JP6987745B2 - Thermosetting resin composition, cured product, molding material, and molded product - Google Patents

Description

The present invention relates to a thermosetting resin composition. The present invention also relates to a cured product, a molding material, and a molded product using the thermosetting resin composition.

Conventionally, epoxy resins have been widely used as a sealing material for electronic devices because they have advantages such as low warpage, low stress, high thermal conductivity, and high insulation. However, due to higher performance of devices and harsher usage conditions, it is difficult for conventional epoxy resins to meet the requirements for heat resistance and the like. In particular, in the area of power devices, which has been attracting attention due to the trend of energy saving in recent years, silicon carbide devices and gallium nitride devices are being developed, and these devices are required to be guaranteed to operate at a temperature of 200 ° C or higher. There is. Therefore, there is a demand for a new sealing material capable of guaranteeing operation at a temperature of 200 ° C. or higher, and maleimide resin is attracting attention as a sealing material in place of 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 for improving the molecular structure of the maleimide resin (Patent Document 1) and a method for adding rubber or a thermoplastic resin (Patent Documents 2 and 3) are disclosed.

Japanese Unexamined Patent Publication No. 5-295111 Japanese Unexamined Patent Publication No. 7-149952 Japanese Unexamined Patent Publication No. 6-413332

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 at the same time. It turned out to be. Further, 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 in order to obtain the required toughness. As a result, it was found that there is a problem that the mechanical strength and heat resistance are lowered.
An object of the present invention is to provide a thermosetting resin composition capable of obtaining a cured product having excellent toughness and adhesiveness without significantly reducing mechanical strength and heat resistance. Another object of the present invention is to provide a cured product, a molding material, and a molded product using the thermosetting resin composition.

The present invention comprises a compound having a maleimide group, a cyclic molecule, a linear molecule that penetrates the opening of the cyclic molecule in a skewered manner, and a polyrotaxane that comprises a blocking group that seals both ends of the linear molecule. An aromatic compound having two or more alkenyl groups in one molecule, a compound having two or more amino groups in one molecule, and an alkenyl group and an amino group in one molecule, respectively. It is a thermosetting resin composition containing at least one compound selected from the group consisting of aromatic compounds having one molecule at a time.
The present invention will be 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 in combination with polyrotaxane, and have completed the present invention. rice field.

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 a tetracarboxylic dianhydride and a diamine, the molecule grows linearly. This polyimide compound has high strength and is mainly excellent in adhesiveness to metals. For example, it is used for a flexible copper-clad laminate, but voids (air bubbles) are likely to be generated by the by-product of water or alcohol during curing. There is a problem. On the other hand, the maleimide compound used in the thermosetting resin composition of the present invention has an advantage that curing proceeds by an addition reaction, so that there are no by-products and virtually no voids are generated. In addition, the maleimide compound has excellent strength and the molecules grow into a three-dimensional network structure in the curing reaction, so that it has excellent adhesion to a wide range of materials such as glass and organic materials in addition to metals, for example. It is used in glass-based copper-clad laminates, organic-based copper-clad laminates, and the like. Since the thermosetting resin composition of the present invention is used in combination with such a maleimide compound and polyrotaxane, it is possible to impart high toughness to the cured product while maintaining the above-mentioned excellent properties of the maleimide compound. , 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.
Further, 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 a compound represented by the following formula (1).

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

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

Among the compounds represented by the formula (1), the compound represented by the following formula (2) and the compound represented by the following formula (3) are preferable from the viewpoint of heat resistance of the cured product. In addition to the compound represented by the formula (1), a compound having a structure represented by the following formula (4) is preferable from the viewpoint of heat resistance of the cured product.

In formula (2), Y is 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-, divalently substituted or unsubstituted cyclic aliphatic hydrocarbon group, or divalent substituted or unsubstituted aromatic hydrocarbon group R ¹ and R ² are independently substituted or unsubstituted hydrocarbon groups having 1 to 6 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 6 carbon atoms, or halogen groups, respectively. o and p are independently integers of 0 to 4. When o is 2 or more, R ¹ there are a plurality of each may be the same or different, when p is 2 or more, R ² there are a plurality of, may each be the same And may be different.

In the 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, plural R ³ may each be the same or may be different.

In the 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, a plurality of R ⁴ may each be the same or may be different.

The aromatic hydrocarbon group in Y of the formula (2), R ¹ and R ^{2 of the formula (2), R 3} of the formula (3), and the hydrocarbon group and the alkoxy group in ^{R 4} of the formula (4) When 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, a heterocyclic group and the like.

Specific examples of the maleimide compound include 4,4'-bismaleimidebiphenyl, bis (4-maleimidephenyl) methane, bis (3-maleimidephenyl) methane, bis (4-maleimidecyclohexyl) methane, and bis ( 3-maleimidecyclohexyl) methane, bis (3-methyl-4-maleimidephenyl) methane, bis (3,5-dimethyl-4-maleimidephenyl) methane, bis (3-ethyl-4-maleimidephenyl) methane, bis ( 3,5-diethyl-4-maleimidephenyl) methane, bis (3-propyl-4-maleimidephenyl) methane, bis (3,5-dipropyl-4-maleimidephenyl) methane, bis (3-butyl-4-maleimide) Phenyl) methane, bis (3,5-dibutyl-4-maleimidephenyl) methane, bis (3-ethyl-4-maleimide-5-methylphenyl) methane, 1,6'-bismaleimide- (2,2,4) -Trimethyl) hexane, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (4-maleimidephenyloxy) phenyl] propane, 1,1,1,3,3,3 -Hexafluoro-2,2-bis (4-maleimidephenyl) propane, 2,2-bis (4-maleimidephenyl) propane, 2,2-bis [4- (4-maleimidephenyloxy) phenyl] propane, bis (4-maleimidephenyl) ether, bis (3-maleimidephenyl) ether, bis (4-maleimidephenyl) ketone, bis (4-maleimidephenyl) sulfone, bis (3-maleimidephenyl) sulfone, bis [4- (4) -Maleimidephenyloxy) phenyl] sulfone, bis (4-maleimidephenyl) sulfide, bis (3-maleimidephenyl) sulfide, bis (4-maleimidephenyl) sulfoxide, bis (3-maleimidephenyl) sulfoxide, bis (4-maleimide) Phenyl) diphenylsilane, 1,4-bis (4-maleimidephenyl) cyclohexane, 4-methyl-1,3-phenylenebismaleimide, 1,3-phenylenebismaleimide, 1,4-phenylenebismaleimide, 1,2- Examples thereof include phenylene bismaleimide, naphthalene-1,5-dimaleimide, 4-chloro-1,3-phenylene bismaleimide, novolak type polymaleimide, and zylock type polymaleimide. These maleimide compounds may be used alone or in combination of two or more.
From the viewpoint of heat resistance of the cured product, 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.

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-allyl maleimide, N-methacrylmaleimide, N-ethylmaleimidyl methacrylate, N-ethylmaleimidyl acrylate and the like.
Examples of the maleimide compound having an amino group include N-aminomethylmaleimide, N- (2-aminoethyl) maleimide, N- (4-aminophenyl) maleimide and the like.

The preferable lower limit of the content of the maleimide compound in the entire thermosetting resin composition of the present invention is 30% by mass, the preferable upper limit is 95% by mass, the more preferable lower limit is 50% by mass, and the more preferable upper limit is 85% by mass. Is.

The thermosetting resin composition of the present invention comprises a cyclic molecule, a linear molecule that penetrates the opening of the cyclic molecule in a skewered manner, and a polyrotaxane that comprises a sealing group that seals both ends of the linear molecule. contains.

The cyclic molecule is a compound that can be encapsulated so that the linear molecule penetrates the opening in a skewered manner and is movable on the linear molecule.
As a method for encapsulating the linear molecule with the cyclic molecule, a conventionally known method (for example, the method described in JP-A-2005-154675) can be used.
In the present specification, the "cyclic" of the cyclic molecule means that it is substantially cyclic, and if it can move on the linear molecule, it does not have to be a completely ring-closed structure. It may be, for example, a spiral structure.

Examples of the cyclic molecule include cyclic polymers such as cyclic polyethers, cyclic polyesters, and cyclic polyether amines, pillar alles, cyclophanes, ring-expanded porphyrins, cyclodextrins, and the like.
Examples of the cyclic polymer include crown ether and its derivative, calixarene and its derivative, cyclophane and its derivative, cryptond and its derivative, and the like.
The cyclic molecule is appropriately selected depending on the type of linear molecule to be used, but since it is easily available and a large number of types of blocking groups can be selected, α-cyclodextrin, β-cyclodextrin, and γ-cyclo Cyclodextrins such as dextrins are preferred. For example, as will be described later, when polyethylene glycol is selected as the linear molecule, α-cyclodextrin is preferable from the viewpoint of the stability of the obtained inclusion body.

When cyclodextrins are used as the cyclic molecule, some of the hydroxyl groups of the cyclodextrins are modified with a modifying group (hereinafter, also referred to as “solubility-imparting group”) that improves compatibility with the maleimide compound. 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, a polyacrylic acid ester chain and the like. These modifying groups may be introduced alone or in combination of two or more. When introducing two or more kinds of modifying groups, for example, when introducing an oxyethylene chain and a polyester chain, the hydroxyl group of cyclodextrins is first modified with an oxyethylene chain, and the hydroxyl group at the end of the introduced oxyethylene chain is used. As a starting point, a method of introducing a polyester chain or the like can be used. Specifically, after adding a hydroxypropyl group to the hydroxyl group existing in cyclodextrin itself, ring-opening polymerization of ε-caprolactone is carried out via the hydroxyl group of the hydroxypropyl group to introduce a polycaprolactone (polyester) chain. Can be done.

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

The polyrotaxan contained in the thermosetting resin composition of the present invention may have a substituent (hereinafter, also referred to as “curing reactive substituent”) that can be directly involved in the thermosetting reaction. When the polyrotaxane has a cure-reactive substituent, the cure-reactive substituent may be directly introduced into a cyclic molecule, for example, a hydroxyl group of a cyclodextrin, or a terminal reaction point of the solubility-imparting group. For example, after adding a hydroxypropyl group to the hydroxyl group of cyclodextrins, a polycaprolactone (polyester) chain is introduced by carrying out ring-opening polymerization of ε-caprolactone via the hydroxyl group of the hydroxypropyl group to introduce a poly. It may be introduced into the terminal hydroxyl group of the caprolactone chain. If the polyrotaxane has a cure-reactive substituent, the compatibility is improved. Further, since polyrotaxane also causes a curing reaction, the polyrotaxane is dispersed at the molecular level (on the order of nm), and a transparent cured product can be obtained. On the other hand, when the polyrotaxane does not have a curing reactive substituent, the polyrotaxane is dispersed in 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 a (meth) acryloyl group, a vinyl group, an allyl group and the like.
In addition, in this specification, the said "(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 of a cyclic molecule before the introduction of the curing-reactive substituent, a functional group capable of reacting with the reactive group, and a curing-reactive substituent. It can be introduced by reacting with.

When a (meth) acryloyl group is introduced as a compound having a functional group capable of reacting with the reactive group and a curing reactive substituent, for example, (meth) acryloyl chloride, (meth) acrylic acid anhydride, 2 -(Meta) acryloyloxyethyl isocyanate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, α-methacryloyloxy-γ-butyrolactone, β-methacryloyloxy-γ-butyrolactone and the like can be mentioned.
When a vinyl group is introduced, for example, p-vinylbenzoic acid, p-vinylbenzoic acid chloride, 3-isocyanate 3-isopropenyl-α, α-dimethylbenzyl, vinyl chloroacetate and the like can be mentioned.
When an allyl group is introduced, for example, p-allyl benzoic acid, p-allyl benzoic acid chloride, allyl isocyanate, allyl isothiocyanate and the like can be mentioned.
Among them, (meth) acryloyl chloride, 2- (meth) acryloyloxyethyl isocyanate, glycidyl (meth) acrylate, and 3-isopropenyl-isocyanate-α, α from the viewpoint of availability and high reactivity. -Dimethylbenzyl, vinyl chloroacetate, allyl isocyanate are preferred.
In addition, in this specification, the said "(meth) acrylate" means at least one of "acrylate" and "methacrylate".

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

When the inclusion ratio is the percentage of the inclusion amount of the cyclic molecule relative to the maximum inclusion amount (maximum inclusion amount) when the cyclic molecule encapsulates the linear molecule, the inclusion ratio is used. The preferred lower limit of the contact rate is 0.1%, the preferred upper limit is 60%, the more preferred lower limit is 1%, the more preferred upper limit is 50%, the further preferred lower limit is 5%, and the further preferred 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 inclusion amount when the linear molecule is polyethylene glycol and the cyclic molecule is α-cyclodextrin has been experimentally determined (see Macromolecules 1993, 26, 5698-5703).

The linear molecule can be included in the opening of the cyclic molecule in a skewered manner, and is, for example, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyvinylmethyl ether, polytetrachloride. , Polyaniline, acrylonitrile-butadiene-styrene copolymer (ABS resin), casein, gelatin, starch, cellulose resin (carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polyolefin resin (polyethylene, polypropylene, polyisobutylene, and Copolymers of these with other olefin-based monomers), polyester resins, polyvinyl chloride-based resins (vinyl chloride-vinyl acetate copolymers, etc.), polystyrene-based resins (polystyrene, acrylonitrile-styrene copolymers, etc.) ), Acrylic resin (poly (meth) acrylic acid, polymethylmethacrylate, (meth) acrylic acid ester copolymer, acrylonitrile-methyl acrylate copolymer, etc.), polycarbonate resin, polyurethane resin, polyvinyl acetal resin (polyvinyl butyral resin, etc.) ), Polypolymer resin (nylon (registered trademark), etc.), polyimide resin, polydiene resin (polyisoprene, polybutadiene, etc.), polysiloxane resin (polydimethylsiloxane, etc.), polysulfone resin, polyimine resin (polyethyleneimine, etc.), polyamine resin, Examples thereof include polyanhydrous acetic acid-based resins, polyurea-based resins, polysulfide resins, polyphosphazene resins, polyketone resins, polyphenylene resins, polyhaloolefin resins, and copolymers, derivatives, and modified products thereof. Of these, polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, polypropylene, polyvinyl alcohol, and polyvinylmethyl ether are preferable, and polyethylene glycol, polypropylene glycol, polytetrahydrofuran, and polydimethylsiloxane. Polyethylene and polypropylene are more preferable, and polyethylene glycol is further preferable.
In addition, in this specification, the said "(meth) acrylic" means at least one of "acrylic" and "methacryl".

The preferable lower limit of the mass average molecular weight of the linear molecule is 3000, and the preferable upper limit is 300,000. When the mass average molecular weight of the linear molecule is in this range, the effect of improving the toughness of the obtained cured product without deteriorating the compatibility between the polyrotaxane and the maleimide compound becomes more excellent. The more preferable lower limit of the mass average molecular weight of the linear molecule is 5000, the more preferable upper limit is 100,000, the further preferable lower limit is 10,000, and the further preferable upper limit is 50,000.
The mass average molecular weight of the linear molecule is a value obtained by measuring with gel permeation chromatography (GPC) and converting it into polyethylene glycol. 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 obtained by measuring with GPC and converting into polystyrene, 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, it is preferable that the linear molecule is polyethylene glycol and the cyclic molecule is a molecule derived from α-cyclodextrin.

The blocking group is arranged at both ends of the linear molecule encapsulated in the cyclic molecule and has a role of acting to prevent the cyclic molecule from being detached. As a method for sealing both ends of the linear molecule with a blocking group, a conventionally known method (for example, the 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, and a mass average molecular weight of 10 to 1,000,000. Examples thereof include a main chain or a side chain of a polymer.
Among them, 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 10 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.

Regarding the content of the polyrotaxane, the preferable lower limit is 1 part by mass and the 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 in this range, the obtained cured product has particularly excellent toughness and mechanical strength. The more preferable lower limit of the content of the polyrotaxane is 3 parts by mass, and the more preferable upper limit is 10 parts by mass.
Further, the preferable lower limit of the content of the polyrotaxane in the entire thermosetting resin composition of the present invention is 0.5% by mass, and the preferable upper limit is 10% by mass. When the content of the polyrotaxane is in this range, the obtained cured product has particularly excellent toughness and mechanical strength. The more preferable lower limit of the content of the polyrotaxane is 2% by mass, and the more preferable upper limit is 5% by 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 having two or more amino groups in one molecule. It is preferable to contain at least one compound selected from the group consisting of a compound and an aromatic compound 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 obtained cured product.

Examples of the aromatic compound having two or more alkenyl groups in one molecule include a compound 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 residue of divalent or higher. Group, l is an integer of 1 or more, X is free of alkenyl groups, at least one of s and l is 2 or more, and X is a monovalent atom or atomic group, l Is 1. If R ⁵ is more, each R ⁵ may be the same or different.

In the formula (5), examples of the monovalent atom or atomic group represented by X include a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and the like.
In the above 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 or unsubstituted cyclic aliphatic hydrocarbon group, divalent substitution Alternatively, an unsubstituted aromatic hydrocarbon group or the like can be mentioned.

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

In formula (6), W is 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-, divalently substituted or unsubstituted cyclic aliphatic hydrocarbon group, or divalent substituted or unsubstituted aromatic hydrocarbon group R ⁶ and R ⁷ are independently substituted or unsubstituted alkenyl groups having 2 to 6 carbon atoms, t and u are independently integers of 0 to 4, and t + u is 2. That is all. 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'-diallyl bisphenol A, 2,2'-diallyl bisphenol 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] Fluolene, 3,3-bis [4-hydroxy-3- (2-propenyl) phenyl] phthalide, 2,2-bis [4-hydroxy-3-methyl-5- (2-propenyl) phenyl] propane, 2, Examples thereof include 2-bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] propane and bis [4-hydroxy-3- (2-methyl-2-propenyl) phenyl] methane.

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 divalently 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 metaphenylenediamine, paraphenylenediamine, 2,2-bis (4-aminophenyl) propane, and 4,4'-diamino. Diphenylmethane, bis (4-aminophenyl) diphenylsilane, bis (4-aminophenyl) methylphosphine oxide, bis (3-aminophenyl) methylphosphinoxide, bis (4-aminophenyl) phenylphosphinoxide, metaxylylene diamine, Paraxylylene diamine, 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 (4-aminophenyl) cyclohexane, 1,1-bis (4-amino-3-methylphenyl) cyclohexane, 2,5-bis (m-aminophenyl)- 1,3,4-oxadiazole, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether, 2,6-diaminopyridine, 1,5- Diaminonaphthalin, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 2,5-diamino-1,3,4-oxadiazole, 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-aminopentyl) benzene, 1-isopropyl-2,4-m-phenyldiamine, 4,4`-methylenebiscyclohexanediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexane Examples thereof include diamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, isophoronediamine, norbornenediamine and the like.

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 used from the viewpoint of heat resistance of the cured product. It is preferable that the molecule is present at a position where it has linear 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, and 4-isopropenylaniline. Examples thereof include 2-methyl-4-isopropenylaniline, 3-methyl-4-isopropenylaniline, 3-chloro-4-isopropenylaniline, 4-isobutenylaniline and the like.

When the thermosetting resin composition of the present invention contains the curing agent, the preferable lower limit of the maleimide compound / curing agent (molar ratio) is 0.5, which is preferable as the content ratio of the maleimide compound to the curing agent. The upper limit is 5. When the maleimide compound / curing agent (molar ratio) is in this range, the obtained cured product has particularly excellent 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.
Further, the preferable lower limit of the content of the curing agent in the entire thermosetting resin composition of the present invention is 4.5% by mass, the preferable upper limit is 60% by mass, the more preferable lower limit is 10% by mass, and the more preferable upper limit. Is 45% by mass.

The thermosetting resin composition of the present invention can be used for other resins, curing accelerators, reinforcing fiber materials, antioxidants, pigments (dye), and ultraviolet absorption, if necessary, as long as the object of the present invention is not impaired. It may contain various additives such as agents, flame retardants, and coupling agents.

Examples of the other resin include rubber components such as natural rubber, butadiene rubber, nitrile rubber, and carboxy-modified nitrile rubber, and polyolefins, acid-modified polyolefins, polyesters, polyethers, polyether sulfones, polyether ether ketones, and polyethers. 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, and 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, tricyclohexylphosphine, 1,2-bis (diphenylphosphine) ethane, Phosphines such as bis (diphenylphosphine) methane, metal compounds such as tin octylate, tin chloride and aluminum chloride, and quaternary phosphonium salts such as tetrabutylphosphonium bromide, tetraphenylphosphonium bromide and methyltriphenylphosphonium bromide. , Boron compounds such as boron trifluoride-diethyl ether complex, boron trichloride-amine complex, organic peroxides such as benzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, and azobisisobuty. Examples thereof include azo compounds such as lonitrile and dimethyl-2,2-azobis (2-methylpyropionate).

Examples of the reinforcing fiber material include plant fibers such as paper, cotton, linen, banana fiber, bamboo fiber and bagasse fiber, animal fiber such as silk and wool, glass fiber, ceramic fiber, carbon fiber and silicon carbide fiber. Examples thereof include inorganic fibers such as aramid fibers, polyester fibers, synthetic polymer fibers such as nylon fibers, and the like. Examples of the form of these reinforcing fiber materials include non-woven fabrics, woven fabrics, filaments, strands, chopped strands, yarns, rovings and the like.

Examples of the antioxidant include 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-p-ethylphenol, and stearyl-β- (3,). 5-Di-tert-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t-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 , Tetrakiss- [methylene-3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3'-bis- (4'-hydroxy-3'-tert) -Butylphenyl) Butylic acid] glycol ester, 1,3,5-tris (3', 5'-di-tert-butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 1H, 3H, 5H) Trion, tocophenol, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyllu-3,3'-thiodipropionate, rephenylphosphite, Diphenylisodecylphosphite, phenyldiisodecylphosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetraylbis (octadecyl) Phosphite, Cyclic Neopentantetraylbis (2,4-di-tert-butylphenyl) Phosphite, Cyclic Neopentantetraylbis (2,4-di-tert-butyl-4-methylphenyl) Phosphite, Bis [2-tert-Butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] Hydrogen Phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9- Examples thereof include 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, navy blue, ultramarine, red iron oxide, carbon black and the like.

Examples of the ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 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 '-Di-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" -tetrahydrophthalimidemethyl) -5'-methylphenyl} benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) Sevacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [{3,5-bis (1,1-dimethyl) Ethyl) -4-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 novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylene bis (pentabromophenyl), and ethylene bistetra. Bromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene, 2, Bromine flame retardants such as 4,6-tris (tribromophenoxy) -1,3,5-triazine, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresyldi-2,6 -Examples include phosphorus-based flame retardants such as xylenyl phosphate, resorcinol bis (diphenyl phosphate) and red phosphorus, and metal hydroxides such as aluminum hydroxide and 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-benzenedimethaneamine, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epylcyclohexyl) ethyltriethoxysilane, 2- (3,4-epylcyclohexyl) ethylmethyldimethoxysilane, γ-methacryloxyloxypropyltrimethoxylan, vinyltri (β-methoxyethoxy) silane, γ -Mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropylisostearoyl diacrylic titanate, acetalkoxyaluminum diisopropyrate and the like.

In the thermosetting resin composition of the present invention, the maleimide compound, the polyrotaxane, and additives such as a curing agent and a curing accelerator used as necessary are uniformly dissolved in an organic solvent, and then the organic solvent is used. It can be produced by a method of removing the above-mentioned material, a method of uniformly kneading using a melt-mixing device such as a roll or a kneader, or the like.

A cured product obtained by curing the thermosetting resin composition of the present invention is also one of the present inventions.
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 the solution mixing temperature when producing the thermosetting resin composition. The obtained thermosetting resin composition can be cured by further heating.
The curability when curing the thermosetting resin composition of the present invention differs depending on the presence or absence of a curing accelerator, the heating temperature, the method of raising the temperature, and the like, and the curing reaction is controlled by adjusting these conditions. be able to.

The curing temperature at the time of curing the thermosetting resin composition of the present invention is usually 80 to 350 ° C., preferably 120 to 300 ° C., more preferably 150 to 250 ° C. The curing time for curing the thermosetting resin composition of the present invention is usually 6 to 24 hours, 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 of the present inventions. By blending the filler, functions such as high conductivity, high thermal conductivity, insulating property, and low hygroscopicity can be improved, and a thermosetting resin composition suitable for the intended use can be obtained.
As the filler, various shapes of inorganic fillers or organic fillers can be used. Specifically, for example, metal particles such as aluminum powder, iron powder, and copper powder, fumed silica, calcined silica, precipitated silica, ground silica, molten silica, clay, mica, talc, iron oxide, zinc oxide, titanium oxide, etc. Inorganic particles such as barium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, zinc carbonate, aluminum hydroxide, alumina, glass, wood powder, pulp powder, crushed fabrics, crushed heat-curable resin, etc. Examples include organic particles.

The preferable lower limit of the content of the filler in the entire molding material of the present invention is 1% by mass, and the preferable upper limit is 90% by mass. When the content of the filler is in this range, the effect of improving functions such as high conductivity without deteriorating workability becomes more excellent. The more preferable lower limit of the content of the filler is 5% by mass, and the more preferable upper limit is 80% by 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 product obtained by curing the molding material of the present invention is also one of the present inventions.
As a method of curing the molding material of the present invention to obtain a molded product of the present invention, a conventionally known method can be used. Specifically, for example, injection molding method, melt casting method, compression molding method, transfer molding method, prepreg laminated 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 Combine) 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 form a prepreg by dissolving it in a solvent, impregnating and drying the reinforcing fiber material as a varnish, a hand lay-up method, a spray-up method, or the like. can.

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

According to the present invention, it is possible to provide a thermosetting resin composition capable of obtaining a cured product having excellent toughness and adhesiveness without significantly reducing mechanical strength and heat resistance. Further, according to the present invention, it is possible to provide a cured product, a molding material, and a molded product using the thermosetting resin composition.

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

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Hereinafter, the polyrotaxane used in the production example was prepared with reference to the method described in JP-A-2011-241401.

(Manufacturing Example 1)
(Manufacturing of polyrotaxane)
Polyethylene glycol (mass average molecular weight 35000) as a linear molecule, α-cyclodextrin (hydroxypropyl group introduction rate 51 mol%) obtained by graft-polymerizing ε-caprolactone after introducing a hydroxypropyl group as a cyclic molecule, A polymerization inhibitor is added to 300 g of a 35 mass% xylene solution of a polyrotaxan having an adamantanamine group as a blocking group (inclusion rate of cyclic molecule 25%, mass average molecular weight 470000, hydroxyl value 74 mgKOH / g, hereinafter also referred to as “PR”). Dibutyl hydroxytoluene was completely dissolved by adding 50 mg of dibutyl hydroxytoluene and stirring at 25 ° C. for 30 minutes. Then, 11.8 g of 2-methacryloyloxyethyl isocyanate was added, and the mixture was stirred at 25 ° C. for 30 minutes, heated to 60 ° C., and reacted as it was for 4 hours. The obtained reaction solution was cooled to 25 ° C., added to a large amount of methanol, stirred, and the precipitate was taken out by a centrifugation method. The obtained precipitate was dissolved in a large amount of acetone, added to a large amount of methanol, stirred and reprecipitated, and the precipitate was taken out by a centrifugation method. The obtained precipitate was dried to obtain 108.9 g of a polyrotaxane (hereinafter, also referred to as “MPR”) having a methacryloyloxyethyl carbamoyl group as 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%.

(Manufacturing Example 2)
(Manufacturing of caprolactone grafted ring)
30 g of hydroxypropylated β-cyclodextrin (hydroxypropyl group introduction rate 25.9 mol%) having a hydroxypropyl group introduced as a cyclic molecule was dried at 120 ° C. for 1 hour under normal pressure using a hot air dryer. .. To 27 g of dried hydroxypropylated β-cyclodextrin (dry weight loss 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. To obtain 149 g of a caprolactone-grafted cyclic product (hereinafter, also referred to as “PCL-PO-β-CD”) grafted with ε-caprolactone.

(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'-diallyl bisphenol A heated to 90 ° C. Acetone was removed by vacuum degassing at 110 ° C. for 60 minutes. Next, 116.2 g of bis (4-maleimidephenyl) 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 a mold of an aluminum plate using a 3 mm thick Teflon (registered trademark) plate as a spacer, and sequentially at 160 ° C. for 2 hours, 180 ° C. for 2 hours, and 200 ° C. for 2 hours. A cured product was obtained by heating at 230 ° C. for 2 hours and 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 compounded 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 6.5 g of MPR was used instead of 6.6 g of PR.

(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)
Thermosetting resin composition and cured product in the same manner as in Example 1 except that 4-methyl-1,3-phenylene bismaleimide 183 g was used instead of 116.2 g of bis (4-maleimidephenyl) 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 6.6 g of PR.

(Example 7)
5.8 g of PR was dissolved in 3 times the amount of acetone and heated to 170 ° C. 100 g of bis (4-maleimidephenyl) methane, 4-methyl-1,3-phenylene bismaleimide 50 g, 1,6-bismaleimide- A mixture of 16.7 g of (2,2,4-trimethyl) hexane was added and vacuum degassed at 130 ° C. for 20 minutes to remove acetone. To this, 25 g of heat-melted meta-phenylenediamine was added to obtain a thermosetting resin composition. The obtained thermosetting resin composition was cast into a mold of an aluminum plate using a 3 mm thick Teflon (registered trademark) plate as a spacer, and sequentially at 160 ° C. for 2 hours, 180 ° C. for 2 hours, and 200 ° C. for 2 hours. A cured product was obtained by heating at 230 ° C. for 2 hours and 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)
Thermosetting resin composition and cured product in the same manner as in Comparative Example 4 except that 4-methyl-1,3-phenylene bismaleimide 183 g was used instead of 116.2 g of bis (4-maleimidephenyl) 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 evaluations were performed on each of the cured products obtained in Examples and Comparative Examples. The results are shown in Tables 1 and 2.

(Fracture toughness)
For each of the cured products obtained in Examples and Comparative Examples, the distance between the fulcrums was 40 mm by the three-point bending method according to ASTM D5045 using a universal material testing machine (Minebea, "Technograph AL-50kNB"). 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)
For each cured product obtained in Examples and Comparative Examples, the distance between the fulcrums was measured by a three-point bending method according to JIS K-7203 using a universal material testing machine (Minebea, "Technograph AL-50kNB"). The bending strength and flexural modulus were measured under the conditions of 48 mm and a load speed of 1.5 mm / min.

(Coefficient of linear expansion)
For each cured product obtained in Examples and Comparative Examples, a heating rate of 5 ° C./min was used in accordance with JIS K-7197 using a thermomechanical property measuring device (“TG-DTA220” manufactured by Hitachi High-Tech Science Co., Ltd.). , The coefficient of linear expansion was measured under the condition of a load of 5N.

(Dynamic viscoelasticity measurement)
For each cured product obtained in Examples and Comparative Examples, a viscoelasticity measuring device (“Rheogel-4000FZ” manufactured by UBM) was used, and the frequency was 1 Hz, the temperature rise rate was 2 ° C./min, and -100 ° C. to 350 ° C. The storage elastic modulus E', the loss elastic modulus E'', and the loss tangent tan δ were measured in the temperature range of ° C. The measurement was performed in the bending mode, and the peak temperature of the tangent loss was taken as the glass transition temperature.
FIGS. 1 to 3 show a graph showing the relationship between the storage elastic modulus E'and the temperature in the cured products obtained in Example 1, Example 2, and Comparative Example 1, respectively, and the loss elastic modulus E''. It is a graph which shows the relationship with temperature, and the graph which shows the relationship between loss tangent tan δ and temperature.

(Pyrolysis temperature)
For each of the cured products obtained in Examples and Comparative Examples, 25 ° C to 600 at a heating rate of 10 ° C / min using a differential thermogravimetric simultaneous measuring device (“TG-DTA220” manufactured by Hitachi High-Tech Science Co., Ltd.). It was heated to ° C. in an air atmosphere, and the 5% weight loss temperature was measured as the thermal decomposition temperature.

(Tension shear adhesion strength)
The tensile shear adhesive strength was measured for the thermosetting resin compositions prepared by the same methods as in Examples and Comparative Examples.
Oxygen-free copper (JIS C1020P) was used as the test piece. The pretreatment of the test piece was performed by degreasing with acetone, polishing with No. 240 abrasive paper, washing with running cold water, and then with warm water, and drying. The prepared thermosetting resin composition is applied to a test piece and stretched by heating 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. The tensile shear adhesive strength was measured under the condition of a load speed of 5 mm / min according to JIS K-6850 using a material universal testing machine (“Technograph AL-50kNB” manufactured by Minebea).

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

According to the present invention, it is possible to provide a thermosetting resin composition capable of obtaining a cured product having excellent toughness and adhesiveness without significantly reducing mechanical strength and heat resistance. Further, according to the present invention, it is possible to provide a cured product, a molding material, and a molded product using the thermosetting resin composition.

Claims (7)

Compounds with maleimide groups and
It contains a cyclic molecule, a linear molecule that penetrates the opening of the cyclic molecule in a skewered manner, and a polyrotaxane consisting of a blocking group that blocks both ends of the linear molecule.
Furthermore, aromatic compounds having two or more alkenyl groups per molecule, and contains at least one compound selected from the compounds or Ranaru group having 2 or more amino groups in one molecule ,
The aromatic compound having two or more alkenyl groups in one molecule is a compound represented by the following formula (5).
The compound having two or more amino groups in one molecule is a compound represented by the following formula (7) . The thermosetting resin composition.

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 residue of divalent or higher. Group, l is an integer of 1 or more, X is free of alkenyl groups, at least one of s and l is 2 or more, and X is a monovalent atom or atomic group, l Is 1. If R ⁵ there are a plurality each
R ⁵ may be the same or different.

In formula (7), V is a divalently substituted or unsubstituted aromatic hydrocarbon group, or a divalent substituted or unsubstituted alicyclic hydrocarbon group. 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. The thermosetting resin composition according to claim 1, 2 or 3, wherein the polyrotaxane is a molecule in which the linear molecule is polyethylene glycol and the cyclic molecule is derived from α-cyclodextrin. A cured product obtained by curing the thermosetting resin composition according to claim 1, 2, 3 or 4. A molding material obtained by blending a filler with the thermosetting resin composition according to claim 1, 2, 3 or 4. A molded product obtained by curing the molding material according to claim 6.

Images