Curable composition, compound, heat-resistant resin material, adhesive, sealing material, potting agent, encapsulant, carbon material, and prepreg

Abstract

The present invention addresses the problem of: providing a curable resin composition which can be cured at a low curing temperature and in a short time, the reaction conditions for curing of which are less restricted, the glass transition temperature of a cured product obtained by curing of which is high, and which makes it possible to obtain a cured product having excellent heat resistance; and providing a novel compound which has an ethynyl group, in which the ethynyl group exhibits high reactivity, which can be cured at a low curing temperature and in a short time, the reaction conditions for curing of which are less restricted, the glass transition temperature of a cured product obtained by curing of which is high, and which makes it possible to obtain a cured product having excellent heat resistance. The problem is solved by providing a curable composition comprising a compound which has an ethynyl group represented by formula (A1).

Description

Curable compositions, compounds, heat-resistant resin materials, adhesives, sealing materials, potting agents, encapsulants, carbon materials, and prepregs

[0001] The present invention relates to a curable composition containing an ethynyl group-containing compound, a novel ethynyl group-containing compound, and a heat-resistant resin material. More specifically, the present invention relates to a curable composition containing a highly reactive ethynyl group as a crosslinking group, which undergoes regioselective metal-free cyclotrimerization of an alkyne to give 1,3,5-triacylarylene, a heat-resistant resin material obtained by curing the curable composition, a novel ethynyl group-containing compound that is a component of the curable composition, and a heat-resistant resin material obtained by curing the compound or a composition containing the compound and an additive.

[0002] Curable compositions can provide high heat resistance and dimensional stability, and are therefore used in a variety of applications, such as electronic materials, matrix materials for composite materials, and coating materials. For example, in the field of electronic materials, they are essential materials for semiconductor encapsulation materials and interlayer insulating materials for printed wiring boards. In recent years, in the field of semiconductor encapsulation materials, studies have been conducted to replace silicon (Si) semiconductor elements with silicon carbide (SiC) and other materials with the aim of reducing power loss. Because SiC semiconductors operate at higher temperatures than Si semiconductors, encapsulation materials for SiC semiconductors are required to have higher heat resistance than conventional semiconductor encapsulation materials, and heat resistance of over 200°C is required. Furthermore, because semiconductor encapsulation materials for SiC semiconductors are exposed to high temperatures for long periods of time, the curable resin compositions used must have high long-term heat resistance (chemical heat resistance). Therefore, curable resin compositions usable as semiconductor encapsulation materials for SiC semiconductors have high long-term heat resistance and can be applied not only to encapsulation materials but also to adhesives, insulating materials, paints, and matrix resins for fiber-reinforced composites that require heat resistance, and are expected to be extremely useful.

[0003] Patent Documents 1 to 3 disclose curable compositions for encapsulating semiconductor elements, including epoxy resin compositions containing an epoxy resin such as bisphenol A epoxy resin as the main component, a liquid acid anhydride or phenol novolac as a curing agent, and additives such as inorganic fillers. Patent Documents 4 to 7 disclose curable compositions containing cyanate ester compounds. These curable compositions cure via a cyclotrimerization reaction of the cyanate group (cyanate ester group; -OCN group) of the cyanate ester compound, yielding cured products exhibiting excellent properties such as high heat resistance, low water absorption, and high insulation. Furthermore, curable compositions containing a combination of epoxy resin and maleimide resin offer excellent electrical properties, mechanical properties, chemical resistance, and other properties, making them promising candidates for encapsulating resins for SiC power semiconductors. Patent Document 8 discloses soluble polymers obtained by the cyclotrimerization reaction of dialkyne compounds.

[0004] Japanese Patent Application Publication No. 2003-160639 Japanese Patent Application Publication No. 2009-292996 Japanese Patent Application Publication No. 2008-255367 Japanese Patent Application Publication No. 7-70315 Japanese Patent Application Publication No. 2011-6683 Japanese Patent Application Publication No. 2010-53085 Japanese Patent Application Publication No. 8-176299 U.S. Patent Application Publication No. 2006 / 0247410

[0005] Epoxy resin compositions have low glass transition temperatures (physical heat resistance) and are unsatisfactory in terms of heat resistance. Curable compositions containing cyanate ester compounds have excellent heat resistance, but generally require the use of a transition metal catalyst for curing. Without the use of a transition metal catalyst, prolonged heating at high temperatures (e.g., 250°C or higher) is required. Furthermore, the curing reaction forms a highly crosslinked three-dimensional network structure, resulting in unsatisfactory brittle cured products. These issues have hindered their widespread application and have prevented their widespread adoption.

[0006] Curable compositions containing compounds having an ethynyl group have attracted attention because they produce a highly heat-resistant aromatic ring upon curing. However, due to the low reactivity of the ethynyl group, curing requires conditions such as the use of a transition metal catalyst, UV light irradiation, and high-temperature heating. This may adversely affect the materials to which the curable composition is applied, limiting their applications and commercialization. The present inventors have discovered that alkynes conjugated with electron-withdrawing substituents exhibit high reactivity and can react with a wide range of substrates under mild reaction conditions, with fewer limitations on reaction conditions and the ability to control the reaction direction.

[0007] One of the problems that the present invention aims to solve is to provide a curable resin composition that can be cured at a low curing temperature in a short time, has few limitations on the reaction conditions during curing, and can give a cured product that has a high glass transition temperature and excellent heat resistance.One of the problems that the present invention aims to solve is to provide a novel compound having an ethynyl group, in which the ethynyl group exhibits high reactivity, can be cured at a low curing temperature in a short time, has few limitations on the reaction conditions during curing, and can give a cured product that has a high glass transition temperature and excellent heat resistance.

[0008] In order to solve the above problems, the present inventors have conducted extensive research into a curing system that cures at low temperatures, contains few volatile components, and the cured product maintains high stability even at high temperatures. As a result, they have found a compound represented by formula (A1), which contains an electron-withdrawing group X １１ The present inventors have found that a curable composition containing a compound having an ethynyl group conjugated with the compound exhibits a weight loss of 5% or less when heated from 30°C to 300°C at a temperature increase rate of 10°C / min in a nitrogen atmosphere in TG-DTA (thermogravimetric-differential thermal analysis) measurement, and has characteristics suitable for use in the periphery of high-temperature operating semiconductor devices, leading to the completion of the present invention.

[0009] [Term 1] Formula (A1): (In formula (A1), Z １１ is Ar １１ , -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R １１ -, -P(=O)(OR １２ ) -, -NR １３ CO-, -COO-, -NR １４ an n-valent aromatic organic group consisting of one or more groups selected from the group consisting of - and a direct bond, １１ , Ar １３ , Ar １４ and Ar １６ each independently represents a monovalent or higher aromatic ring which may have a substituent, １２ represents a divalent or higher aromatic ring which may have a substituent, and Ar １５ represents a tetravalent or higher aromatic ring which may have a substituent, and -X １１ -C≡CH is Ar １１ ~Ar １６ is bonded to either of R １１ ~R １４ are each independently hydrogen or a monovalent organic group; Z １１ In which -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R １１ -, -P(=O)(OR １２ ) -, -NR １３ CO—, —COO—, and —NR １４ - are not directly bonded to each other. １１ - is -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R １５ - and -P(=O)(OR １６ )- is a divalent group selected from the group consisting of R １５ , R １６ are each independently hydrogen or a monovalent organic group. １１ is an integer of 1 or more. １１ ~Ar １６ , R １１ ~R １６ , -X １１When there are a plurality of -, they may be the same or different.

[0010] [Item 2] In the formula (A1), n １１ is 2, -X １１ - is -C(=O)-, Z １１ but In the case of , two -X １１ -C≡CH is in the ortho or meta position, １１ is 2, -X １１ - is -C(=O)-, Z １１ but In the case of １１ Item 2. The curable composition according to Item 1, wherein —C≡CH is in the ortho or meta position relative to the N.

[0011] [Item 3] The compound having an ethynyl group represented by the formula (A1) is n １１ is an integer of 2 or more, and n １１ Item 3. The curable composition according to item 1 or 2, wherein the average of

[0012] [Item 4] The curable composition according to any one of Items 1 to 3, which satisfies the following requirements (I) and / or (II): (I) in a TG-DTA (thermogravimetric-differential thermal analysis) measurement of the curable composition, the weight loss when heated in a nitrogen atmosphere from 30°C to 300°C at a heating rate of 10°C / min is 10% or less; and (II) in a TG-DTA (thermogravimetric-differential thermal analysis) measurement of a cured product of the curable composition obtained by heating under conditions of 50°C to 250°C for 48 hours or less, the weight loss when heated in a nitrogen atmosphere from 30°C to 300°C at a heating rate of 10°C / min is 10% or less.

[0013] [Item 5] The curable composition according to any one of Items 1 to 4, wherein a cured product obtained by heating the curable composition under conditions of 50°C to 250°C for 48 hours or less is immersed in boiling tetrahydrofuran for 2 hours, followed by solvent replacement in acetone at 25°C ± 5°C for 6 hours or more, and then dried in an 80°C atmosphere under a reduced pressure of -0.1 MPa until no change in mass is observed for 3 hours or more when the mass is measured every hour.

[0014] [Item 6] The compound having an ethynyl group represented by the formula (A1) is represented by the following formula (A2): (In formula (A2), Ar ２１ ~Ar ２３ are each independently Ar ２４ , Ar is an n-valent aromatic organic group consisting of one or more groups selected from the group consisting of ２４ , Ar ２６ , Ar ２７ and Ar ２９ each independently represents a monovalent or higher aromatic ring which may have a substituent, ２５ represents a divalent or higher aromatic ring which may have a substituent, and Ar ２８ represents an aromatic ring having a valence of 4 or more which may have a substituent, and Q ２１ and Q ２２ are each independently -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ２１ -, -P(=O)(OR ２２ ) -, -NR ２３ CO-, -COO-, -NR ２４ - and a direct bond, R ２１ ~R ２４ are each independently hydrogen or a monovalent organic group. ２１ --X ２３ - is each independently -C(=O)-, -S(=O)-, or -S(=O) ２ -, -P(=O)R ２５ - and -P(=O)(OR ２６ )- is a divalent group selected from the group consisting of R ２５ , R２６ are each independently hydrogen or a monovalent organic group. ２１ ~n ２４ is an integer of 0 or 1 or more, and n ２５ is an integer of 1 or more, and n ２４ If is 0, n ２５ is an integer of 2 or more, and n ２４ is an integer of 1 or more, and n ２３ If is 0, n ２１ +n ２５ is an integer of 2 or more, and n ２３ and n ２４ are each an integer of 1 or more, n ２１ +n ２２ +n ２５ is an integer of 2 or more. ２１ ~Ar ２９ , -X ２１ --X ２３ -, R ２１ ~R ２６ When there are a plurality of n, they may be the same or different. ２４ is 0, n ２５ is 2, -X ２３ - is -C(=O)-, -Ar ２３ -but In the case of , two -X ２３ -C≡CH is in the ortho or meta position. ２１ is 1, n ２３ is 0, n ２４ is 1, -X ２１ - and -X ２３ - is -C(=O)-, -Ar ２１ -Q ２２ -Ar ２３ -but In the case of ２３ Item 6. The curable composition according to any one of items 1 to 5, wherein —C≡CH is in the ortho or meta position relative to the N.

[0015] [Item 7] The compound having an ethynyl group represented by formula (A2) is represented by the following formula (A3): (In formula (A3), Q ２１ and Q ２２are each independently -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ２１ -, -P(=O)(OR ２２ ) -, -NR ２３ CO-, -COO-, -NR ２４ - and a direct bond, R ２１ ~R ２４ are each independently hydrogen or a monovalent organic group. ２１ --X ２３ - is each independently -C(=O)-, -S(=O)-, or -S(=O) ２ -, -P(=O)R ２５ - and -P(=O)(OR ２６ )- is a divalent group selected from the group consisting of R ２５ , R ２６ are each independently hydrogen or a monovalent organic group. ２１ ~n ２４ is an integer of 0 or 1 or more, and n ２５ is an integer of 1 or more, and n ２４ If is 0, n ２５ is an integer of 2 or more, and n ２４ is an integer of 1 or more, and n ２３ If is 0, n ２１ +n ２５ is an integer of 2 or more, and n ２３ and n ２４ are each an integer of 1 or more, n ２１ +n ２２ +n ２５ is an integer of 2 or more. ２１ --X ２３ -, R ２１ ~R ２６ When there are a plurality of n, they may be the same or different. ２４ is 0, n ２５ is 2, -X ２３ When - is -C(=O)-, two -X ２３ -C≡CH is in the ortho or meta position. ２１ , n ２４ and n ２５ is 1, n ２３ is 0, -X２１ - and -X ２３ - is -C(=O)-, Q ２２ NR ２４ , R ２４ When is phenyl, -X ２１ Item 7. The curable composition according to Item 6, wherein —C≡CH is in the ortho or meta position relative to the N.

[0016] [Item 8] The curable composition according to any one of Items 1 to 6, which is a one-component or multi-component type.

[0017] [Term 9] Formula (B); (In formula (B), Z ３１ is Ar ３１ , -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ３１ -, -P(=O)(OR ３２ ) -, -NR ３３ CO-, -COO-, -NR ３４ an n-valent aromatic organic group consisting of one or more groups selected from the group consisting of - and a direct bond, ３１ , Ar ３３ , Ar ３４ and Ar ３６ each independently represents a monovalent or higher aromatic ring which may have a substituent, ３２ represents a divalent or higher aromatic ring which may have a substituent, and Ar ３５ represents a tetravalent or higher aromatic ring which may have a substituent, and -X ３１ -C≡CH is Ar ３１ ~Ar ３６ is bonded to either of R ３１ ~R ３４ are each independently hydrogen or a monovalent organic group; Z ３１ In which -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ３１ -, -P(=O)(OR ３２ ) -, -NR ３３ CO—, —COO—, and —NR ３４ - are not directly bonded to each other.３１ - is -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ３５ - and -P(=O)(OR ３６ )- is a divalent group selected from the group consisting of R ３５ , R ３６ are each independently hydrogen or a monovalent organic group. ３１ is an integer of 2 or more. ３１ ~Ar ３６ , R ３１ ~R ３６ , -X ３１ When there are a plurality of -, they may be the same or different. ３１ - is -C(=O)-, Z ３１ When is an unsubstituted phenyl ring, n ３１ is an integer from 3 to 6. ３１ is 2, -X ３１ - is -C(=O)-, Z ３１ but In the case of ３１ -C≡CH is in the ortho position relative to N, or two -X ３１ -C≡CH is in the para and meta positions relative to N. ３１ is 2, -X ３１ - is -C(=O)- or -S(=O) ２ -, Z ３１ but In the case of ３１ -C≡CH is in the ortho or meta position relative to O. ３１ is 2, -X ３１ - is -C(=O)-, Z ３１ but In the case of ３１ -C≡CH is in the ortho or meta position relative to the amide bond. ３１ is 2, -X ３１ - is -C(=O)-, Z ３１ but In the case of ３１ -C≡CH is in the ortho or para position relative to the amide bond.

[0018] [Item 10] A heat-resistant resin material obtained by curing the curable composition according to any one of items 1 to 8 or the compound according to item 9.

[0019] [Item 11] An adhesive comprising the curable composition according to any one of items 1 to 8 or the compound according to item 9.

[0020] [Item 12] A sealant containing the curable composition according to any one of items 1 to 8 or the compound according to item 9.

[0021] [Item 13] A potting material containing the curable composition according to any one of items 1 to 8 or the compound according to item 9.

[0022] [Item 14] A sealant containing the curable composition according to any one of items 1 to 8 or the compound according to item 9.

[0023] [Term 15] Formula (A): (In formula (A), -X- is -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ａ - and -P(=O)(OR ｂ When there are a plurality of —X—, they may be the same or different, and R ａ is hydrogen or a monovalent organic group, and R ａ When there are a plurality of R ｂ is hydrogen or a monovalent organic group, and R ｂ wherein when there are a plurality of groups, they may be the same or different, Z is an n-valent organic group, and n is an integer of 1 or more.

[0024] [Term 16] Formula (A): (In formula (A), -X- is -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ａ - and -P(=O)(OR ｂWhen there are a plurality of —X—, they may be the same or different, and R ａ is hydrogen or a monovalent organic group, and R ａ When there are a plurality of R ｂ is hydrogen or a monovalent organic group, and R ｂ and a fibrous reinforcing material.

[0025] According to the present invention, there is provided a curable resin composition which can be cured at a low curing temperature in a short time, which has few limitations on the reaction conditions during curing, and which can give a cured product having a high glass transition temperature and excellent heat resistance. According to the present invention, there is provided a novel compound having an ethynyl group, which exhibits high reactivity in the ethynyl group, which can be cured at a low curing temperature in a short time, which has few limitations on the reaction conditions during curing, and which can give a cured product having a high glass transition temperature and excellent heat resistance.

[0026] The curable composition containing the compound having an ethynyl group according to the present invention is highly reactive because the ethynyl group is an alkyne conjugated with a specific electron-withdrawing group, and can be cured at a low curing temperature in a short time. Furthermore, there are fewer restrictions on reaction conditions during curing, such as the use of transition metal catalysts, UV light irradiation, and high-temperature heating, and the amount of reaction accelerator used can be reduced, and the reaction orientation can be controlled. Furthermore, the inclusion of a filler can further reduce the thermal expansion of the cured product.

[0027] FIG. 1 shows the results of TG-DTA analysis of curable composition 1B according to an embodiment of the present invention. FIG. 2 shows the results of TG-DTA analysis of curable composition 2B according to an embodiment of the present invention. FIG. 3 shows the results of TG-DTA analysis of curable composition 3B according to an embodiment of the present invention. FIG. 4 shows the results of TG-DTA analysis of curable composition 4B according to an embodiment of the present invention. FIG. 5 shows the results of TG-DTA analysis of curable composition 5B according to an embodiment of the present invention. FIG. 6 shows the results of TG-DTA analysis of curable composition 6B according to an embodiment of the present invention. FIG. 7 shows the results of TG-DTA analysis of curable composition 8B according to an embodiment of the present invention. FIG. 8 shows the results of TG-DTA analysis of curable composition 9B according to an embodiment of the present invention. FIG. 9 shows the results of TG-DTA analysis of heat-resistant resin material 1Ca (cured product 1Ca) obtained by curing curable composition 1B according to an embodiment of the present invention. FIG. 1 shows the results of TG-DTA analysis of a heat-resistant resin material 2C (cured product 2C) obtained by curing a curable composition 2B according to an embodiment of the present invention. FIG. 2 shows the results of TG-DTA analysis of a heat-resistant resin material 3C (cured product 3C) obtained by curing a curable composition 3B according to an embodiment of the present invention. FIG. 3 shows the results of TG-DTA analysis of a heat-resistant resin material 4C (cured product 4C) obtained by curing a curable composition 4B according to an embodiment of the present invention. FIG. 4 shows the results of TG-DTA analysis of a heat-resistant resin material 5C (cured product 5C) obtained by curing a curable composition 5B according to an embodiment of the present invention. FIG. 5 shows the results of TG-DTA analysis of a heat-resistant resin material 6C (cured product 6C) obtained by curing a curable composition 6B according to an embodiment of the present invention. FIG. 6 shows the results of TG-DTA analysis of a heat-resistant resin material 7C (cured product 7C) obtained by curing a curable composition 7B according to an embodiment of the present invention. 1 is a diagram showing the results of TG-DTA analysis of a heat-resistant resin material 8C (cured product 8C) obtained by curing a curable composition 8B according to an embodiment of the present invention. 2 is a diagram showing the results of TG-DTA analysis of a heat-resistant resin material 9C (cured product 9C) obtained by curing a curable composition 9B according to an embodiment of the present invention. 3 is a diagram showing the results of DMA measurement when measuring the dynamic viscoelasticity (Tg) of a heat-resistant resin material 1Cb (cured product 1Cb) obtained by curing a curable composition 1B according to an embodiment of the present invention.1 is a diagram showing the results of DMA measurement when measuring the dynamic viscoelasticity (Tg) of a heat-resistant resin material 2C (cured product 2C) obtained by curing a curable composition 2B according to an embodiment of the present invention. 2 is a diagram showing the results of TG-DTA analysis when measuring the residual carbon percentage of a heat-resistant resin material 1C (cured product 1C) obtained by curing a curable composition 1B according to an embodiment of the present invention. 3 is a diagram showing the results of TG-DTA analysis when measuring the residual carbon percentage of a heat-resistant resin material 2C (cured product 2C) obtained by curing a curable composition 2B according to an embodiment of the present invention.

[0028] The present invention will be described in detail below.

[0029] [Curable Composition] The curable composition according to the present invention containing a compound having a specific ethynyl group is represented by the formula (A1); The curable composition contains a compound having an ethynyl group represented by the formula:

[0030] The curable composition according to the present invention, which contains the compound having an ethynyl group represented by formula (A1), has as its main curing reaction a crosslinking reaction in which the ethynyl group in the compound having an ethynyl group represented by formula (A1) undergoes cyclotrimerization. The crosslinking reaction in which the ethynyl group undergoes cyclotrimerization is a reaction in which a phenyl ring is formed, and is a reaction in which no low-molecular-weight compound components are generated or eliminated as a result of the crosslinking reaction.

[0031] <Compound Having an Ethynyl Group Represented by Formula (A1)> The compound having an ethynyl group represented by formula (A1) is as follows. (Z in formula (A1) １１ is Ar １１ , -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R １１ -, -P(=O)(OR １２ ) -, -NR １３ CO-, -COO-, -NR １４ an n-valent aromatic organic group consisting of one or more groups selected from the group consisting of - and a direct bond, １１ , Ar １３ , Ar １４ and Ar １６each independently represents a monovalent or higher aromatic ring which may have a substituent, １２ represents a divalent or higher aromatic ring which may have a substituent, and Ar １５ represents a tetravalent or higher aromatic ring which may have a substituent, and -X １１ -C≡CH is Ar １１ ~Ar １６ is bonded to either of R １１ ~R １４ are each independently hydrogen or a monovalent organic group; Z １１ In which -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R １１ -, -P(=O)(OR １２ ) -, -NR １３ CO—, —COO—, and —NR １４ - are not directly bonded to each other. １１ - is -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R １５ - and -P(=O)(OR １６ )- is a divalent group selected from the group consisting of R １５ , R １６ are each independently hydrogen or a monovalent organic group. １１ is an integer of 1 or more. １１ ~Ar １６ , R １１ ~R １６ , -X １１ When there are multiple -'s, they may be the same or different.

[0032] In the curable composition containing the specific ethynyl group-containing compound of the present invention, the ethynyl group-containing compound represented by formula (A1) is １１ is 2, -X １１ - is -C(=O)-, Z １１ but In the case of , two -X １１ Preferably, the -C≡CH is in the ortho or meta position.

[0033] In the curable composition of the present invention containing the specific ethynyl group-containing compound, the ethynyl group-containing compound represented by formula (A1) is １１ is 2, -X １１ - is -C(=O)-, Z １１ but In the case of , two -X １１ Preferably, the -C≡CH is in the ortho or meta position.

[0034] In the curable composition of the present invention containing the specific ethynyl group-containing compound, the ethynyl group-containing compound represented by formula (A1) is １１ is 2, -X １１ - is -C(=O)-, Z １１ but In the case of １１ Preferably, the -C≡CH is in the ortho or meta position relative to the N.

[0035] Z in formula (A1) １１ Ar in １１ ~Ar １６ Examples of the aromatic ring constituting the ring include hydrocarbon aromatic rings and heteroaromatic rings. These may be either monocyclic or polycyclic. They may be any of a ring that exhibits aromaticity itself, a ring condensed with an aromatic ring, and a ring formed by bonding multiple such rings.

[0036] Examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pyrene ring, a spirodifluorene ring, a phenanthrene ring, and a perylene ring.

[0037] Examples of the heteroaromatic ring include a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring, a pyridazine ring, a pyrrole ring, an imidazole ring, an oxazole ring, an oxadiazole ring, a thiadiazole ring, a thiazole ring, a phenoxazine ring, an isoquinoline ring, a benzopyran ring, an indole ring, a cridine ring, an acridine ring, a quinoline ring, a carbazole ring, a quinoxaline ring, a furan ring, a benzofuran ring, a dibenzofuran ring, a benzopyran ring, a dibenzodioxin ring, a thiophene ring, a benzothiophene ring, a thienylene ring, a phenothiazine ring, a thienothiophene ring, a dithienothiophene ring, a pyrazole ring, a phosphole ring, a dibenzophosphole ring, a dibenzosilole ring, and a dibenzoborole ring.

[0038] Z in formula (A1) １１ Ar in １１ , Ar １３ , Ar １４ and Ar １６ Examples of the "monovalent or more aromatic ring" as the aromatic ring include a monovalent or more aromatic ring obtained by removing one or more hydrogen atoms directly bonded to carbon atoms or heteroatoms (nitrogen atoms, sulfur atoms, etc.) constituting the aromatic ring, and one or more aromatic rings formed by bonding two or more of the monovalent or more aromatic rings. １１ Ar in １２ Examples of the "divalent or higher aromatic ring" as the aromatic ring include a divalent or higher aromatic ring obtained by removing two or more hydrogen atoms directly bonded to carbon atoms or heteroatoms (nitrogen atoms, sulfur atoms, etc.) constituting the aromatic ring, and one or more aromatic rings formed by bonding two or more monovalent or higher aromatic rings. １１ Ar in １５ Examples of the "tetravalent or higher aromatic ring" as used herein include a tetravalent or higher aromatic ring obtained by removing four or more of the hydrogen atoms directly bonded to carbon atoms or heteroatoms (nitrogen atoms, sulfur atoms, etc.) that constitute the aromatic ring, and one or more aromatic rings consisting of a tetravalent or higher aromatic ring formed by bonding two or more monovalent or higher aromatic rings.

[0039] Z in formula (A1) １１ Ar in １１ ~Ar１６ The substituent that may be present in １１ There are no particular limitations on the group, as long as it does not inhibit the crosslinking reaction due to cyclotrimerization of the ethynyl group in the -C≡CH group. Examples include one or more selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a cyanate group (-OCN group), an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, a ketoalkyl group having 2 to 20 carbon atoms, a ketoaryl group having 7 to 30 carbon atoms, an amino group, an alkylamino group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, a carboxyl group, a hydroxyl group, a carboxylic acid alkyl ester group having 1 to 21 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms. １１ Ar in １１ ~Ar １６ The number of substituents that the has is not particularly limited and is 0 or more.

[0040] Z in formula (A1) １１ R in １１ ~R １４ and X １１ R in １５ ~R １６ As the monovalent organic group, -X １１ There are no particular limitations on the type of group as long as it does not inhibit the crosslinking reaction due to cyclotrimerization of the ethynyl group in the -C≡CH group, and examples thereof include one or more groups selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, halogenated alkyl groups having 1 to 20 carbon atoms, and aryl groups having 6 to 30 carbon atoms.

[0041] n in formula (A1) １１ is an integer of 1 or more, and n in the entire curable composition １１ The average of (apparent n １１) is, for example, 1.3 or more, preferably 1.5 or more, more preferably 1.7 or more, even more preferably 1.9 or more, and particularly preferably 2.0 or more, and is, for example, 10.0 or less, preferably 8.0 or less, more preferably 6.0 or less, even more preferably 4.0 or less, and particularly preferably 3.0 or less. In the curable composition of the present invention, the compound having an ethynyl group represented by formula (A1) is １１ A mixture of compounds having different values ​​of n in the entire curable composition can be used. １１ If the average of n in the entire curable composition is small, the molecular weight of the cured product obtained from the curable composition will not be large, and the degree of crosslinking of the cured product will be insufficient, which may cause problems in terms of heat resistance and mechanical properties. １１ If the average is too large, the curability of the curable composition will be too high, which may cause problems in terms of storage stability and handling, and may also make the cured product brittle.

[0042] Here, "n in the entire curable composition" １１ The "average of n" in formula (A1) in the curable composition １１ and the abundance ratio of the corresponding compound, and can be calculated by the following formula: １１ Average of ] = {1 × [n １１ Proportion (mol%) of compounds with n = 1] + 2 × [n １１ Proportion of compounds with a value of 2 (mol%)] + ... + n × [n １１ Proportion of compounds where n is (mol%)} / 100

[0043] In the curable composition of the present invention containing a specific compound having an ethynyl group, the compound having an ethynyl group represented by formula (A1) is a compound represented by the following formula (A2): (In formula (A2), Ar ２１ ~Ar ２３ are each independently Ar ２４ , Ar is an n-valent aromatic organic group consisting of one or more groups selected from the group consisting of ２４ , Ar ２６ , Ar ２７ and Ar ２９each independently represents a monovalent or higher aromatic ring which may have a substituent, ２５ represents a divalent or higher aromatic ring which may have a substituent, and Ar ２８ represents an aromatic ring having a valence of 4 or more which may have a substituent, and Q ２１ and Q ２２ are each independently -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ２１ -, -P(=O)(OR ２２ ) -, -NR ２３ CO-, -COO-, -NR ２４ - and a direct bond, R ２１ ~R ２４ are each independently hydrogen or a monovalent organic group. ２１ --X ２３ - is each independently -C(=O)-, -S(=O)-, or -S(=O) ２ -, -P(=O)R ２５ - and -P(=O)(OR ２６ )- is a divalent group selected from the group consisting of R ２５ , R ２６ are each independently hydrogen or a monovalent organic group. ２１ ~n ２４ is an integer of 0 or 1 or more, and n ２５ is an integer of 1 or more, and n ２４ If is 0, n ２５ is an integer of 2 or more, and n ２４ is an integer of 1 or more, and n ２３ If is 0, n ２１ +n ２５ is an integer of 2 or more, and n ２３ and n ２４ are each an integer of 1 or more, n ２１ +n ２２ +n ２５ is an integer of 2 or more. ２１ ~Ar ２９ , -X ２１ --X ２３ -, R ２１ ~R ２６When there are a plurality of n, they may be the same or different. ２４ is 0, n ２５ is 2, -X ２３ - is -C(=O)-, -Ar ２３ -but In the case of , two -X ２３ -C≡CH is in the ortho or meta position. ２１ is 1, n ２３ is 0, n ２４ is 1, -X ２１ - and -X ２３ - is -C(=O)-, -Ar ２１ -Q ２２ -Ar ２３ -but In the case of １１ -C≡CH is in the ortho or meta position relative to N.

[0044] Ar in formula (A2) ２１ ~Ar ２９ The aromatic ring constituting the formula (A1) is Z １１ Ar in １１ ~Ar １６ Ar in formula (A2) is the same as the aromatic ring constituting the formula (A2). ２１ ~Ar ２９ The substituent that may be possessed by Z in formula (A1) １１ Ar in １１ ~Ar １６ The substituents are the same as those that may be possessed by Q in formula (A2). ２１ and Q ２２ R in １１ ~R １４ and -X ２１ --X ２３ R in - １５ ~R １６ The monovalent organic group represented by the formula (A1) is Z １１ R in １１ ~R １４ and -X ２１ --X ２３ R in - １５ ~R １６ The monovalent organic group is the same as the monovalent organic group represented by the formula (I).

[0045] In the curable composition of the present invention containing a compound having a specific ethynyl group, the compound having an ethynyl group represented by formula (A2) is preferably a compound having an ethynyl group represented by formula (A3): (In formula (A3), Q ２１ and Q ２２ are each independently -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ２１ -, -P(=O)(OR ２２ ) -, -NR ２３ CO-, -COO-, -NR ２４ - and a direct bond, R ２１ ~R ２４ are each independently hydrogen or a monovalent organic group. ２１ --X ２３ - is each independently -C(=O)-, -S(=O)-, or -S(=O) ２ -, -P(=O)R ２５ - and -P(=O)(OR ２６ )- is a divalent group selected from the group consisting of R ２５ , R ２６ are each independently hydrogen or a monovalent organic group. ２１ ~n ２４ is an integer of 0 or 1 or more, and n ２５ is an integer of 1 or more, and n ２４ If is 0, n ２５ is an integer of 2 or more, and n ２４ is an integer of 1 or more, and n ２３ If is 0, n ２１ +n ２５ is an integer of 2 or more, and n ２３ and n ２４ are each an integer of 1 or more, n ２１ +n ２２ +n ２５ is an integer of 2 or more. ２１ --X ２３ -, R ２１ ~R ２６ When there are a plurality of n, they may be the same or different. ２４ is 0, n ２５ is 2, -X２３ When - is -C(=O)-, two -X ２３ -C≡CH is in the ortho or meta position. ２１ , n ２４ and n ２５ is 1, n ２３ is 0, -X ２１ - and -X ２３ - is -C(=O)-, Q ２２ NR ２４ , R ２４ When is phenyl, -X ２１ -C≡CH is in the ortho or meta position relative to the N.

[0046] Among the compounds having an ethynyl group represented by formula (A1) contained in the curable composition of the present invention, -X １１ Examples of compounds in which - is -C(=O)- include the following compounds (Aa1) to (Aa98).

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053] Among the compounds having an ethynyl group represented by formula (A1) contained in the curable composition of the present invention, -X １１ Examples of compounds in which - is -S(=O)- include the following compounds (Ab1) to (Ab35).

[0054]

[0055]

[0056] Among the compounds having an ethynyl group represented by formula (A1) contained in the curable composition of the present invention, -X １１ - is -S (=O) ２Examples of the compound in which - is 1 include the following compounds (Ac1) to (Ac35).

[0057]

[0058]

[0059] Among the compounds having an ethynyl group represented by formula (A1) contained in the curable composition of the present invention, -X １１ - is -P(=O)R １５ Examples of the compound in which - is 1 include the following compounds (Ad1) to (Ad64).

[0060]

[0061]

[0062]

[0063] Among the compounds having an ethynyl group represented by formula (A1) contained in the curable composition of the present invention, -X １１ - is -P(=O)(OR １６ )-, for example, the following compounds (Ae1) to (Ae32) can be mentioned.

[0064]

[0065]

[0066] In the compound having an ethynyl group represented by formula (A1) contained in the curable composition of the present invention, X １１ As the compound in which - is -C(=O)-, the compounds represented by the above (Aa1), (Aa4) to (Aa6), and (Aa8) to (Aa95)) are １１ As the compound where - is -S(=O)-, the compounds represented by (Ab1) to (Ab2) and (Aa5) to (Ab34) are １１ - is -S (=O) ２ -, the compounds represented by (Ac1) to (Ac2) and (Ac5) to (Ac34) are １１ - is -P(=O)R １５-, the compounds represented by (Ad1) to (Ad2), (Ad5) to (Ad34), and (Ad37) to (Ad63) are １１ - is -P(=O)(OR １６ )- are preferably the compounds represented by (Ae1) to (Ae2) and (Ae5) to (Ae34).

[0067] Among these, from the viewpoint of the reactivity of compounds having an ethynyl group, -X １１ - is -C(=O)-, -S(=O)- and -S(=O) ２ More preferably, it is one or more selected from the group consisting of -X １１ - is -C(=O)- or -S(=O) ２ More preferably, the compound is —X １１ - is -C(=O)-, and the compounds represented by (Aa1), (Aa4) to (Aa6), and (Aa8) to (Aa95) above, -X １１ - is -S (=O) ２ -, and the compounds represented by (Ac1) to (Aa35) are particularly preferred.

[0068] Among the compounds having an ethynyl group represented by formula (A1) contained in the curable composition of the present invention, n １１ Examples of the compound in which is 1 include the compounds (Aa1) to (Aa95) in which there is only one -C(=O)-C≡CH, the compounds (Ab1) to (Ab35) in which there is only one -S(=O)-C≡CH, and the compounds (Ac1) to (Ac35) in which there is only one -S(=O) ２ Compounds having only one —C≡CH, compounds (Ad1) to (Ad64) having —P(═O)R １５ Compounds having only one —C≡CH, compounds (Ae1) to (Ae32) having —P(═O)(OR １６ ) a compound having only one —C≡CH;

[0069] <Content of Compound Having an Ethynyl Group Represented by Formula (A1)> In the curable composition containing a compound having an ethynyl group represented by Formula (A1) according to the present invention, the content of the compound having an ethynyl group represented by Formula (A1) is not particularly limited. It can be appropriately adjusted depending on the application, desired properties, and the like. For example, the total amount of the curable composition can be the compound having an ethynyl group represented by Formula (A1). For example, when the total amount of the curable composition is taken as 100 mass%, the compound having an ethynyl group represented by Formula (A1) can be contained in an amount of less than 100 mass%, preferably 99.7 mass% or less, more preferably 99.5 mass% or less, and for example, 10 mass% or more, preferably 30 mass% or more, more preferably 50 mass% or more.

[0070] <Additives> In addition to the compound having an ethynyl group represented by Formula (A1), the curable composition according to the present invention containing the compound having an ethynyl group represented by Formula (A1) may, if necessary, be blended with one or more additives selected from the group consisting of curable components other than the compound having an ethynyl group represented by Formula (A1), curing accelerators, fillers, fibers, flame retardants, solvents, antioxidants, light stabilizers, ultraviolet absorbers, resins, coupling agents, conductive colorants, release agents, dispersants, adhesion promoters, tackifiers, anti-sagging agents, thixotropic agents, pore-forming agents, foaming agents, emulsifiers, plasticizers, and the like.

[0071] (Curable Components Other Than Compounds Having an Ethynyl Group Represented by Formula (A1)) The curable components other than the compound having an ethynyl group represented by formula (A1) are not particularly limited, as long as they are components that react with the compound having an ethynyl group represented by formula (A1) or components that can form an interpenetrating polymer network structure (IPN structure) when the curable composition containing the compound having an ethynyl group represented by formula (A1) according to the present invention is cured. Examples thereof include ethynyl group-containing compounds other than the compound having an ethynyl group represented by formula (A1), compounds having an ethylenically unsaturated group such as a vinyl group, an allyl group, a (meth)acryloyloxy group, or a maleimide group, and compounds having one or more reactive groups selected from the group consisting of a cyanate group (-OCN group), a hydroxyl group, an epoxy group, an isocyanate group, an amino group, a mercapto group, a carboxyl group, and a hydrolyzable silicon group.

[0072] Examples of the curable component other than the compound having an ethynyl group represented by formula (A1) include the following (C): (In the formula, Z ４１ represents Z in formula (A1). １１ is a group different from X ４１ represents X in formula (A1). １１ is the same as or different from, and n ４１ is an integer of 1 or more.), terephthaloylacetylene, N,N'-bis(4-ethynylcarbonylphenylene aniline, ethynyl group-containing compounds other than the ethynyl group-containing compound represented by formula (A1) and the ethynyl group-containing compound represented by formula (C), vinyl compounds having one or more vinyl groups in the molecule, allyl compounds having one or more allyl groups in the molecule, (meth)acrylic compounds having one or more (meth)acryloyloxy groups in the molecule, maleimide compounds having one or more maleimide groups in the molecule, cyanate ester compounds having one or more cyanate groups (-OCN groups) in the molecule, polyhydroxy compounds, epoxy resins, polyisocyanate compounds, polyamine compounds, polymercapto compounds, polycarboxylic acid compounds, hydrolyzable silicon compounds, phenolic resins, active ester compounds, unsaturated polyester resins, polybutadiene resins, benzoxazine resins, and the like.

[0073] The content of the curable components other than the compound having an ethynyl group represented by formula (A1) is not particularly limited. It can be appropriately adjusted depending on the application, desired properties, etc. For example, when the total amount of the curable composition is 100 mass%, the content of the curable components other than the compound having an ethynyl group represented by formula (A1) is 90 mass% or less, preferably 70 mass% or less, more preferably 50 mass% or less, and for example, 10 mass% or more, preferably 20 mass% or more, more preferably 30 mass% or more.

[0074] (Curing Accelerator) The curing accelerator is not particularly limited as long as it can promote the curing of a compound having an ethynyl group represented by formula (A1), a component that reacts with the compound having an ethynyl group represented by formula (A1), and a component that can form an interpenetrating polymer network structure (IPN structure) when a curable composition containing the compound having an ethynyl group represented by formula (A1) is cured. Examples of the curing accelerator include one or more selected from the group consisting of amine compounds (primary amines, secondary amines, tertiary amines, guanidines, aminosilanes, amino acids, ketimines, etc.), imidazole compounds, organic peroxides, organic phosphorus compounds, azo compounds, organic acid metal salts, and organic metal compounds.

[0075] Examples of the amine compounds include octylamine, 2-ethylhexylamine, laurylamine, stearylamine, diaminodiphenylmethane, morpholine, piperidine, piperazine, pyrrolidine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, dibenzylamine, dicyclohexylamine, N-alkylarylamine, diallylamine, thiazoline, thiomorpholine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(diaminomethyl)phenol, N,N,N',N'-tetramethyl-1,3-diaminopropane, N,N,N',N'-tetramethyl-1,6-diaminohexane, N,N-dimethylbenzylamine, N-methyl-N-(dimethylaminopropyl)aminoethanol, (dimethyl and at least one selected from the group consisting of amino acid compounds such as 2,4,6-tris(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, tripropylamine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1,5-diazabicyclo[4,3,0]nonene-5 (DBN), guanidine, phenylguanidine, diphenylguanidine, butylbiguanide, 1-o-tolylbiguanide, 1-phenylbiguanide, dicyandiamide, DL-alanine, γ-aminobutyric acid, δ-aminovaleric acid, L-glutamic acid, glutamine, glycine, L-theanine, glycylglycine, γ-aminocaproic acid, L-glutamine, aspartic acid, asparagine, L-citrulline, L-arginine, L-leucine, and L-serine; ketimine group-containing compounds; and salts of these amine compounds.

[0076] Examples of the imidazole compound include one or more selected from the group consisting of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, and 2-phenyl-4-methylimidazoline. The imidazole compound may be masked with a masking agent such as acrylonitrile, phenylene diisocyanate, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, or melamine acrylate.

[0077] Examples of organic peroxides include dicumyl peroxide, benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, di-t-butyl peroxide, t-butylcumyl peroxide, t-butyl hydroperoxide, α,α'-di(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)

[0033] Examples of the tertiary ester include one or more selected from the group consisting of 2,2-bis(t-butylperoxy)hexane, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide, trimethylsilyltriphenylsilyl peroxide, dodecanoyl peroxide, and methyl ethyl ketone peroxide.

[0078] Examples of the organic phosphorus compound include one or more compounds selected from the group consisting of ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine / triphenylborane complex, and tetraphenylphosphonium tetraphenylborate.

[0079] Examples of azo compounds include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyronitrile), 2,2'-azobis-2-methylbutyronitrile, 1,1-azobis(1-cyclohexanecarbonitrile), 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(methylisobutyrate), and azobisisobutyronitrile.

[0080] Examples of organic acid metal salts include metal salts (one or more selected from the group consisting of magnesium salts, calcium salts, zinc salts, cobalt salts, nickel salts, tin salts, barium salts, iron salts, aluminum salts, copper salts, manganese salts, zirconium salts, titanium salts, indium salts, lead salts, etc.) of one or more fatty acids selected from the group consisting of aliphatic carboxylic acids having 6 to 18 carbon atoms (octylic acid, lauric acid, stearic acid, neodecanoic acid, oleic acid, etc.) and aromatic carboxylic acids having 6 to 18 carbon atoms (benzoic acid, naphthyl acid, etc.).

[0081] The organometallic compound is preferably a metal chelate compound having one or more β-diketones (acetylacetone, benzoylacetone, stearoylbenzoylmethane, dibenzoylmethane, ethyl acetoacetate, dehydroacetic acid, etc.) as a chelate component. The metal may be one or more selected from the group consisting of magnesium, calcium, zinc, cobalt, nickel, tin, barium, iron, aluminum, copper, manganese, zirconium, titanium, indium, lead, etc.

[0082] In the curable composition of the present invention containing the compound having an ethynyl group represented by formula (A1), it is preferable to use an amine compound as a curing accelerator. The curable composition of the present invention containing the compound having an ethynyl group represented by formula (A1) can accelerate curing without using a metal component such as an organic acid metal salt or an organometallic compound.

[0083] The content of the curing accelerator is not particularly limited. It can be appropriately adjusted depending on the reactivity of the curable component in the curable composition, the curing conditions, etc. For example, it is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more, and for example, 5.0 parts by mass or less, preferably 1.0 part by mass or less, relative to 100 parts by mass of the compound having an ethynyl group represented by Formula (1A).

[0084] (Filler) Examples of the filler include one or more selected from the group consisting of oxides, hydroxides, sulfates, carbonates, borates, phosphates, titanates, nitrides, carbides, and the like. For example, one or more selected from the group consisting of silicon oxides such as spherical silica (amorphous silica, crystalline silica, fused silica, spherical silica, precipitated silica, silicic anhydride, hydrous silicic acid, etc.), aluminum oxide (alumina), titanium oxide, magnesium oxide, aluminum oxide (alumina, etc.), beryllium oxide, zinc oxide, aluminum, magnesium carbonate, calcium carbonate (heavy calcium carbonate, colloidal calcium carbonate, etc.), diamond, aluminum hydroxide, magnesium hydroxide, barium sulfate, diatomaceous earth, clay, talc, mica, barium titanate, crystalline silica, Neuburg silica, fused silica, spherical silica, silicon nitride, aluminum nitride, boron nitride, aluminum borate, carbon black, ferric oxide, resin powders (styrene-based resin powder, acrylic-based resin powder, vinyl chloride-based resin powder, olefin-based resin powder, urethane-based resin powder, polyamide-based resin powder, polyester-based resin powder, etc.), glass balloons, shirasu balloons, etc. may be mentioned.

[0085] The shape of the filler is not particularly limited. For example, it may be spherical, amorphous (crushed), fibrous, etc. The volume average particle diameter of the filler is not particularly limited. For example, it is 0.01 μm or more, preferably 0.1 μm or more, and for example, 100 μm or less, preferably 50 μm or less. The filler may be surface-treated. Examples of surface treatment agents used for surface treatment of the filler include one or more selected from the group consisting of silane coupling agents such as epoxysilane, vinylsilane, (meth)acrylicsilane, aminosilane, and alkoxysilane, titanium coupling agents, etc.

[0086] The content of the filler is not particularly limited and can be appropriately adjusted depending on the application, desired properties, etc. For example, the content of the filler is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and for example, 1200 parts by mass or less, preferably 1000 parts by mass or less, relative to 100 parts by mass of the compound having an ethynyl group represented by formula (1A).

[0087] (Fibers) The fibers may be twisted, untwisted, or untwisted. When forming a fiber-reinforced composite material, untwisted or untwisted fibers are preferred from the standpoint of moldability, etc. Furthermore, fibers with fibers aligned in one direction or woven fabrics can be used. As woven fabrics, plain weave, satin weave, and the like can be used. As fibers, for example, one or more fibers selected from the group consisting of carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber, potassium titanate fiber, and the like can be used.

[0088] The fiber diameter of the fibers is not particularly limited. For example, it is 0.01 μm or more, preferably 0.1 μm or more, and for example, 100 mm or less, preferably 50 mm or less. The fibers may be surface-treated. Examples of the surface treatment agent used for the surface treatment of the filler include one or more selected from the group consisting of silane coupling agents such as epoxysilane, vinylsilane, (meth)acrylicsilane, aminosilane, and alkoxysilane, titanium coupling agents, etc.

[0089] The content of the fibers is not particularly limited and can be appropriately adjusted depending on the application, desired properties, etc. For example, the content of the fibers is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and for example, 1200 parts by mass or less, preferably 1000 parts by mass or less, per 100 parts by mass of the compound having an ethynyl group represented by formula (1A).

[0090] (Flame Retardant) The flame retardant is not particularly limited as long as it can impart flame retardancy to the curable composition and / or a cured product of the curable composition. For example, one or more selected from the group consisting of halogen-based flame retardants (bromine-based flame retardants (pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, etc.), chlorine-based flame retardants (chlorinated paraffin, etc.)), phosphorus-based flame retardants (phosphate ester compounds such as condensed phosphate esters and cyclic phosphate esters, phosphazene compounds such as cyclic phosphazenes, phosphinate-based flame retardants such as aluminum dialkylphosphinate salts, melamine phosphate compounds such as melamine polyphosphate, and phosphine oxide compounds having a diphenylphosphine oxide group) can be used. The content of the flame retardant is not particularly limited. An amount that can impart the required flame retardancy to the curable composition and / or a cured product of the curable composition without impairing their properties can be used.

[0091] (Solvent) The curable composition may contain, as necessary, a solvent capable of dissolving or dispersing the compound having an ethynyl group represented by formula (A1) and not reacting with the compound having an ethynyl group represented by formula (A1). The solvent is not particularly limited, and may be one or more selected from the group consisting of ketone solvents such as methyl ethyl ketone, ether solvents such as dibutyl ether and tetrahydrofuran, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide, hydrocarbon solvents such as benzene, toluene, and xylene, and chlorinated hydrocarbon solvents such as trichloroethylene. The content of the solvent is not particularly limited. When the curable composition is impregnated into fibers or applied to articles, an amount sufficient to impart impregnation or application properties can be used.

[0092] (Antioxidant) The antioxidant is not particularly limited as long as it can impart antioxidant properties (antiaging properties) and weather resistance to the curable composition and / or a cured product of the curable composition. Examples thereof include one or more antioxidants selected from the group consisting of hindered phenol antioxidants, monophenol antioxidants, bisphenol antioxidants, polyphenol antioxidants, etc.

[0093] (Light Stabilizer) The light stabilizer is not particularly limited as long as it can impart light stability (resistance to photo-oxidative degradation) to the curable composition and / or the cured product of the curable composition. For example, one or more types selected from the group consisting of benzotriazole-based light stabilizers, hindered amine-based light stabilizers, benzoate-based light stabilizers, etc. may be used.

[0094] (Ultraviolet Absorber) The ultraviolet absorber is not particularly limited as long as it can impart ultraviolet resistance stability (surface weather resistance) to the curable composition and / or the cured product of the curable composition. For example, one or more selected from the group consisting of benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, substituted acrylonitrile-based ultraviolet absorbers, and metal chelate-based ultraviolet absorbers can be used.

[0095] (Resin) The resin is not particularly limited as long as it is a resin having a weight-average molecular weight of 500 or more. Examples thereof include one or more selected from the group consisting of polyimide resins, polyamide resins, polybenzimidazole resins, polybenzoxazole resins, polyester resins, polyurethane resins, phenolic resins, polyether ether ketone resins, polyether ketone resins, polyethersulfone resins, polyphenylene ether resins, polyether resins, polyketone resins, acetal resins, polyolefin resins, polystyrene resins, vinyl chloride resins, fluororesins, vinyl ester resins, vinyl alcohol resins, vinyl acetal resins, acrylic resins, synthetic rubbers, diene resins, graft resins, core-shell resins, and block resins.

[0096] (Coupling Agent) Examples of the coupling agent include one or more selected from the group consisting of silane coupling agents such as epoxy silane, vinyl silane, (meth)acrylic silane, amino silane, and alkoxy silane, titanium coupling agents, phosphorus-based coupling agents, aluminum-based coupling agents, boron-based coupling agents, and zirconium-based coupling agents.

[0097] (Conductive Material) The conductive material is not particularly limited as long as it is a material that can impart conductivity to the curable composition, and examples thereof include one or more materials selected from the group consisting of metal powder, metal-plated particles, metal vapor deposition materials, conductive polymers, etc.

[0098] <Form of Curable Composition> The form of the curable composition containing the compound having an ethynyl group represented by formula (A1) of the present invention is not particularly limited. For example, it can be in the form of a powder, a solution, or a dispersion. In the case of a solution, it may be a one-component type or a multi-component type (for example, a two-component type).

[0099] <Weight Loss in TG-DTA (Thermogravimetric-Differential Thermal Analysis) Measurement> The curable composition according to the present invention, which contains a compound having an ethynyl group represented by formula (A1), may be a curable composition which satisfies the following requirements (I) and / or (II): (I) in a TG-DTA (thermogravimetric-differential thermal analysis) measurement of the curable composition, the weight loss when heated in a nitrogen atmosphere from 30°C to 300°C at a heating rate of 10°C / min is 10% or less; and (II) in a TG-DTA (thermogravimetric-differential thermal analysis) measurement of a cured product of the curable composition obtained by heating under conditions of 50°C to 250°C for 48 hours or less, the weight loss when heated in a nitrogen atmosphere from 30°C to 300°C at a heating rate of 10°C / min is 10% or less. It is preferable that the curable composition according to the present invention, which contains a compound having an ethynyl group represented by formula (A1), satisfies the requirements (I) and / or (II).

[0100] Requirement (I) indicates the behavior of the "curable composition" when measured by TG-DTA (thermogravimetric-differential thermal analysis), and in the TG-DTA measurement, when heated from 30°C to 300°C at a heating rate of 10°C / min in a nitrogen atmosphere, the weight loss is 10% or less, preferably 7% or less, and more preferably 5% or less. Requirement (I) can be confirmed, for example, by the same method as the measurement of the 5% weight loss temperature described in the Examples below.

[0101] Requirement (II) indicates the behavior when "a cured product of the curable composition obtained by heating under conditions of 50°C or higher and 250°C or lower for 48 hours or shorter" is measured by TG-DTA (thermogravimetric-differential thermal analysis), and in the TG-DTA measurement, when heated from 30°C to 300°C at a heating rate of 10°C / min in a nitrogen atmosphere, the weight loss is 10% or less, preferably 7% or less, and more preferably 5% or less. Requirement (II) can be confirmed, for example, by a method similar to the measurement of the 5% weight loss temperature described in the Examples below.

[0102] In requirement (II), the lower limit of the heating time under the condition of 50° C. or higher and 250° C. or lower is not particularly limited as long as it is the time required for curing of the curable composition to be completed and a cured product to be formed, and is 48 hours or shorter. For example, it can be 15 minutes or longer, preferably 1 hour or longer, more preferably 2 hours or longer, and even more preferably 4 hours or longer.

[0103] Conditions for obtaining "a cured product of the curable composition obtained by heating at 50°C or higher and 250°C or lower for 48 hours or shorter" can be, for example, the same as the method for producing a cured product used to measure the 5% weight loss temperature described in the Examples below.

[0104] <Solvent-Insoluble Content> The curable composition according to the present invention, which contains a compound having an ethynyl group represented by formula (A1), may be a curable composition which satisfies the following requirement: a cured product obtained by heating the curable composition under conditions of 50°C to 250°C for 48 hours or less, immersing the curable composition in boiling tetrahydrofuran for 2 hours, subjecting the cured product to solvent replacement in acetone at 25°C ± 5°C for 6 hours or more, and drying the cured product under a reduced pressure of -0.1 MPa at 80°C until no mass change is observed for 3 hours or more when the mass is measured every hour. The solvent-insoluble content is preferably 75% or more, more preferably 85% or more, and even more preferably 90% or more. A cured product having a solvent-insoluble content of more than 70% even after immersion in boiling tetrahydrofuran for 2 hours can be said to have excellent resistance to various solvents. The conditions for obtaining "a cured product of the curable composition obtained by heating under conditions of 50°C or higher and 250°C or lower for 48 hours or shorter" can be the same as the conditions in the above <Weight loss in TG-DTA (thermogravimetric-differential thermal analysis) measurement>, and for example, a method similar to the method for producing a cured product used to measure the 5% weight loss temperature described in the Examples below can be used.

[0105] <Exothermic Onset Temperature (Tonset (°C)) and Exothermic Peak Temperature (Tpeak (°C))> The curable composition containing the compound having an ethynyl group represented by Formula (A1) according to the present invention has an exothermic onset temperature (Tonset (°C)) of less than 250°C, for example, less than 200°C, preferably less than 170°C, and more preferably less than 120°C. When the exothermic onset temperature (Tonset (°C)) is less than 250°C, for example, less than 200°C, the curable composition can have excellent low-temperature curing properties. As a method for measuring the exothermic onset temperature (Tonset (°C)) and the exothermic peak temperature (Tpeak (°C)), for example, the same method as for measuring the exothermic onset temperature (Tonset (°C)) and the exothermic peak temperature (Tpeak (°C)) described in the Examples below can be used.

[0106] <Glass transition point> A cured product of the curable composition containing the compound having an ethynyl group represented by formula (A1) according to the present invention preferably has a glass transition point of 300°C or higher as determined by dynamic viscoelasticity measurement. The glass transition point is more preferably 330°C or higher. When the cured product of the curable composition has a glass transition point of 300°C or higher, it can be said that a cured product having excellent heat resistance has been formed. The glass transition point determined by dynamic viscoelasticity measurement can be measured, for example, by the same method as the method for measuring the glass transition point determined by dynamic viscoelasticity measurement described in the Examples below.

[0107] <Residual Carbon Fraction> The curable composition containing the compound having an ethynyl group represented by formula (A1) according to the present invention is preferably a cured product obtained by heating the curable composition under conditions of 50°C to 250°C for 48 hours or less. When the cured product is heated from 100°C to 800°C in a nitrogen atmosphere and held at 800°C for 1 hour in TG-DTA, the residual carbon fraction (residual mass) is preferably 60% by mass or more. The residual carbon fraction is more preferably 63% by mass or more, and even more preferably 65% ​​by mass or more. A residual carbon fraction of 60% by mass or more can be said to be a cured product with excellent heat resistance, particularly flame retardancy. The residual carbon fraction is determined by heating the cured product in a non-oxidizing atmosphere from 100°C to 800°C at a heating rate of 10°C / min and holding at 800°C for 1 hour, with the mass fraction of the cured product at 100°C set to 100. For example, a method similar to that for measuring the residual carbon fraction described in the Examples below can be used.

[0108] <Method for Producing Curable Composition> There is no particular limitation on the method for producing the curable composition containing the compound having an ethynyl group represented by formula (A1) according to the present invention. For example, the curable composition can be obtained by mixing the compound having an ethynyl group represented by formula (A1) with additives that are blended as needed. Examples of the mixing method include a method in which the composition is thoroughly mixed using a mixer such as an extruder, kneader, or roll until the mixture is homogeneous.

[0109] <Applications> The curable composition containing the compound having an ethynyl group represented by formula (A1) according to the present invention can be used in a variety of applications, such as adhesives, sealants, potting agents, encapsulants, carbon material raw materials, prepregs, circuit connecting materials, conductive compositions, molded articles, insulating materials, paints, laminates, prepreg cured products, fiber-reinforced composite materials, automobile parts, electrical and electronic materials, civil engineering and construction materials, structural materials, and films.

[0110] [Compound] <Compound represented by formula (B)> Formula (B); (In formula (B), Z ３１ is Ar ３１ , -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ３１ -, -P(=O)(OR ３２ ) -, -NR ３３ CO-, -COO-, -NR ３４ an n-valent aromatic organic group consisting of one or more groups selected from the group consisting of - and a direct bond, ３１ , Ar ３３ , Ar ３４ and Ar ３６ each independently represents a monovalent or higher aromatic ring which may have a substituent, ３２ represents a divalent or higher aromatic ring which may have a substituent, and Ar ３５ represents a tetravalent or higher aromatic ring which may have a substituent, and -X ３１ -C≡CH is Ar ３１ ~Ar ３６ is bonded to either of R ３１ ~R ３４ are each independently hydrogen or a monovalent organic group; Z ３１ In which -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ３１ -, -P(=O)(OR ３２ ) -, -NR ３３ CO—, —COO—, and —NR ３４ - are not directly bonded to each other. ３１- is -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ３５ - and -P(=O)(OR ３６ )- is a divalent group selected from the group consisting of R ３５ , R ３６ are each independently hydrogen or a monovalent organic group. ３１ is an integer of 2 or more. ３１ ~Ar ３６ , R ３１ ~R ３６ , -X ３１ When there are a plurality of -, they may be the same or different. ３１ - is -C(=O)-, Z ３１ When is an unsubstituted phenyl ring, n ３１ is an integer from 3 to 6. ３１ is 2, -X ３１ - is -C(=O)-, Z ３１ but In the case of ３１ -C≡CH is in the ortho position relative to N, or two -X-C≡CH are in the para and meta positions relative to N. ３１ is 2, -X ３１ - is -C(=O)- or -S(=O) ２ -, Z ３１ but In the case of ３１ -C≡CH is in the ortho or meta position relative to O. ３１ is 2, -X ３１ - is -C(=O)-, Z ３１ but In the case of ３１ -C≡CH is in the ortho or meta position relative to the amide bond. ３１ is 2, -X ３１ - is -C(=O)-, Z ３１ but In the case of ３１ -C≡CH is in the ortho or para position relative to the amide bond.

[0111] Z in formula (B)３１ , X ３１ and n ３１ are Z in formula (A1), respectively. １１ , X １１ and n １１ In addition, Z in formula (B) is the same as ３１ Ar in ３１ ~Ar ３６ , R ３１ ~R ３４ , an aromatic ring and a monovalent organic group, X ３１ R in ３５ ~R ３６ and the monovalent organic group are each represented by Z in formula (A1). １１ Ar in １１ ~Ar １６ , R １１ ~R １４ , an aromatic ring and a monovalent organic group, X １１ R in １５ ~R １６ and the monovalent organic group.

[0112] Examples of the compound having an ethynyl group represented by formula (B) of the present invention include the compound represented by formula (A2) in the above [Curable Composition]. Also, examples of the compound having an ethynyl group represented by formula (B) of the present invention include the compound represented by formula (A3) in the above [Curable Composition].

[0113] Among the compounds having an ethynyl group represented by formula (B) of the present invention, -X ３１ Examples of the compound in which - is -C(=O)- include the compounds (Aa2) to (Aa19) and (Aa21) to (Aa95). ３１ Examples of the compound in which - is -S(=O)- include the compounds (Ab1) to (Ab35). ３１ - is -S (=O) ２ Examples of the compound having an ethynyl group represented by formula (B) of the present invention include the compounds (Ac1) to (Ac13) and (Ac15) to (Ac35). ３１- is -P(=O)R ３５ Examples of the compound having an ethynyl group represented by formula (B) of the present invention include the compounds (Ad1) to (Ad64). ３１ - is -P(=O)(OR ３６ )--, for example, the compounds (Ae1) to (Ae32) mentioned above.

[0114] In the compound having an ethynyl group represented by formula (B) of the present invention, X ３１ As the compound in which - is -C(=O)-, the compounds represented by (Aa4) to (Aa19) and (Aa21) to (Aa95) are ３１ As the compound where - is -S(=O)-, the compounds represented by (Ab1) to (Ab2) and (Ab5) to (Ab34) are ３１ - is -S (=O) ２ -, the compounds represented by (Ac1) to (Ac2) and (Ac5) to (Ac34) are ３１ - is -P(=O)R ３５ -, the compounds represented by (Ad1) to (Ad2), (Ad5) to (Ad34), and (Ad37) to (Ad64) are １１ - is -P(=O)(OR ３６ )- are preferably the compounds represented by (Ae1) to (Ae2) and (Ae5) to (Ae32).

[0115] Among these, from the viewpoint of the reactivity of compounds having an ethynyl group, -X ３１ - is -C(=O)-, -S(=O) ２ More preferably, it is one or more selected from the group consisting of -X ３１ - is -C(=O)- or -S(=O) ２ More preferably, the compound is —X ３１ In particular, - is -C(=O)-, and the compounds represented by (Aa4) to (Aa18), (Aa21) to (Aa38), and (Aa41) to (Aa95) are preferred.

[0116] <Method for Producing a Compound Having an Ethynyl Group Represented by Formula (B)> The compound having an ethynyl group represented by formula (B) according to the present invention can be produced by industrial synthesis means, for example, the following reaction (i) or (ii).

[0117] (i) Z ３１ -(X ３１ -Hal ３１ ) n ３１ (In the formula, Z ３１ , X ３１ and n ３１ are Z in formula (B), respectively. ３１ , X ３１ and n ３１ is the same as Hal ３１ is a halogen atom.) and an acid halide represented by CH≡C-M ３１ -Hal ３２ (M in the formula ３１ are alkaline earth metals, alkali metals, manganese, palladium, titanium, zinc, aluminum, bismuth, indium, germanium, silicon, and samarium; Hal ３１ is a halogen atom.) in the presence of an organic solvent and a base.

[0118] (ii) (S1) Z ３１ -(X ３１ -Hal ３１ ) n ３１ (In the formula, Z ３１ , X ３１ and n ３１ are Z in formula (B), respectively. ３１ , X ３１ and n ３１ is the same as Hal ３１ is a halogen atom.) with a bis(trialkylsilyl)acetylene in the presence of an organic solvent and a Lewis acid catalyst, and then (S2) eliminating the trialkylsilyl group in the presence of an organic solvent and a base.

[0119] Examples of the organic solvent in the reactions (i) and (ii) include one or more selected from the group consisting of hydrocarbon solvents (benzene, toluene, xylene, etc.), halogenated hydrocarbon solvents (chlorobenzene, dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, etc.), ether solvents (diethyl ether, dimethyl ether, tetrahydrofuran, dioxane, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), nitrile solvents (acetonitrile, propionitrile, benzonitrile, etc.), amide solvents (dimethylformamide, N-methyl-2-pyrrolidone, etc.), sulfoxide solvents (dimethyl sulfoxide, etc.), and the like.

[0120] The base used in the reactions (i) and (ii) may be one or more of various bases such as inorganic bases and organic bases, for example, one or more selected from the group consisting of metal carbonates (sodium carbonate, sodium bicarbonate, etc.), metal carboxylates (sodium acetate, calcium acetate, etc.), metal hydroxides (sodium hydroxide, calcium hydroxide, etc.), metal borates (sodium borate, etc.), and amines (primary amines, secondary amines, tertiary amines, etc., such as ammonia, triethylamine, triisopropylamine, tributylamine, methylamine, benzylamine, N,N-dimethylaniline, piperazine, and pyridine).

[0121] Examples of the Lewis acid in the reactions (i) and (ii) include one or more selected from the group consisting of aluminum chloride, chromium oxide, alumina, silica-alumina, zeolite, boron trifluoride, tin tetrachloride, titanium tetrachloride, phosphorus pentafluoride, phosphorus pentachloride, and antimony pentafluoride.

[0122] In the present invention, the reaction (i) is preferably used because it is simple and advantageous in terms of reaction yield and the like.

[0123] Furthermore, the (meth)acrylate reaction may be carried out in the presence of a polymerization inhibitor (thermal polymerization inhibitor) as necessary. Examples of polymerization inhibitors include hydroquinone compounds, catechol compounds, amine compounds, 2,2-diphenyl-1-picrylhydrazyl, 4-hydroxy-2,2,6,6-tetramethylpiperazine-1-oxyl, and the like. Examples of hydroquinone compounds include hydroquinone; hydroquinone monoalkyl ethers such as hydroquinone monomethyl ether (methoquinone); and the like. Examples of catechol compounds include alkylcatechols such as t-butylcatechol; and the like. Examples of amine compounds include diphenylamine. These polymerization inhibitors may be used alone or in combination of two or more.

[0124] The reaction conditions for producing the compound having an ethynyl group represented by formula (B) are not particularly limited. The reaction may be carried out under cooling or heating, or at room temperature (25°C ± 5°C). The reaction may also be carried out under pressure or reduced pressure.

[0125] In producing the compound having an ethynyl group represented by formula (B), after completion of the reaction, operations such as neutralization, washing with water, concentration, crystallization, filtration, etc. can be carried out as necessary. Further, the compound can be purified by operations such as recrystallization, distillation, adsorption, column chromatography, etc.

[0126] [Heat-Resistant Resin Material] The heat-resistant resin material according to the present invention is a heat-resistant resin material obtained by curing a curable composition containing a compound having an ethynyl group represented by formula (A1) or a compound having an ethynyl group represented by formula (B). The heat-resistant resin material may be a fully cured product obtained by completely curing the curable composition containing the compound having an ethynyl group represented by formula (A1) or the compound having an ethynyl group represented by formula (B), or a partially cured product obtained by partially curing the curable composition. For example, the heat-resistant resin material can be obtained by heating the curable composition containing the compound having an ethynyl group represented by formula (A1) or the compound having an ethynyl group represented by formula (B) at 50°C or higher and 250°C or lower for 48 hours or less. The heating temperature is preferably 50°C or higher, for example 60°C or higher, preferably 70°C or higher, and more preferably 100°C or higher, and 250°C or lower, for example 200°C or lower, preferably 180°C or lower, and more preferably 150°C or lower. The heating time among the heating conditions is 48 hours or less, for example, preferably 36 hours or less, more preferably 24 hours or less, and for example, preferably 15 minutes or more, preferably 1 hour or more, more preferably 2 hours or more, and even more preferably 4 hours or more.

[0127] A cured product obtained from a heat-resistant resin material (cured product of the curable composition) obtained by curing the curable composition containing the compound having an ethynyl group represented by formula (A1) according to the present invention or the compound having an ethynyl group represented by formula (B) preferably satisfies the following requirement (II): (II) in TG-DTA (thermogravimetric-differential thermal analysis) measurement of the cured product of the curable composition obtained by heating under conditions of 50°C or higher and 250°C or lower for 48 hours or shorter, the weight loss when heated from 30°C to 300°C at a heating rate of 10°C / min in a nitrogen atmosphere is 10% or less.

[0128] [Adhesive] The adhesive according to the present invention is a curable composition containing a compound having an ethynyl group represented by formula (A1) or an adhesive containing a compound having an ethynyl group represented by formula (B). The adhesive may contain any additive, if necessary. The ethynyl group of the compound having an ethynyl group represented by formula (A1) or the compound having an ethynyl group represented by formula (B) undergoes a cyclization reaction or the like, thereby exhibiting strong adhesive strength. The curable composition containing a compound having an ethynyl group represented by formula (A1) or the adhesive containing a compound having an ethynyl group represented by formula (B) according to the present invention can be used as an adhesive for electrical and electronic applications, a structural adhesive, a heat-resistant adhesive for aerospace applications, etc.

[0129] [Sealant] The sealant according to the present invention is a curable composition containing a compound having an ethynyl group represented by formula (A1) or a sealant containing a compound having an ethynyl group represented by formula (B). The sealant may contain any additive, if necessary. The ethynyl group in the compound having an ethynyl group represented by formula (A1) or the compound having an ethynyl group represented by formula (B) undergoes a cyclization reaction or the like, thereby exhibiting a powerful sealing effect. The curable composition containing a compound having an ethynyl group represented by formula (A1) or the sealant containing a compound having an ethynyl group represented by formula (B) according to the present invention can be used as a sealant for civil engineering and construction, a sealant for various structures, a heat-resistant sealant for aerospace applications, etc.

[0130] [Potting Material] The potting material according to the present invention is a curable composition containing a compound having an ethynyl group represented by formula (A1) or a potting material containing a compound having an ethynyl group represented by formula (B). The potting material may contain any additive, if necessary. The ethynyl group in the compound having an ethynyl group represented by formula (A1) or the compound having an ethynyl group represented by formula (B) undergoes a cyclization reaction or the like, thereby exhibiting the function of a powerful potting material. The potting material according to the present invention, which includes a curable composition containing a compound having an ethynyl group represented by formula (A1) or a compound having an ethynyl group represented by formula (B), can be used as a material for insulating electrical components, electronic components, motor components, battery components, etc., or for protecting electrical components, electronic components, motor components, battery components, etc. from thermal shock or mechanical shock.

[0131] [Sealing Material] The sealing material according to the present invention is a curable composition containing a compound having an ethynyl group represented by formula (A1) or a sealing material containing a compound having an ethynyl group represented by formula (B). The sealing material may contain any component as an additive, if necessary. The ethynyl group of the compound having an ethynyl group represented by formula (A1) or the compound having an ethynyl group represented by formula (B) undergoes a cyclization reaction or the like, thereby exhibiting the function as a powerful sealing material. The curable composition containing a compound having an ethynyl group represented by formula (A1) or the sealing material containing a compound having an ethynyl group represented by formula (B) according to the present invention can be used as a sealing material for electrical components, electronic components, motor components, battery components, etc., particularly as a sealing material for electronic components such as semiconductors.

[0132] [Carbon Material] The carbon material according to the present invention is a carbon material represented by formula (A): (In formula (A), -X- is -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ａ - and -P(=O)(OR ｂ When there are a plurality of —X—, they may be the same or different, and R ａis hydrogen or a monovalent organic group, and R ａ When there are a plurality of R ｂ is hydrogen or a monovalent organic group, and R ｂ When there are a plurality of groups, they may be the same or different, Z is an n-valent organic group, and n is an integer of 1 or more.) A carbon material is obtained by baking a compound having an ethynyl group represented by formula (A), a cured product of a compound having an ethynyl group represented by formula (A), a curable composition containing a compound having an ethynyl group represented by formula (A), or a cured product of the curable composition. Examples of the obtained carbon material include glassy carbon, graphene, carbon fiber, carbon sheet, molded carbon product, porous carbon material, and carbon particles. It can also be used as a raw material for these.

[0133] Examples of the n-valent organic group for Z in formula (A) include an n-valent aromatic group, an n-valent alicyclic group, and an n-valent aliphatic group.

[0134] When the n-valent organic group for Z in formula (A) is an n-valent aromatic group, the compound having an ethynyl group represented by formula (A) can be a compound represented by formula (A1) described above in [Curable composition].

[0135] When the n-valent organic group for Z in formula (A) is an n-valent alicyclic group, the alicyclic group is not particularly limited as long as it is an n-valent group having an alicyclic ring that is formed only by carbon and is a ring other than a conjugated unsaturated ring structure (aromatic ring). Examples of the alicyclic ring include a cycloalkyl ring having 3 to 20 carbon atoms (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.), a cycloalkene ring having 3 to 20 carbon atoms (e.g., cyclopentene, cyclohexene, cyclopentadiene, etc.), a fused ring having 8 to 30 carbon atoms (e.g., bicycloalkane), and a bridged ring having 6 to 30 carbon atoms (e.g., tricyclo[5.2.1.02,6]decane, norbornene, norbornane, adamantane, etc.).

[0136] When the n-valent organic group for Z in formula (A) is an n-valent aliphatic group, the aliphatic group is not particularly limited as long as it is a saturated or unsaturated n-valent aliphatic hydrocarbon group having 2 to 30 carbon atoms. Examples of the alkyl group include those having 1 to 20 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, and octyl groups) as an n-valent group; those having 1 to 24, preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8, alkenyl groups (e.g., ethenyl, propenyl, butenyl, pentenyl, hexenyl, and octenyl groups) as an n-valent group; and those having 1 to 24, preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8, alkynyl groups (e.g., ethynyl, propynyl, butynyl, pentynyl, hexynyl, and octynyl groups) as an n-valent group.

[0137] In formula (A), n is an integer of 1 or more. In the present invention, it is preferable to use a compound containing an ethynyl group where n is 2 or more. When a plurality of compounds containing an ethynyl group represented by formula (A) are used, the average of n (apparent n) is, for example, 1.3 or more, preferably 1.5 or more, more preferably 1.7 or more, even more preferably 1.9 or more, particularly preferably 2.0 or more, and for example, 10.0 or less, preferably 8.0 or less, more preferably 6.0 or less, even more preferably 4.0 or less, particularly preferably 3.0 or less. The average of n can be calculated in the same manner as the above-mentioned "average of n in the entire curable composition".

[0138] In the carbon material of the present invention, examples of the ethynyl group-containing compound represented by formula (A) include the compounds (Aa1) to (Aa98), (Ab1) to (Ab35), (Ac1) to (Ac35), (Ad1) to (Ad64), and (Ae1) to (Ae32), as well as the following compounds (Aa99) to (Aa111), (Ab36) to (Ab52), (Ac36) to (Ac52), (Ad65) to (Ad98), and (Ae33) to (Ae49).

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145] [Prepreg] The prepreg according to the present invention is a prepreg having the formula (A): (In formula (A), -X- is -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ａ - and -P(=O)(OR ｂ When there are a plurality of —X—, they may be the same or different, and R ａ is hydrogen or a monovalent organic group, and R ａ When there are a plurality of R ｂ is hydrogen or a monovalent organic group, and R ｂ When there are a plurality of groups, they may be the same or different, Z is an n-valent organic group, and n is an integer of 1 or more. The prepreg contains a compound having an ethynyl group represented by the following formula (1), and a fibrous reinforcing material.

[0146] The repreg according to the present invention is obtained by applying a compound having an ethynyl group or a composition containing a compound having an ethynyl group to a fibrous reinforcing material by means of pre-impregnation, coating or the like.

[0147] Examples of the compound having an ethynyl group represented by formula (A) include the compounds having an ethynyl group described above in the section [Carbon Material].

[0148] Examples of fibrous reinforcing materials include one or more of inorganic fibers such as carbon fiber, glass fiber, potassium titanate fiber, and metal fiber, and organic fibers such as heat-resistant polymers. The form of the fibrous reinforcing material is not particularly limited, but examples include woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat. As the woven fabric, for example, plain weave, sieve weave, twill weave, and the like can be used. The fibrous reinforcing material can be subjected to fiber opening treatment or surface treatment with a silane coupling agent or the like, as necessary.

[0149] The prepreg can be molded as necessary and then heat-cured, for example, at a temperature range of 50°C or higher and 250°C or lower, or at a temperature range of 50°C or higher and 200°C or lower, to obtain a fiber-reinforced material.

[0150] The present invention will be explained in more detail below by way of examples, but it goes without saying that these examples are given for illustrative purposes and should not be construed as limiting.

[0151] {Synthesis of Compounds Represented by Formula (A1) / Formula (B)} [Example 1A] <Synthesis of 1-(3-(4-propioloylphenoxy)phenyl)prop-2-yn-1-one> (Step 1: Synthesis of 3-(4-formylphenoxy)benzaldehyde) Under an argon atmosphere, 4-fluorobenzaldehyde (4.96 g, 40.0 mmol) was dissolved in 20 mL of dehydrated dimethyl sulfoxide. 3-Hydroxybenzaldehyde (4.44 g, 20.0 mmol) and potassium carbonate (5.53 g, 40.0 mmol) were added, followed by heating and stirring at 110°C for 43 hours. The solution was allowed to cool to room temperature (25°C), 200 mL of water was added, and the mixture was extracted three times with 200 mL of a 4:1 hexane:ethyl acetate mixed solvent. The solvent was removed from the resulting organic phase by distillation under reduced pressure, and the mixture was dried under vacuum. This afforded 3-(4-formylphenoxy)benzaldehyde (4.24 g, 18.7 mmol) as a pale yellow liquid in a 93.6% yield.

[0152] (Step 2: Synthesis of 1-(3-(4-propioloylphenoxy)phenyl)prop-2-yn-1-one) Under an argon atmosphere, 3-(4-Formylphenoxy)benzaldehyde (3.39 g, 15.0 mmol) was dissolved in 150 mL of anhydrous tetrahydrofuran. After cooling to 0°C, 120 mL (60.0 mmol) of a 0.5 M tetrahydrofuran solution of ethynylmagnesium chloride was added dropwise over 30 minutes. The mixture was warmed to room temperature (25°C) and stirred at room temperature (25°C) for 19 hours. 200 mL of saturated aqueous ammonium chloride was added to the solution, and the mixture was extracted three times with 50 mL of dichloromethane. The solvent was removed from the organic phase by distillation under reduced pressure, and the mixture was dried under vacuum to obtain a crude product. The resulting crude product was dissolved in 150 mL of dichloromethane under air, and manganese dioxide (52.1 g, 600 mmol) was added. The mixture was stirred at room temperature (25°C) for 1 hour. The solution was filtered, and the solvent was removed from the organic phase by distillation under reduced pressure, followed by drying under vacuum. This was purified by column chromatography using a mixed solvent of hexane:ethyl acetate = 4:1 (volume ratio), to obtain a pale yellow solid, 1-(3-(4-Propioloylphenoxy)phenyl)prop-2-yn-1-one (2.68 g, 9.77 mmol), in a yield of 65.2%.

[0153] Reference Example 1A: Synthesis of 1,1'-(1,3-phenylene)bis(prop-2-yn-1-one) Under an argon atmosphere, isophthaldialdehyde (3.35 g, 25.0 mmol) was dissolved in 250 mL of dehydrated tetrahydrofuran. After cooling to 0°C, 200 mL (100 mmol) of a 0.5 M tetrahydrofuran solution of ethynylmagnesium chloride was added dropwise over 30 minutes. The mixture was warmed to room temperature (25°C) and stirred at room temperature (25°C) for 19 hours. 200 mL of saturated aqueous ammonium chloride was added to the solution, and the mixture was extracted three times with 50 mL of dichloromethane. The solvent was removed from the organic phase by distillation under reduced pressure, and the mixture was dried under vacuum to obtain a crude product. The resulting crude product was dissolved in 200 mL of dichloromethane under air, and manganese dioxide (43.5 g, 500 mmol) was added. The mixture was stirred at room temperature (25°C) for 1 hour. The solution was filtered, and the solvent was removed from the organic phase by distillation under reduced pressure, followed by drying under vacuum. This was purified by column chromatography using a mixed solvent of hexane:ethyl acetate = 4:1 (volume ratio), yielding 1,1'-(1,3-phenylene)bis(prop-2-yn-1-one) (2.26 g, 12.4 mmol) as a red solid in a yield of 49.6%.

[0154] Example 2A Synthesis of 1,1'-((1,2-phenylenebis(oxy))bis(2,1-phenylene))bis(prop-2-yn-1-one) (Step 1: Synthesis of 2,2'-(1,2-phenylenebis(oxy))bis(benzaldehyde) Under an argon atmosphere, 2-fluorobenzaldehyde (2.48 g, 20.0 mmol) was dissolved in 8 mL of anhydrous dimethyl sulfoxide. Catechol (0.551 g, 5.0 mmol) and potassium carbonate (2.76 g, 20.0 mmol) were added, and the mixture was heated and stirred at 110°C for 3 hours. The solution was allowed to cool to room temperature (25°C), 20 mL of water was added, and the mixture was extracted three times with 20 mL of a 4:1 hexane:ethyl acetate mixed solvent. The solvent was removed from the resulting organic phase by distillation under reduced pressure, and the mixture was dried under vacuum. This afforded 2,2'-(1,2-phenylenebis(oxy))bis(benzaldehyde) (1.41 g, 4.43 mmol) as a pale yellow liquid in an 88.6% yield.

[0155] (Step 2: Synthesis of 1,1'-((1,2-phenylenebis(oxy))bis(2,1-phenylene))bis(prop-2-yn-1-one)) Under an argon atmosphere, 2,2'-(1,2-phenylenebis(oxy))bis(benzaldehyde) (1.27 g, 4.00 mmol) was dissolved in 40 mL of anhydrous tetrahydrofuran. After cooling to 0°C, 32.0 mL (16.0 mmol) of a 0.5 M tetrahydrofuran solution of ethynylmagnesium chloride was added dropwise over 30 minutes. The mixture was warmed to room temperature (25°C) and stirred at room temperature (25°C) for 19 hours. 200 mL of saturated aqueous ammonium chloride was added to the solution, and the mixture was extracted three times with 50 mL of dichloromethane. The solvent was removed from the organic phase by distillation under reduced pressure, and the mixture was dried under vacuum to obtain a crude product. The resulting crude product was dissolved in 150 mL of dichloromethane under air, and manganese dioxide (13.9 g, 160 mmol) was added. The mixture was stirred at room temperature (25°C) for 1 hour. The solution was filtered, and the solvent was removed from the organic phase by distillation under reduced pressure, followed by drying under vacuum. This was purified by column chromatography using a mixed solvent of hexane:ethyl acetate = 4:1 (volume ratio), yielding a pale yellow solid, 1,1'-((1,2-phenylenebis(oxy))bis(2,1-phenylene))bis(prop-2-yn-1-one) (0.500 g, 1.36 mmol), in a yield of 34.1%.

[0156] Example 3A Synthesis of 1,1'-((1,2-phenylenebis(oxy))bis(4,1-phenylene))bis(prop-2-yn-1-one) (Step 1: Synthesis of 4,4'-(1,2-phenylenebis(oxy))bis(benzaldehyde) Under an argon atmosphere, 4-fluoroobenzaldehyde (2.48 g, 20.0 mmol) was dissolved in 8 mL of anhydrous dimethyl sulfoxide. Catechol (0.551 g, 5.00 mmol) and potassium carbonate (2.76 g, 20.0 mmol) were added, and the mixture was heated and stirred at 110°C for 3 hours. The solution was allowed to cool to room temperature (25°C), 20 mL of water was added, and the mixture was extracted three times with 20 mL of a 4:1 hexane:ethyl acetate mixed solvent. The solvent was removed from the resulting organic phase by distillation under reduced pressure, and the mixture was dried under vacuum. This afforded 4,4'-(1,2-phenylenebis(oxy))bis(benzaldehyde) (1.44 g, 4.53 mmol) as a pale yellow solid in a 90.6% yield.

[0157] (Step 2: Synthesis of 1,1'-((1,2-phenylenebis(oxy))bis(4,1-phenylene))bis(prop-2-yn-1-one)) Under an argon atmosphere, 4,4'-(1,2-phenylenebis(oxy))bis(benzaldehyde) (1.44 g, 4.53 mmol) was dissolved in 45 mL of anhydrous tetrahydrofuran. After cooling to 0°C, 36.2 mL (18.1 mmol) of a 0.5 M tetrahydrofuran solution of ethynylmagnesium chloride was added dropwise over 30 minutes. The mixture was warmed to room temperature (25°C) and stirred at room temperature (25°C) for 19 hours. 200 mL of saturated aqueous ammonium chloride was added to the solution, and the mixture was extracted three times with 50 mL of dichloromethane. The solvent was removed from the organic phase by distillation under reduced pressure, and the mixture was dried under vacuum to obtain a crude product. The resulting crude product was dissolved in 45 mL of dichloromethane under air, and manganese dioxide (15.8 g, 182 mmol) was added. The mixture was stirred at room temperature (25°C) for 1 hour. The solution was filtered, and the solvent was removed from the organic phase by distillation under reduced pressure, followed by drying under vacuum. This was purified by column chromatography using a mixed solvent of hexane:ethyl acetate = 4:1 (volume ratio), yielding a pale yellow solid, 1,1'-((1,2-phenylenebis(oxy))bis(4,1-phenylene))bis(prop-2-yn-1-one) (1.11 g, 3.03 mmol), in a yield of 67.0%.

[0158] Example 4A Synthesis of 4,4'-oxybis((ethynylsulfonyl)benzene) (Step 1: Synthesis of 4,4'-oxydibenzenethiol) Under an argon atmosphere, 4,4'-oxydibenzenesulfonyl chloride (5.51 g, 15.0 mmol) was dissolved in 30 mL of dehydrated toluene and heated to 60°C. Triphenylphosphine (23.6 g, 90.0 mmol) was added, and the mixture was heated and stirred at 60°C for 15 minutes. The solution was allowed to cool to room temperature (25°C), 10 mL of water was added, and the mixture was extracted three times with 20 mL of ethyl acetate. The solvent was removed from the resulting organic phase by distillation under reduced pressure, and the mixture was dried under vacuum. The resulting pale yellow solid was dissolved in 400 mL of 10% aqueous sodium hydroxide solution and neutralized with 1.0 L of 1 M hydrochloric acid. The precipitated pale yellow solid was filtered, washed with 100 mL of water, and dried under vacuum. This afforded a pale yellow solid, 4,4'-oxydibenzenethiol (3.24 g, 13.8 mmol), in a yield of 92.1%.

[0159] (Step 2: Synthesis of 1,1'-((oxybis(4,1-phenylene))bis(sulfanediyl))bis(pyrrolidine-2,5-dione)) Under an argon atmosphere, N-chlorosuccinimide (2.81 g, 21.0 mmol) was dissolved in 40 mL of dry dichloromethane and cooled to 0°C. 4,4'-oxydibenzenethiol (2.34 g, 10.0 mmol) was added, and the mixture was heated and stirred at 0°C for 30 minutes. 40 mL (22.0 mmol) of 0.55 M triethylamine dichloromethane solution was added dropwise, and the mixture was stirred at 0°C for an additional 2 hours. 20 mL of water was added, and the mixture was extracted three times with 30 mL of dichloromethane. The solvent was removed from the resulting organic phase by distillation under reduced pressure, and the mixture was dried under vacuum. The resulting mixture was purified by column chromatography using a mixed solvent of methanol and dichloromethane (volume ratio: 1:50). As a result, a colorless, transparent solid, 1,1'-((oxybis(4,1-phenylene))bis(sulfanediyl))bis(pyrrolidine-2,5-dione) (4.30 g, 10.0 mmol) was quantitatively obtained.

[0160] (Step 3: Synthesis of (((oxybis(4,1-phenylene))bis(sulfanediyl))bis(ethyne-2,1-diyl))bis(trimethylsilane)) Under an argon atmosphere, trimethylsilylacetylene (2.46 g, 25.0 mmol) was dissolved in 70 mL of dry tetrahydrofuran and cooled to -78°C. 7.81 mL of a 2.69 M n-butyllithium tetrahydrofuran solution was added dropwise, and the mixture was stirred at -78°C for 30 minutes. 20 mL (10.0 mmol) of a 0.5 M 1,1'-((oxybis(4,1-phenylene))bis(sulfanediyl))bis(pyrrolidine-2,5-dione) tetrahydrofuran solution was added dropwise, and the mixture was warmed to room temperature (25°C) and stirred for 2 hours. 100 mL of saturated aqueous sodium bicarbonate solution was added, and the mixture was extracted five times with 40 mL of dichloromethane. The solvent was removed from the resulting organic phase by distillation under reduced pressure, and the mixture was dried under vacuum. The resulting mixture was purified by column chromatography using a mixed solvent of hexane:ethyl acetate = 50:1 by volume. As a result, a pale yellow solid (((oxybis(4,1-phenylene))bis(sulfanediyl))bis(ethyne-2,1-diyl))bis(trimethylsilane) (3.71 g, 8.72 mmol) was obtained in a yield of 87.2%.

[0161] (Step 4: Synthesis of 4,4'-oxybis((ethynylsulfonyl)benzene)) Under an argon atmosphere, (((oxybis(4,1-phenylene))bis(sulfanediyl))bis(ethyne-2,1-diyl))bis(trimethylsilane) (2.80 g, 6.55 mmol) was dissolved in 125 mL of dry dichloromethane, to which m-chloroperoxybenzoic acid (contains ca. 30% water) (9.69 g, 39.3 mmol) was added, followed by stirring at room temperature (25°C) for 27 hours. To this was added 100 mL of a 10% by weight aqueous solution of sodium thiosulfate, followed by extraction three times with 40 mL of dichloromethane. The resulting organic phase was further washed with 40 mL of saturated aqueous sodium bicarbonate. The solvent was removed from the resulting organic phase by distillation under reduced pressure, and the mixture was dried under vacuum to obtain a crude product. The resulting crude product was dissolved in 125 mL of ethanol, to which 12 mL of a 1.64 M aqueous solution of sodium fluoride was added, followed by stirring at room temperature (25°C) for 30 minutes. After adding 20 mL of water, the mixture was extracted three times with 40 mL of dichloromethane. The solvent was removed from the resulting organic phase by distillation under reduced pressure, and the resulting mixture was dried under vacuum. The resulting mixture was purified by column chromatography using a 2:1 volumetric mixture of hexane and ethyl acetate. This afforded a colorless, transparent solid, 4,4'-oxybis((ethynylsulfonyl)benzene) (1.47 g, 4.25 mmol), in a yield of 64.9%.

[0162] Example 5A Synthesis of 1,1'-(oxydi-1,4-phenylene)bis(prop-2-yn-1-one) Under an argon atmosphere, Bis(triphenylphosphine)palladium(II) dichloride (1.97 g, 2.80 mmol) was dissolved in 700 mL of dry tetrahydrofuran. Copper iodide (1.07 g, 5.60 mmol), 4,4'-Oxybis(benzoylchloride) (20.7 g, 70.0 mmol), triethylamine (14.2 g, 140 mmol), and trimethylsilylacetylene (16.5 g, 168 mmol) were added and stirred at room temperature for 2 hours. After adding 30 mL of water, the mixture was extracted three times with 20 mL of dichloromethane. The solvent was removed from the resulting organic phase by evaporation under reduced pressure, and the mixture was dried under vacuum to obtain a crude product. This crude product was dissolved in 500 mL of dry tetrahydrofuran, and 0.0100 M borax solution (50.5 mL, 0.505 mmol) was added dropwise. The mixture was stirred at room temperature for 15 minutes. After adding 800 mL of water, the mixture was extracted three times with 200 mL of dichloromethane. The solvent was removed from the resulting organic phase by distillation under reduced pressure, and the resulting mixture was dried under vacuum. The resulting mixture was purified by column chromatography using a 1:1 volumetric mixture of hexane and ethyl acetate. This afforded a pale yellow solid, 1,1'-(oxydi-1,4-phenylene)bis(prop-2-yn-1-one) (9.36 g, 34.1 mmol), in a yield of 48.7%.

[0163] Example 6A Synthesis of 1,1'-((1,4-phenylenebis(oxy))bis(4,1-phenylene))bis(prop-2-yn-1-one) (Step 1: Synthesis of 4,4'-(1,4-Phenylenebis(oxy))bis(benzaldehyde) Under an argon atmosphere, 4-fluoroobenzaldehyde (2.48 g, 20.0 mmol) was dissolved in 8 mL of anhydrous dimethyl sulfoxide. Hydroquinone (0.550 g, 5.00 mmol) and potassium carbonate (2.76 g, 20.0 mmol) were added, and the mixture was heated and stirred at 110°C for 5 hours. The solution was allowed to cool to room temperature (25°C), 20 mL of water was added, and the mixture was extracted three times with 20 mL of a 4:1 hexane:ethyl acetate mixed solvent. The solvent was removed from the resulting organic phase by distillation under reduced pressure, and the mixture was dried under vacuum. This afforded 4,4'-(1,4-Phenylenebis(oxy))bis(benzaldehyde) (1.25 g, 3.93 mmol) as a pale yellow solid in a 78.4% yield.

[0164] (Step 2: Synthesis of 1,1'-((1,4-phenylenebis(oxy))bis(4,1-phenylene))bis(prop-2-yn-1-one)) Under an argon atmosphere, 4,4'-(1,4-Phenylenebis(oxy))bis(benzaldehyde) (0.934 g, 2.94 mmol) was dissolved in 30 mL of anhydrous tetrahydrofuran. After cooling to 0°C, 23.6 mL (11.8 mmol) of a 0.5 M tetrahydrofuran solution of ethynylmagnesium chloride was added dropwise over 30 minutes. The mixture was warmed to room temperature (25°C) and stirred at room temperature (25°C) for 1 hour. 200 mL of saturated aqueous ammonium chloride was added to the solution, and the mixture was extracted three times with 50 mL of dichloromethane. The solvent was removed from the organic phase by distillation under reduced pressure, and the mixture was dried under vacuum to obtain a crude product. The resulting crude product was dissolved in 30 mL of dichloromethane under air, and manganese dioxide (10.2 g, 118 mmol) was added. The mixture was stirred at room temperature (25°C) for 2 hours. The solution was filtered, and the solvent was removed from the organic phase by distillation under reduced pressure, followed by drying under vacuum. This was purified by column chromatography using a mixed solvent of hexane:ethyl acetate = 4:1 (volume ratio), yielding a pale yellow solid, 1,1'-((1,4-phenylenebis(oxy))bis(4,1-phenylene))bis(prop-2-yn-1-one) (0.962 g, 2.62 mmol), in a yield of 89.1%.

[0165] {Production of Curable Composition} [Example 1B] <Preparation of Curable Composition 1B> 16.4644 g (60 mmol) of 1-(3-(4-propioloylphenoxy)phenyl)prop-2-yn-1-one was weighed out, and 0.1292 g (1.50 mmol) of piperazine was added. This was ground and mixed in a mortar for 30 minutes to obtain 16.5936 g of Curable Composition 1B.

[0166] [Example 2B] <Preparation of curable composition 2B> 11.0612 g of curable composition 2B was obtained in the same manner as in Example 1B, except that 10.9320 g (60 mmol) of 1,1'-(1,3-phenylene)bis(prop-2-yn-1-one) was used instead of 16.4644 g (60 mmol) of 1-(3-(4-propioloylphenoxy)phenyl)prop-2-yn-1-one.

[0167] [Example 3B] <Preparation of curable composition 3B> 16.4640 g (60 mmol) of 1-(3-(4-propioloylphenoxy)phenyl)prop-2-yn-1-one was weighed out and pulverized and mixed in a mortar for 30 minutes to obtain 16.4640 g of curable composition 3B.

[0168] [Example 4B] <Preparation of curable composition 4B> 10.9321 g of curable composition 4B was obtained in the same manner as in Example 3B, except that 10.9321 g (60 mmol) of 1,1'-(1,3-phenylene)bis(prop-2-yn-1-one) was used instead of 16.4644 g (60 mmol) of 1-(3-(4-propioloylphenoxy)phenyl)prop-2-yn-1-one.

[0169] [Example 5B] <Preparation of curable composition 5B> 0.080600 g (0.22 mmol) of 1,1'-((1,2-phenylenebis(oxy))bis(2,1-phenylene))bis(prop-2-yn-1-one) was weighed out, and 0.000474 g (0.00550 mmol) of piperazine was added. This was ground and mixed in a mortar for 30 minutes, thereby obtaining 0.081074 g of curable composition 5B.

[0170] Example 6B Preparation of Curable Composition 6B 0.081074 g of curable composition 6B was obtained in the same manner as in Example 5B, except that 0.080600 g (0.22 mmol) of 1,1′-((1,2-phenylenebis(oxy))bis(4,1-phenylene))bis(prop-2-yn-1-one) was used instead of 1,1′-((1,2-phenylenebis(oxy))bis(2,1-phenylene))bis(prop-2-yn-1-one).

[0171] Example 7B Preparation of Curable Composition 7B 0.06920 g (0.20 mmol) of 4,4'-oxybis((ethynylsulfonyl)benzene) was weighed out, and 0.00431 g (0.00500 mmol) of piperazine was added. The mixture was ground and mixed in a mortar for 30 minutes to obtain 0.07351 g of Curable Composition 7B.

[0172] [Example 8B] <Preparation of curable composition 8B> 16.5936 g of curable composition 8B was obtained in the same manner as in Example 1B, except that 16.4644 g (60 mmol) of 1,1′-(oxydi-1,4-phenylene)bis(prop-2-yn-1-one) was used instead of 16.4644 g (60 mmol) of 1-(3-(4-propioloylphenoxy)phenyl)prop-2-yn-1-one.

[0173] Example 9B Preparation of Curable Composition 9B 0.081074 g of curable composition 9B was obtained in the same manner as in Example 5B, except that 0.080600 g (0.22 mmol) of 1,1′-((1,4-phenylenebis(oxy))bis(4,1-phenylene))bis(prop-2-yn-1-one) was used instead of 1,1′-((1,2-phenylenebis(oxy))bis(2,1-phenylene))bis(prop-2-yn-1-one).

[0174] {Measurement of Properties of Curable Composition and Cured Product} [5% Weight Loss Temperature of Curable Composition] <Measurement of 5% Weight Loss Temperature of Curable Composition 1B> 7.8 mg of curable composition 1B was weighed out into a platinum pan, and the platinum pan was placed in a thermogravimetric analyzer ("STA7200" manufactured by Hitachi High-Tech Science Corporation). Under a nitrogen atmosphere, curable composition 1B weighed out into the platinum pan was heated from 30°C to 800°C at a heating rate of 10°C / min, and TG-DTA analysis was performed to measure the 5% weight loss temperature Td5, which was 475°C. FIG. 1 shows the results of TG-DTA analysis of curable composition 1B.

[0175] <Measurement of 5% Weight Loss Temperature of Curable Composition 2B> The 5% weight loss temperature Td5 of curable composition 2B was measured in the same manner as in <Measurement of 5% weight loss temperature of curable composition 1B>, and was found to be 419° C. The TG-DTA analysis results of curable composition 2B are shown in FIG.

[0176] <Measurement of 5% Weight Loss Temperature of Curable Composition 3B> The 5% weight loss temperature Td5 of curable composition 3B was measured in the same manner as in <Measurement of 5% weight loss temperature of curable composition 1B>, and was found to be 397° C. The TG-DTA analysis results of curable composition 3B are shown in FIG.

[0177] <Measurement of 5% Weight Loss Temperature of Curable Composition 4B> The 5% weight loss temperature Td5 of curable composition 4B was measured in the same manner as in <Measurement of 5% weight loss temperature of curable composition 1B>, and was found to be 155° C. The TG-DTA analysis results of curable composition 4B are shown in FIG.

[0178] <Measurement of 5% Weight Loss Temperature of Curable Composition 5B> The 5% weight loss temperature Td5 of curable composition 5B was measured in the same manner as in <Measurement of 5% weight loss temperature of curable composition 1B>, and was found to be 342° C. The TG-DTA analysis results of curable composition 5B are shown in FIG.

[0179] <Measurement of 5% Weight Loss Temperature of Curable Composition 6B> The 5% weight loss temperature Td5 of curable composition 6B was measured in the same manner as in <Measurement of 5% weight loss temperature of curable composition 1B>, and was found to be 481° C. The TG-DTA analysis results of curable composition 6B are shown in FIG.

[0180] <Measurement of 5% Weight Loss Temperature of Curable Composition 8B> The 5% weight loss temperature Td5 of curable composition 8B was measured in the same manner as in <Measurement of 5% weight loss temperature of curable composition 1B>, and was found to be 437° C. The TG-DTA analysis results of curable composition 8B are shown in FIG.

[0181] <Measurement of 5% Weight Loss Temperature of Curable Composition 9B> The 5% weight loss temperature Td5 of curable composition 9B was measured in the same manner as in <Measurement of 5% weight loss temperature of curable composition 1B>, and was found to be 418° C. The TG-DTA analysis results of curable composition 9B are shown in FIG.

[0182] [5% Weight Loss Temperature of Heat-Resistant Resin Material Obtained by Curing Curable Composition] <Measurement of 5% Weight Loss Temperature of Heat-Resistant Resin Material (Cured Product) 1Ca> 65.0 mg of curable composition 1B was melted at 120°C and poured into a 1 cm x 2 cm aluminum mold. Heat-resistant resin material (cured product) 1Ca was obtained by heating at 120°C for 6 hours in an oven under an air atmosphere. 5.7 mg of the obtained heat-resistant resin material (cured product) 1Ca was placed in a platinum pan, and the platinum pan was placed in a thermogravimetric analyzer ("STA7200" manufactured by Hitachi High-Tech Science Corporation). Heat-resistant resin material (cured product) 1Ca placed in a platinum pan was heated from 100°C to 800°C under a nitrogen atmosphere at a heating rate of 10°C / min. TG-DTA analysis was performed to measure the 5% weight loss temperature Td5, which was 480°C. Figure 9 shows the TG-DTA analysis results.

[0183] <Measurement of 5% Weight Loss Temperature of Heat-Resistant Resin Material (Cured Product) 2C> 65.0 mg of curable composition 2B was melted at 130°C and poured into a 1 cm x 2 cm aluminum mold. The mixture was then heated in an oven under air at 130°C for 6 hours to obtain heat-resistant resin material (cured product) 2C. The 5% weight loss temperature Td5 of heat-resistant resin material (cured product) 2C was measured in the same manner as in <Measurement of 5% weight loss temperature of heat-resistant resin material (cured product) 1Ca> above, and was found to be 427°C. Figure 10 shows the results of the TG-DTA analysis.

[0184] <Measurement of 5% Weight Loss Temperature of Heat-Resistant Resin Material (Cured Product) 3C> 65.2 mg of curable composition 3B was melted at 120°C and poured into a 1 cm x 2 cm aluminum mold. The mixture was then heated in an oven under air in stages at 120°C for 1 hour, 150°C for 2 hours, and 180°C for 2 hours to obtain heat-resistant resin material (cured product) 3C. The 5% weight loss temperature Td5 of heat-resistant resin material (cured product) 3C was measured in the same manner as in <Measurement of 5% Weight Loss Temperature of Heat-Resistant Resin Material (Cured Product) 1C> above, and was found to be 436°C. Figure 11 shows the TG-DTA analysis results.

[0185] <Measurement of 5% Weight Loss Temperature of Heat-Resistant Resin Material (Cured Product) 4C> 65.0 mg of curable composition 4B was melted at 130°C and poured into a 1 cm x 2 cm aluminum mold. The mixture was then heated in an oven under air in stages at 130°C for 1 hour, 150°C for 2 hours, and 180°C for 2 hours to obtain heat-resistant resin material (cured product) 4C. The 5% weight loss temperature Td5 of heat-resistant resin material (cured product) 4C was measured in the same manner as in <Measurement of 5% Weight Loss Temperature of Heat-Resistant Resin Material (Cured Product) 1C> above, and was found to be 398°C. The TG-DTA analysis results are shown in Figure 12.

[0186] <Measurement of 5% Weight Loss Temperature of Heat-Resistant Resin Material (Cured Product) 5C> 65.0 mg of Curable Composition 5B was melted at 120°C and poured into a 1 cm x 2 cm aluminum mold. The mixture was then heated at 120°C for 6 hours in an oven under an air atmosphere to obtain Heat-Resistant Resin Material (Cured Product) 5C. The 5% weight loss temperature Td5 of Heat-Resistant Resin Material (Cured Product) 5C was measured in the same manner as in <Measurement of 5% Weight Loss Temperature of Heat-Resistant Resin Material (Cured Product) 1Ca> above, and was found to be 341°C. Figure 13 shows the results of the TG-DTA analysis.

[0187] <Measurement of 5% Weight Loss Temperature of Heat-Resistant Resin Material (Cured Product) 6C> 65.0 mg of curable composition 6B was melted at 120°C and poured into a 1 cm x 2 cm aluminum mold. The mixture was then heated at 120°C for 6 hours in an oven under an air atmosphere to obtain heat-resistant resin material (cured product) 6C. The 5% weight loss temperature Td5 of heat-resistant resin material (cured product) 6C was measured in the same manner as in <Measurement of 5% weight loss temperature of heat-resistant resin material (cured product) 1Ca> above, and was found to be 458°C. Figure 14 shows the TG-DTA analysis results.

[0188] <Measurement of 5% Weight Loss Temperature of Heat-Resistant Resin Material (Cured Product) 7C> 65.0 mg of curable composition 7B was melted at 150°C and poured into a 1 cm x 2 cm aluminum mold. The mixture was then heated in an oven under air at 150°C for 1 hour, then at 160°C for 1 hour, and then at 180°C for 2 hours to obtain heat-resistant resin material (cured product) 7C. The 5% weight loss temperature Td5 of heat-resistant resin material (cured product) 7C was measured in the same manner as in <Measurement of 5% Weight Loss Temperature of Heat-Resistant Resin Material (Cured Product) 1Ca> above, and was found to be 292°C. The TG-DTA analysis results are shown in Figure 15.

[0189] <Measurement of 5% Weight Loss Temperature of Heat-Resistant Resin Material (Cured Product) 8C> 65.0 mg of curable composition 8B was heated at 120°C, placed in a 1 cm x 2 cm aluminum mold, and heated in an oven under air at 120°C for 2 hours, 150°C for 2 hours, and then 180°C for 2 hours to obtain heat-resistant resin material (cured product) 8C. The 5% weight loss temperature Td5 of heat-resistant resin material (cured product) 8C was measured in the same manner as in <Measurement of 5% Weight Loss Temperature of Heat-Resistant Resin Material (Cured Product) 1Ca> above, and was found to be 401°C. Figure 16 shows the TG-DTA analysis results.

[0190] <Measurement of 5% Weight Loss Temperature of Heat-Resistant Resin Material (Cured Product) 9C> 65.0 mg of curable composition 9B was heated at 120°C, placed in a 1 cm x 2 cm aluminum mold, and heated in an oven under air at 120°C for 2 hours, 150°C for 2 hours, and then 180°C for 2 hours to obtain heat-resistant resin material (cured product) 9C. The 5% weight loss temperature Td5 of heat-resistant resin material (cured product) 9C was measured in the same manner as in <Measurement of 5% Weight Loss Temperature of Heat-Resistant Resin Material (Cured Product) 1Ca> above, and was found to be 420°C. Figure 17 shows the results of TG-DTA analysis.

[0191] [Glass Transition Temperature (Tg) of Heat-Resistant Resin Material Obtained by Curing Curable Composition] <Measurement of Glass Transition Point (Tg) of Heat-Resistant Resin Material (Cured Product) 1Cb> 163 mg of curable composition 1B was melted at 120°C and poured into an 8 mm x 50 mm aluminum mold. The mixture was then heated in an oven under air in stages at 120°C for 1 hour, 150°C for 2 hours, and 180°C for 2 hours to obtain a 290 μm thick heat-resistant resin material (cured product) 1Cb. The obtained heat-resistant resin material (cured product) 1Cb was placed in a dynamic viscoelasticity measuring device (Hitachi High-Tech Science Corporation, "DMA7100"). The heat-resistant resin material (cured product) 1Cb was heated from 30°C to 450°C at a heating rate of 10°C / min under air, and the dynamic viscoelasticity was measured. The glass transition temperature (Tg) of the heat-resistant resin material (cured product) 1Cb obtained from the peak top of Tan δ was 351° C. The results of the DMA measurement are shown in FIG.

[0192] <Measurement of the glass transition point (Tg) of heat-resistant resin material (cured product) 2C> 163.3 mg of curable composition 2B was melted at 130°C and poured into an 8 mm x 50 mm aluminum mold. The mixture was heated at 130°C for 8 hours in an oven under air to obtain a 360 μm thick heat-resistant resin material (cured product) 2C. The obtained heat-resistant resin material (cured product) 2C was placed in a dynamic viscoelasticity measuring device (Hitachi High-Tech Science Corporation, "DMA7100"). The heat-resistant resin material (cured product) 2C was heated from 30°C to 400°C at a heating rate of 10°C / min under air, and the dynamic viscoelasticity was measured. No peak top of Tanδ was observed, and the glass transition point (Tg) was above 400°C. The DMA measurement results are shown in FIG. 19.

[0193] [Exothermic Onset Temperature (Tonset (°C)) and Exothermic Peak Temperature (Tpeak (°C)) of Curable Composition] <Measurement of Exothermic Onset Temperature and Exothermic Peak Temperature of Curable Composition 1B> 7.1 mg of curable composition 1B was weighed into an aluminum pan, and the aluminum pan was set in a differential scanning calorimeter (DSC7020, manufactured by Hitachi High-Tech Science Corporation). Under a nitrogen atmosphere, the composition was heated from 30°C to 300°C at a temperature increase rate of 5°C / min, and an exothermic spectrum was obtained to measure the exothermic onset temperature (Tonset (°C)) and exothermic peak temperature (Tpeak (°C)). In the present invention, the exothermic onset temperature (Tonset (°C)) is the intersection point between the tangent at the maximum slope point at the start of the peak and the baseline in the DSC exothermic spectrum, and the exothermic peak temperature (Tpeak (°C)) is the peak top temperature in the DES exothermic spectrum. The exotherm onset temperature (Tonset (°C)) of the curable composition 1B was 94.4°C, and the exotherm peak temperature (Tpeak (°C)) was 158°C.

[0194] <Measurement of exothermic onset temperature and exothermic peak temperature of curable composition 2B> The exothermic onset temperature (Tonset (°C)) and exothermic peak temperature (Tpeak (°C)) of curable composition 2B were measured in the same manner as in <Measurement of exothermic onset temperature and exothermic peak temperature of curable composition 1B>. The exothermic onset temperature (Tonset (°C)) of curable composition 2B was 85.0°C, and the exothermic peak temperature (Tpeak (°C)) was 130°C.

[0195] <Measurement of exothermic onset temperature and exothermic peak temperature of curable composition 3B> The exothermic onset temperature (Tonset (°C)) and exothermic peak temperature (Tpeak (°C)) of curable composition 3B were measured in the same manner as in <Measurement of exothermic onset temperature and exothermic peak temperature of curable composition 1B>. The exothermic onset temperature (Tonset (°C)) of curable composition 3B was 172°C, and the exothermic peak temperature (Tpeak (°C)) was 206°C.

[0196] <Measurement of exothermic onset temperature and exothermic peak temperature of curable composition 4B> The exothermic onset temperature (Tonset (°C)) and exothermic peak temperature (Tpeak (°C)) of curable composition 4B were measured in the same manner as in <Measurement of exothermic onset temperature and exothermic peak temperature of curable composition 1B>. The exothermic onset temperature (Tonset (°C)) of curable composition 4B was 179°C, and the exothermic peak temperature (Tpeak (°C)) was 206°C.

[0197] [Insoluble Content of Heat-Resistant Resin Material Obtained by Curing Curable Composition] <Measurement of Insoluble Content of Heat-Resistant Resin Material (Cured Product) 1C> 65 mg of curable composition 1B was placed in a 1 cm x 2 cm mold and heated in an oven under air at 120°C for 6 hours to obtain a film-like cured product of heat-resistant resin material (cured product) 1C. The obtained heat-resistant resin material (cured product) 1C was immersed in boiling tetrahydrofuran for 2 hours, then subjected to solvent replacement in acetone at room temperature (25±5°C) for 20 hours. The mass was measured every hour in an 80°C atmosphere under a reduced pressure of -0.1 MPa and dried until no mass change was observed for 3 hours or more (6 hours). The insoluble content of heat-resistant resin material (cured product) 1C was 100%. Insoluble content = mass of test piece after drying / mass of test piece before extraction × 100

[0198] <Measurement of insoluble fraction of heat-resistant resin material (cured product) 2C> A heat-resistant resin material (cured product) 2C was obtained in the same manner as in <Measurement of insoluble fraction of heat-resistant resin material (cured product) 1C>, except that curable composition 2B was used instead of curable composition 1B. The insoluble fraction of heat-resistant resin material (cured product) 2C was measured in the same manner as in <Measurement of insoluble fraction of heat-resistant resin material (cured product) 1C> described above. The insoluble fraction of heat-resistant resin material (cured product) 2C was 99.5%.

[0199] <Measurement of insoluble content of heat-resistant resin material (cured product) 3C> A heat-resistant resin material (cured product) 3C was obtained in the same manner as in <Measurement of insoluble content of heat-resistant resin material (cured product) 1C>, except that curable composition 3B was used instead of curable composition 1B. The insoluble content of heat-resistant resin material (cured product) 3C was measured in the same manner as in <Measurement of insoluble content of heat-resistant resin material (cured product) 1C> described above. The insoluble content of heat-resistant resin material (cured product) 3C was 99.0%.

[0200] <Measurement of insoluble content of heat-resistant resin material (cured product) 4C> A heat-resistant resin material (cured product) 4C was obtained in the same manner as in <Measurement of insoluble content of heat-resistant resin material (cured product) 1C>, except that curable composition 4B was used instead of curable composition 1B. The insoluble content of heat-resistant resin material (cured product) 4C was measured in the same manner as in <Measurement of insoluble content of heat-resistant resin material (cured product) 1C> described above. The insoluble content of heat-resistant resin material (cured product) 4C was 98.5%.

[0201] [Carbon Residual Ratio of the Cured Heat-Resistant Resin Material Obtained by Curing the Curable Composition] <Measurement of Carbon Residual Ratio of Heat-Resistant Resin Material (Cured Product) 1C> 65.1 mg of curable composition 1B was melted at 120°C and poured into a 1 cm x 2 cm aluminum mold. Heat-resistant resin material (cured product) 1C was obtained by heating at 120°C for 6 hours in an oven under an air atmosphere. 8.5 mg of heat-resistant resin material (cured product) 1C was placed in a platinum pan, and the platinum pan was placed in a thermogravimetric analyzer ("STA7200" manufactured by Hitachi High-Tech Science Corporation). Under a nitrogen atmosphere, the heat-resistant resin material (cured product) 1C placed in the platinum pan was held at 100°C for 30 minutes, heated from 100°C to 800°C at a heating rate of 10°C / min, and held at 800°C for 1 hour to obtain carbon material 1D. The mass fraction of heat-resistant resin material (cured product) 1C after being held at 100°C for 30 minutes was taken as 100, and the mass fraction after being heated at 800°C for 1 hour was used as the residual carbon fraction, which was 66.1%. Figure 20 shows the results of the TG-DTA analysis.

[0202] <Measurement of Residual Carbon Ratio of Heat-Resistant Resin Material (Cured Product) 2C> 65.0 mg of curable composition 2B was melted at 130°C and poured into a 1 cm x 2 cm aluminum mold. Heat-resistant resin material (cured product) 2C was obtained by heating at 130°C for 6 hours in an oven under air. The resulting heat-resistant resin material (cured product) 2C was heated in the same manner as in the above <Measurement of Residual Carbon Ratio of Heat-Resistant Resin Material (Cured Product) 1C> to obtain carbon material 2D. The residual carbon ratio of the resulting heat-resistant resin material (cured product) 2C was measured in the same manner as in the above <Measurement of Residual Carbon Ratio of Heat-Resistant Resin Material (Cured Product) 1C>, and was found to be 65.8%. The TG-DTA analysis results are shown in Figure 21.

[0203] Although the embodiments and examples of the present invention have been described above, the above-described embodiments and examples do not limit the scope of the invention as claimed. It should be noted that not all of the combinations of features described in the embodiments and examples are necessarily essential to the means for solving the problems of the invention, and that various modifications are possible without departing from the technical concept of the present invention.

Claims

1. Formula (A1): (In formula (A1), Z １１ is Ar １１ , -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R １１ -, -P(=O)(OR １２ ) -, -NR １３ CO-, -COO-, -NR １４ an n-valent aromatic organic group consisting of one or more groups selected from the group consisting of - and a direct bond; １１ , Ar １３ , Ar １４ and Ar １６ each independently represents an aromatic ring having a valence of 1 or more and which may have a substituent, １２ Ar is a divalent or higher aromatic ring which may have a substituent; １５ is an aromatic ring having a valence of 4 or more which may have a substituent, １１ -C≡CH is Ar １１ ~Ar １６ is bonded to any one of R １１ ~R １４ are each independently hydrogen or a monovalent organic group; Z １１ In the above, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R １１ -, -P(=O)(OR １２ ) -, -NR １３ CO-, -COO- and -NR １４ - is not directly bonded to another group. １１ - is -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R １５ - and -P(=O)(OR １６ )-, R １５ , R １６ Each of n is independently hydrogen or a monovalent organic group. １１ is an integer of 1 or more. １１ ~Ar １６ , R １１ ~R １６ , -X １１ When there are a plurality of -'s, they may be the same or different.

2. In the formula (A1), n １１ is 2, -X １１ - is -C(=O)-, Z １１ but In the case of , two -X １１ -C≡CH is in the ortho or meta position; １１ is 2, -X １１ - is -C(=O)-, Z １１ but In the case of , at least one -X １１ The curable composition of claim 1 , wherein -C≡CH is in the ortho or meta position relative to the N.

3. The compound having an ethynyl group represented by the formula (A1) is １１ is an integer of 2 or more, and n １１ The curable composition according to claim 1 or 2, wherein the average of is 1.5 or more.

4. The curable composition according to claim 1 or 2, which satisfies the following requirements (I) and / or (II): (I) in a TG-DTA (thermogravimetric-differential thermal analysis) measurement of the curable composition, the weight loss when heated in a nitrogen atmosphere from 30°C to 300°C at a heating rate of 10°C / min is 10% or less; and (II) in a TG-DTA (thermogravimetric-differential thermal analysis) measurement of a cured product of the curable composition obtained by heating under conditions of 50°C to 250°C for 48 hours or less, the weight loss when heated in a nitrogen atmosphere from 30°C to 300°C at a heating rate of 10°C / min is 10% or less.

5. The curable composition according to claim 1 or 2, wherein a cured product obtained by heating the curable composition under conditions of 50°C or higher and 250°C or lower for 48 hours or shorter is immersed in boiling tetrahydrofuran for 2 hours, followed by solvent replacement in acetone at 25°C±5°C for 6 hours or longer, and then dried in an 80°C atmosphere under a reduced pressure of -0.1 MPa until no change in mass is observed for 3 hours or longer when the mass is measured every hour. The insoluble content is 70% or more.

6. The compound having an ethynyl group represented by the formula (A1) is a compound represented by the following formula (A2): (In formula (A2), Ar ２１ ~Ar ２３ Each independently represents Ar ２４ , Ar is an n-valent aromatic organic group consisting of one or more groups selected from the group consisting of ２４ , Ar ２６ , Ar ２７ and Ar ２９ each independently represents an aromatic ring having a valence of 1 or more and which may have a substituent, ２５ Ar is a divalent or higher aromatic ring which may have a substituent; ２８ represents an aromatic ring having a valence of 4 or more which may have a substituent, ２１ and Q. ２２ are each independently -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ２１ -, -P(=O)(OR ２２ ) -, -NR ２３ CO-, -COO-, -NR ２４ - and a direct bond, R ２１ ~R ２４ Each of -X is independently hydrogen or a monovalent organic group. ２１ --X ２３ - is each independently -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ２５ - and -P(=O)(OR ２６ )-, R ２５ , R ２６ Each of n is independently hydrogen or a monovalent organic group. ２１ ~n ２４ is an integer of 0 or 1 or more, ２５ is an integer of 1 or more, and n ２４ If is 0, n ２５ is an integer of 2 or more, ２４ is an integer of 1 or more, and n ２３ If is 0, n ２１ +n ２５ is an integer of 2 or more, ２３ and n ２４ When each of n is an integer of 1 or more, ２１ +n ２２ +n ２５ is an integer of 2 or more. ２１ ~Ar ２９ , -X ２１ --X ２３ -, R ２１ ~R ２６ When there are a plurality of n, they may be the same or different. ２４ is 0, n ２５ is 2, -X ２３ - is -C(=O)-, -Ar ２３ -but In the case of , two -X ２３ -C≡CH is in the ortho or meta position. ２１ is 1, n ２３ is 0, n ２４ is 1, -X ２１ - and -X ２３ - is -C(=O)-, -Ar ２１ -Q ２２ -Ar ２３ -but In the case of , at least one -X ２３ The curable composition according to claim 1 or 2, wherein the compound has an ethynyl group represented by the formula:

7. The compound having an ethynyl group represented by the formula (A2) is represented by the following formula (A3): (In formula (A3), Q ２１ and Q. ２２ are each independently -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ２１ -, -P(=O)(OR ２２ ) -, -NR ２３ CO-, -COO-, -NR ２４ - and a direct bond, R ２１ ~R ２４ Each of -X is independently hydrogen or a monovalent organic group. ２１ --X ２３ - is each independently -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ２５ - and -P(=O)(OR ２６ )-, R ２５ , R ２６ Each of n is independently hydrogen or a monovalent organic group. ２１ ~n ２４ is an integer of 0 or 1 or more, ２５ is an integer of 1 or more, and n ２４ If is 0, n ２５ is an integer of 2 or more, ２４ is an integer of 1 or more, and n ２３ If is 0, n ２１ +n ２５ is an integer of 2 or more, ２３ and n ２４ When each of n is an integer of 1 or more, ２１ +n ２２ +n ２５ is an integer of 2 or more. ２１ --X ２３ -, R ２１ ~R ２６ When there are a plurality of n, they may be the same or different. ２４ is 0, n ２５ is 2, -X ２３ When - is -C(=O)-, two -X ２３ -C≡CH is in the ortho or meta position. ２１ , n ２４ and n ２５ is 1, n ２３ is 0, -X ２１ - and -X ２３ - is -C(=O)-, Q ２２ is NR ２４ , R ２４ When is phenyl, -X ２１ The curable composition according to claim 6, wherein the compound has an ethynyl group represented by the formula:

8. The curable composition according to claim 1 or 2, which is of one-component or multi-component type.

9. Formula (B); (In formula (B), Z ３１ is Ar ３１ , -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ３１ -, -P(=O)(OR ３２ ) -, -NR ３３ CO-, -COO-, -NR ３４ an n-valent aromatic organic group consisting of one or more groups selected from the group consisting of - and a direct bond; ３１ , Ar ３３ , Ar ３４ and Ar ３６ each independently represents an aromatic ring having a valence of 1 or more and which may have a substituent, ３２ Ar is a divalent or higher aromatic ring which may have a substituent; ３５ is an aromatic ring having a valence of 4 or more which may have a substituent, ３１ -C≡CH is Ar ３１ ~Ar ３６ is bonded to any one of R ３１ ~R ３４ are each independently hydrogen or a monovalent organic group; Z ３１ In the above, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ３１ -, -P(=O)(OR ３２ ) -, -NR ３３ CO-, -COO- and -NR ３４ - is not directly bonded to another group. ３１ - is -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ３５ - and -P(=O)(OR ３６ )-, R ３５ , R ３６ Each of n is independently hydrogen or a monovalent organic group. ３１ is an integer of 2 or more. ３１ ~Ar ３６ , R ３１ ~R ３６ , -X ３１ When there are a plurality of -, they may be the same or different. ３１ - is -C(=O)-, Z ３１ When is an unsubstituted phenyl ring, n ３１ is an integer from 3 to 6. ３１ is 2, -X ３１ - is -C(=O)-, Z ３１ but In the case of , at least one -X ３１ -C≡CH is in the ortho position to N, or two -X ３１ -C≡CH is in the para and meta positions relative to N. ３１ is 2, -X ３１ - is -C(=O)- or -S(=O) ２ -, Z ３１ but In the case of , at least one -X ３１ -C≡CH is in the ortho or meta position relative to O. ３１ is 2, -X ３１ - is -C(=O)-, Z ３１ but In the case of , at least one -X ３１ -C≡CH is in the ortho or meta position relative to the amide bond. ３１ is 2, -X ３１ - is -C(=O)-, Z ３１ but In the case of , at least one -X ３１ -C≡CH is in the ortho or para position relative to the amide bond.

10. A heat-resistant resin material obtained by curing the curable composition according to claim 1 or the compound according to claim 9.

11. An adhesive comprising the curable composition according to claim 1 or the compound according to claim 9.

12. A sealant comprising the curable composition according to claim 1 or the compound according to claim 9.

13. A potting material comprising the curable composition according to claim 1 or the compound according to claim 9.

14. An encapsulant comprising the curable composition according to claim 1 or the compound according to claim 9.

15. Formula (A): (In formula (A), -X- is -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ａ - and -P(=O)(OR ｂ When there are a plurality of -X-, they may be the same or different, R ａ is hydrogen or a monovalent organic group, R ａ When there are a plurality of R, they may be the same or different from each other, ｂ is hydrogen or a monovalent organic group, R ｂ wherein, when there are a plurality of groups, they may be the same or different, Z is an n-valent organic group, and n is an integer of 1 or more.

16. Formula (A): (In formula (A), -X- is -C(=O)-, -S(=O)-, -S(=O) ２ -, -P(=O)R ａ - and -P(=O)(OR ｂ When there are a plurality of -X-, they may be the same or different, R ａ is hydrogen or a monovalent organic group, R ａ When there are a plurality of R, they may be the same or different from each other, ｂ is hydrogen or a monovalent organic group, R ｂ wherein, when there are a plurality of groups, they may be the same or different, Z is an n-valent organic group, and n is an integer of 1 or more.

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