied to a test piece and heated at 160 ° C. for 2 hours, 180 ° C. for 2 hours, 200 ° C. for 2 hours, 230 ° C. for 2 hours, and 250 ° C. for 2 hours, A shear bond strength test piece was obtained. Tensile shear adhesive strength was measured under a load speed of 5 mm / min in accordance with JIS K-6850 using a material universal testing machine ("Technograph AL-50kNB" manufactured by Minebea).

When Examples 1-4 are compared with Comparative Example 1, when Examples 5-6 are compared with Comparative Example 2, and when Examples 7-8 are compared with Comparative Example 3, a polyrotaxane is added. It can be seen that the fracture toughness (critical stress intensity factor) is improved by about 1.2 to 1.5 times. It can also be seen that the tensile shear bond strength is improved by about 1.1 to 1.9 times. On the other hand, there is no significant decrease in bending strength and bending elastic modulus. Furthermore, when Examples 1-4 are compared with Comparative Examples 4-5, when Examples 5-6 are compared with Comparative Example 6, and when Examples 7-8 are compared with Comparative Example 7. It can be seen that a structure in which a cyclic molecule slides on an axial molecule is important in order to obtain an effect of improving fracture toughness (critical stress intensity factor) without greatly reducing the bending strength and the flexural modulus.

ADVANTAGE OF THE INVENTION According to this invention, the thermosetting resin composition which can obtain the hardened | cured material which is excellent in toughness and adhesiveness, without significantly reducing mechanical strength and heat resistance can be provided. Moreover, according to this invention, the hardened | cured material, molding material, and molded object which use this thermosetting resin composition can be provided.

Claims (8)

A compound having a maleimide group, and
A thermosetting resin composition comprising a polyrotaxane comprising a cyclic molecule, a linear molecule penetrating through the opening of the cyclic molecule, and a blocking group that blocks both ends of the linear molecule. The thermosetting resin composition according to claim 1, wherein the compound having a maleimide group has two or more maleimide groups in one molecule. The thermosetting resin composition according to claim 1 or 2, wherein the compound having a maleimide group has an alkenyl group and / or an amino group in addition to the maleimide group. Further, an aromatic compound having two or more alkenyl groups in one molecule, a compound having two or more amino groups in one molecule, and one alkenyl group and one amino group each in one molecule The thermosetting resin composition according to claim 1, 2 or 3, comprising at least one compound selected from the group consisting of aromatic compounds. The thermosetting resin composition according to claim 1, 2, 3, or 4, wherein the polyrotaxane has a linear molecule of polyethylene glycol and a cyclic molecule of α-cyclodextrin. Hardened | cured material formed by hardening | curing the thermosetting resin composition of Claim 1, 2, 3, 4 or 5. A molding material obtained by blending a filler with the thermosetting resin composition according to claim 1, 2, 3, 4 or 5. A molded body obtained by curing the molding material according to claim 7.

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