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

Abstract

The present application provides a curable resin composition which can be cured at a low curing temperature and in a short time, has less restrictions on reaction conditions at the time of curing, and has a high glass transition temperature of a cured product obtained by curing, and can obtain a cured product having excellent heat resistance, and a novel compound having an ethynyl group which exhibits high reactivity, can be cured at a low curing temperature and in a short time, has less restrictions on reaction conditions at the time of curing, and has a high glass transition temperature of a cured product obtained by curing, and can obtain a cured product having excellent heat resistance. As a solution, the present application provides a curable composition characterized by containing a compound having an ethynyl group represented by formula (A1).

Description

Technical Field

[0001] This invention relates to a curable composition containing a compound having an acetylene group, a novel acetylene-based compound, and a heat-resistant resin material. More specifically, it relates to a curable composition in which a highly reactive acetylene group is used as a crosslinking group, and 1,3,5-triacylarylene is generated through position-selective metal-free trimerization of an alkyne. A heat-resistant resin material is obtained by curing this curable composition. The invention also relates to a novel acetylene-based compound as a component of this curable composition, and a heat-resistant resin material obtained by curing this compound or a composition containing the compound and additives. Background Technology

[0002] Curable compositions are used in a variety of applications, such as electronic materials, composite material matrices, and coating materials, due to their ability to impart high heat resistance or dimensional stability. For example, in the field of electronic materials, they have become indispensable materials for interlayer insulation in semiconductor packaging materials or printed wiring substrates.

[0003] In recent years, research has been conducted in the field of semiconductor packaging materials to replace silicon (Si) semiconductor devices with silicon carbide (SiC) to reduce power loss. Because SiC semiconductors can operate at higher temperatures than Si semiconductors, packaging materials for SiC semiconductors require significantly higher heat resistance than previously used semiconductor packaging materials, exceeding 200°C. Furthermore, since semiconductor packaging materials for SiC semiconductors are exposed to high temperatures for extended periods, the curable resin compositions used must possess long-term high heat resistance (chemical heat resistance). Therefore, curable resin compositions suitable for use as semiconductor packaging materials for SiC semiconductors, due to their long-term high heat resistance, are expected to become extremely useful materials not only for packaging materials but also for heat-resistant adhesives or insulating materials, coatings, and matrix resins for fiber-reinforced composites.

[0004] Patent documents 1-3 disclose an epoxy resin composition that serves as a curable composition for encapsulating semiconductor elements. The composition is mainly composed of epoxy resins such as bisphenol A type epoxy resin, and contains liquid acid anhydride or phenolic varnish as a curing agent, as well as additives such as inorganic fillers.

[0005] Patent documents 4-7 disclose curable compositions containing cyanate ester compounds. These curable compositions are cured by a cyclization trimerization reaction of the cyanate ester group (-OCN group) of the cyanate ester compound, resulting in cured products exhibiting excellent properties such as high heat resistance, low water absorption, and high insulation. Furthermore, curable compositions using epoxy resin and maleimide resin can impart excellent electrical properties, mechanical properties, and chemical resistance, thus showing promise as candidate materials for encapsulation resins for SiC power semiconductors.

[0006] Patent document 8 discloses a soluble polymer obtained by cyclization trimerization of a diyne compound.

[0007] Patent documents Patent Document 1: Japanese Patent Application Publication No. 2003-160639 Patent Document 2: Japanese Patent Application Publication No. 2009-292996 Patent Document 3: Japanese Patent Application Publication No. 2008-255367 Patent Document 4: Japanese Patent Application Publication No. 7-70315 Patent Document 5: Japanese Patent Application Publication No. 2011-6683 Patent Document 6: Japanese Patent Application Publication No. 2010-53085 Patent Document 7: Japanese Patent Application Publication No. 8-176299 Patent Document 8: U.S. Patent Application Publication No. 2006 / 0247410 Summary of the Invention The epoxy resin composition has a low glass transition temperature (physical heat resistance) and is unsatisfactory in terms of heat resistance.

[0008] While curable compositions containing cyanate esters exhibit excellent heat resistance, they typically require a transition metal catalyst during curing. Without a catalyst, prolonged heating at high temperatures (e.g., above 250°C) is necessary. Furthermore, the curing reaction forms a highly cross-linked three-dimensional network structure, resulting in a brittle and unsatisfactory cured product. These factors hinder widespread application and prevent its widespread adoption.

[0009] Curable compositions containing acetylene groups have attracted considerable attention due to their ability to generate heat-resistant aromatic rings through curing reactions. However, the low reactivity of acetylene groups necessitates the use of transition metal catalysts, UV light irradiation, and high-temperature heating during curing, and poses a risk of adverse effects on the materials used in the curable composition, thus limiting their applications and commercialization.

[0010] The inventors have discovered that alkynes conjugated with electron-withdrawing substituents exhibit high reactivity, can react with a wide range of substrates under mild reaction conditions with fewer condition-dependent limitations, and the reaction orientation can be tunable.

[0011] One of the problems to be solved by the present invention is to provide a curable resin composition that can be cured at a low curing temperature and in a short time, with few restrictions on the reaction conditions during curing, and the resulting cured product has a high glass transition temperature and can obtain a cured product with excellent heat resistance.

[0012] One of the problems to be solved by this invention is to provide a novel compound with an acetylene group, which exhibits high reactivity, can be cured at low curing temperatures and in a short time, has few restrictions on the reaction conditions during curing, and produces a cured product with a high glass transition temperature, thus obtaining a cured product with excellent heat resistance.

[0013] To address the aforementioned issues, the inventors have conducted in-depth research on a curing system that can be cured at low temperatures, has low volatile content, and whose cured product maintains high stability at high temperatures.

[0014] The results showed that the compound containing the electron-withdrawing group X, represented by formula (A1), was found to contain the electron-withdrawing group X. 11 The present invention comprises a curable composition of a conjugated acetylene group compound, which, in TG-DTA (thermogravimetric-differential calorimetry) determination, exhibits a weight loss of less than 5% when heated from 30°C to 300°C at a heating rate of 10°C / min under a nitrogen atmosphere, and is characterized as suitable for use in the peripheral applications of high-temperature driven semiconductor devices. Details are as follows.

[0015] [Item 1] A curable composition, characterized in that it contains a compound having an acetylene group as represented by formula (A1), [Chemistry 1]

[0016] In formula (A1), Z 11 Selected from Ar 11 , [Chemistry 2]

[0017] -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 11 -、-P(=O)(OR 12 )-、-NR 13 CO-, -COO-, -NR 14 - and n-valent aromatic organic groups consisting of one or more groups in direct bonding. Ar11 Ar 13 Ar 14 and Ar 16 Each is an aromatic ring with a valence of more than one valence that can independently have substituents. Ar 12 It can be a divalent or higher aromatic ring that has substituents. Ar 15 It can be an aromatic ring with a valence of 4 or more and have substituents. -X 11 -C≡CH and Ar 11 ~Ar 16 Any one of the bonds in, R 11 ~R 14 Each is independently a hydrogen or monovalent organic group. Z 11 Medium, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 11 -、-P(=O)(OR 12 )-、-NR 13 CO-, -COO- and -NR 14 - They are not directly bonded to each other. -X 11 - is selected from -C (=O)-, -S (=O)-, -S (=O)2-, -P (=O)R 15 - and -P (=O) (OR 16 The divalent group in )- R 15 R 16 Each is independently a hydrogen or monovalent organic group. n 11 Integers greater than or equal to 1 Ar 11 ~Ar 16 R 11 ~R 16 -X 11 When there are multiple, they can be the same as each other or different from each other.

[0018] [Item 2] The curable composition according to Item 1, characterized in that, in the formula (A1), n 11 =2, -X 11 - is -C (=O)-, Z 11 for, [Chemistry 3]

[0019] At that time, 2 -X 11-C≡CH is located in the adjacent or intermediate position. n 11 =2, -X 11 - is -C (=O)-, Z 11 for, [Chemistry 4]

[0020] At least one -X 11 -C≡CH is located adjacent to or between N.

[0021] [Item 3] The curable composition according to item 1 or 2, characterized in that the compound having an acetylene group represented by formula (A1) contains n 11 For compounds that are integers greater than or equal to 2, the total number of n in the curing composition is... 11 The average is above 1.5.

[0022] [Item 4] The curable composition according to any one of items 1 to 3 is characterized in that it satisfies the following requirements (I) and / or (II); (I) In the TG-DTA (thermogravimetric-differential calorimetry) determination of the cured composition, the weight loss when heated from 30°C to 300°C at a heating rate of 10°C / min under a nitrogen atmosphere is less than 10%. (II) In the TG-DTA (thermogravimetric-differential thermal analysis) determination of the cured product of the curable composition obtained by heating at a temperature of 50°C to 250°C and for 48 hours or less, the weight loss when heated from 30°C to 300°C at a heating rate of 10°C / min under a nitrogen atmosphere is less than 10%.

[0023] [Item 5] The curable composition according to any one of items 1 to 4 is characterized in that, for the cured product obtained by heating the curable composition at a temperature of 50°C to 250°C for 48 hours or less, after impregnation in boiling tetrahydrofuran for 2 hours, solvent replacement is carried out in acetone at 25°C ± 5°C for 6 hours or more, and drying is carried out under reduced pressure of -0.1 MPa at an atmosphere of 80°C, with the mass measured every hour until no mass change is observed after 3 hours or more, at which point the insoluble component is 70% or more.

[0024] [Item 6] The curable composition according to any one of items 1 to 5, characterized in that the compound having an acetylene group represented by formula (A1) is the compound having an acetylene group represented by formula (A2) below; [Chemistry 5]

[0025] In formula (A2), Ar 21~Ar 23 Each independently selected from Ar 24 , [Chemistry 6]

[0026] An n-valent aromatic organic group consisting of one or more groups. Ar 24 Ar 26 Ar 27 and Ar 29 Each is an aromatic ring with a valence of more than one valence that can independently have substituents. Ar 25 It can be a divalent or higher aromatic ring that has substituents. Ar 28 It can be an aromatic ring with a valence of 4 or more and have substituents. Q 21 and Q 22 Each is independently selected from -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 21 -、-P(=O)(OR 22 )-、-NR 23 CO-, -COO-, -NR 24 - and groups in direct bonding. R 21 ~R 24 Each is independently a hydrogen or monovalent organic group. -X 21 -~-X 23 - Each is independently selected from -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 25 - and -P (=O) (OR 26 The divalent group in ) R 25 R 26 Each is independently a hydrogen or monovalent organic group. n 21 ~n 24 n is an integer greater than or equal to 0 or 1. 25 n is an integer greater than or equal to 1. 24 When n is 0, 25 Integers greater than 2 n 24 n is an integer greater than or equal to 1, and n 23 When n is 0, 21 +n 25 Integers greater than 2 n 23 and n 24When n is an integer greater than or equal to 1, 21 +n 22 +n 25 Integers greater than 2 Ar 21 ~Ar 29 -X 21 -~-X 23 -、R 21 ~R 26 When there are multiple instances, they can be the same as each other or different from each other.

[0027] n 24 =0, n 25 =2, -X 23 - is -C (=O)-, -Ar 23 -for, [Chemistry 7]

[0028] At that time, 2 -X 23 -C≡CH is located in the adjacent or intermediate position. n 21 For 1, n 23 =0, n 24 =1, -X 21 -and-X 23 - is -C (=O)-, -Ar 21 -Q 22 -Ar 23 -for, [Chemistry 8]

[0029] At least one -X 23 -C≡CH is located adjacent to or between N.

[0030] [Item 7] The curable composition according to item 6 is characterized in that the compound having an acetylene group represented by formula (A2) is the compound having an acetylene group represented by formula (A3) below; [Chemistry 9]

[0031] In equation (A3), Q 21 and Q 22 Each is independently selected from -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 21 -、-P(=O)(OR 22 )-、-NR 23 CO-, -COO-, -NR 24 - and groups in direct bonding. R 21 ~R 24 Each is independently a hydrogen or monovalent organic group. -X 21 -~-X 23 - Each is independently selected from -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 25 - and -P (=O) (OR 26 The divalent group in )- R 25 R 26 Each is independently a hydrogen or monovalent organic group. n 21 ~n 24 n is an integer greater than or equal to 0 or 1. 25 n is an integer greater than or equal to 1. 24 When n is 0, 25 Integers greater than 2 n 24 n is an integer greater than or equal to 1 and 23 When n is 0, 21 +n 25 Integers greater than 2 n 23 and n 24 When n is an integer greater than or equal to 1, 21 +n 22 +n 25 Integers greater than 2 -X 21 -~-X 23 -、R 21 ~R 26 When there are multiple instances, they can be the same as each other or different from each other. n 24 =0, n 25 =2, -X 23 When - is -C (=O)-, there are 2 -X. 23 -C≡CH is located in the adjacent or intermediate position. n 21 n 24 and n 25 For 1, n 23 =0, -X 21 -and-X 23 - is -C (=O)-, Q 22 For NR 24 R 24 When it is phenyl, -X 21 -C≡CH is located adjacent to or between N.

[0032] [Item 8] The curable composition according to any one of items 1 to 6 is characterized in that it is a single-liquid or multi-liquid composition.

[0033] [Item 9] A compound having an acetylene group, characterized by being represented by formula (B); [Chemistry 10]

[0034] In equation (B), Z 31 Selected from Ar 31 , [Chemistry 11]

[0035] -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 31 -、-P(=O)(OR 32 )-、-NR 33 CO-, -COO-, -NR 34 - and n-valent aromatic organic groups consisting of one or more groups in direct bonding. Ar 31 Ar 33 Ar 34 and Ar 36 Each is an aromatic ring with a valence of more than one valence that can independently have substituents. Ar 32 It can be a divalent or higher aromatic ring that has substituents. Ar 35 It can be an aromatic ring with a valence of 4 or more and have substituents. -X 31 -C≡CH and Ar 31 ~Ar 36 Any one of the bonds in, R 31 ~R 34 Each is independently a hydrogen or monovalent organic group. Z 31 Medium, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 31 -、-P(=O)(OR 32 )-、-NR 33 CO-, -COO- and -NR 34 - They are not directly bonded to each other. -X 31 - is selected from -C (=O)-, -S (=O)-, -S (=O)2-, -P (=O)R 35 - and -P (=O) (OR36 The divalent base in )- R 35 R 36 Each is independently a hydrogen or monovalent organic group. n 31 Integers greater than 2 Ar 31 ~Ar 36 R 31 ~R 36 -X 31 When there are multiple instances, they can be the same as each other or different from each other. -X 31 - is -C (=O)-, Z 31 When n is a phenyl ring without substituents, 31 Integers between 3 and 6 n 31 =2, -X 31 - is -C (=O)-, Z 31 for, [Chemistry 12]

[0036] At least one -X 31 -C≡CH is adjacent to N, or two -X 31 -C≡CH is located in the anti- and meta positions relative to N. n 31 =2, -X 31 - is -C (=O)- or -S (=O)2-, Z 31 for, [Chemistry 13]

[0037] At least one -X 31 -C≡CH is located adjacent to or between O. n 31 =2, -X 31 - is -C (=O)-, Z 31 for, [Chemistry 14]

[0038] At least one -X 31 -C≡CH is located in the ortho or meta position relative to the amide bond. n 31 =2, -X 31 - is -C (=O)-, Z 31 for, [Chemistry 15]

[0039] At least one -X 31 -C≡CH is located in the ortho or para position relative to the amide bond.

[0040] [Item 10] A heat-resistant resin material, characterized in that it is obtained by curing the curable composition described in any one of items 1 to 8 or the compound described in item 9.

[0041] [Item 11] An adhesive, characterized in that it contains any one of items 1 to 8 of the curable composition or the compound described in item 9.

[0042] [Item 12] A sealing material, characterized in that it contains any one of items 1 to 8 of the curable composition or the compound described in item 9.

[0043] [Item 13] A potting material, characterized in that it contains any one of items 1 to 8 or the compound described in item 9.

[0044] [Item 14] An encapsulation material, characterized in that it contains a curable composition as described in any one of items 1 to 8 or a compound as described in item 9.

[0045] [Item 15] A carbon material, characterized in that it is obtained by calcining a curable composition or a cured product thereof containing a compound having an acetylene group as represented by formula (A). [Chemistry 16]

[0046] In formula (A), -X- is selected from -C (=O)-, -S (=O)-, -S (=O)2-, -P (=O)R a - and -P (=O) (OR b When there are multiple divalent groups (-X-) in the - group, they can be the same as or different from each other. R a R is a hydrogen or monovalent organic group. a When there are multiple instances, they can be the same as each other or different from each other. R b R is a hydrogen or monovalent organic group. b When there are multiple instances, they can be the same as each other or different from each other. Z is an n-valent organic group. n is an integer greater than or equal to 1.

[0047] [Item 16] A prepreg, characterized in that it contains a compound having an acetylene group as represented by formula (A) and a fibrous reinforcing material. [Chemistry 17]

[0048] In formula (A), -X- is selected from -C (=O)-, -S (=O)-, -S (=O)2-, -P (=O)R a - and -P (=O) (OR b When there are multiple divalent groups (-X-) in the - group, they can be the same as or different from each other. R a R is a hydrogen or monovalent organic group. a When there are multiple instances, they can be the same as each other or different from each other. R b R is a hydrogen or monovalent organic group. b When there are multiple instances, they can be the same as each other or different from each other. Z is an n-valent organic group. n is an integer greater than or equal to 1.

[0049] According to the present invention, a curable resin composition is provided that can be cured at a low curing temperature and in a short time, with few restrictions on the reaction conditions during curing, and the cured product has a high glass transition temperature, resulting in a cured product with excellent heat resistance.

[0050] According to the present invention, a novel compound having an acetylene group is provided, wherein the acetylene group exhibits high reactivity, can be cured at low curing temperatures and in a short time, has few restrictions on the reaction conditions during curing, and the cured product has a high glass transition temperature, thus obtaining a cured product with excellent heat resistance.

[0051] The curable composition containing a compound with an acetylene group involved in this invention has high reactivity because the acetylene group is an acetylene group conjugated with a specific electron-withdrawing group, and can be cured at low curing temperatures and in a short time. Furthermore, it has fewer restrictions on the use of transition metal catalysts, UV light irradiation, high-temperature heating, and other reaction conditions during curing, and can also reduce the amount of reaction promoter used and control the reaction orientation.

[0052] Furthermore, by including filler materials, the thermal expansion of the cured product can be further reduced. Attached Figure Description

[0053] Figure 1 A graph showing the TG-DTA analysis results of a curable composition 1B according to one embodiment of the present invention.

[0054] Figure 2 A graph showing the TG-DTA analysis results of a curable composition 2B according to one embodiment of the present invention.

[0055] Figure 3 A graph showing the TG-DTA analysis results of a curable composition 3B according to one embodiment of the present invention.

[0056] Figure 4 A graph showing the TG-DTA analysis results of a curable composition 4B according to one embodiment of the present invention.

[0057] Figure 5 A graph showing the TG-DTA analysis results of a curable composition 5B according to one embodiment of the present invention.

[0058] Figure 6 A graph showing the TG-DTA analysis results of a curable composition 6B according to one embodiment of the present invention.

[0059] Figure 7 A graph showing the TG-DTA analysis results of a curable composition 8B according to one embodiment of the present invention.

[0060] Figure 8 A graph showing the TG-DTA analysis results of a curable composition 9B according to one embodiment of the present invention.

[0061] Figure 9 A graph showing the TG-DTA analysis results of the heat-resistant resin material 1Ca (cured product 1Ca) obtained by curing the curable composition 1B according to one embodiment of the present invention.

[0062] Figure 10 A graph showing the TG-DTA analysis results of a heat-resistant resin material 2C (cured product 2C) obtained by curing a curable composition 2B according to one embodiment of the present invention.

[0063] Figure 11 A graph showing the TG-DTA analysis results of a heat-resistant resin material 3C (cured product 3C) obtained by curing a curable composition 3B according to one embodiment of the present invention.

[0064] Figure 12 A graph showing the TG-DTA analysis results of a heat-resistant resin material 4C (cured product 4C) obtained by curing a curable composition 4B according to one embodiment of the present invention.

[0065] Figure 13 A graph showing the TG-DTA analysis results of a heat-resistant resin material 5C (cured product 5C) obtained by curing a curable composition 5B according to one embodiment of the present invention.

[0066] Figure 14A graph showing the TG-DTA analysis results of a heat-resistant resin material 6C (cured product 6C) obtained by curing a curable composition 6B according to one embodiment of the present invention.

[0067] Figure 15 A graph showing the TG-DTA analysis results of a heat-resistant resin material 7C (cured product 7C) obtained by curing a curable composition 7B according to one embodiment of the present invention.

[0068] Figure 16 A graph showing the TG-DTA analysis results of a heat-resistant resin material 8C (cured product 8C) obtained by curing a curable composition 8B according to one embodiment of the present invention.

[0069] Figure 17 A graph showing the TG-DTA analysis results of a heat-resistant resin material 9C (cured product 9C) obtained by curing a curable composition 9B according to one embodiment of the present invention.

[0070] Figure 18 A graph showing the DMA measurement results of the heat-resistant resin material 1Cb (cured product 1Cb) obtained by curing the curable composition 1B according to one embodiment of the present invention during the dynamic viscoelasticity (Tg) measurement.

[0071] Figure 19 A graph showing the DMA measurement results of the heat-resistant resin material 2C (cured product 2C) obtained by curing the curable composition 2B according to one embodiment of the present invention during the dynamic viscoelasticity (Tg) measurement.

[0072] Figure 20 A graph showing the TG-DTA analysis results of the char residue of the heat-resistant resin material 1C (cured product 1C) obtained by curing the curable composition 1B according to one embodiment of the present invention.

[0073] Figure 21 A graph showing the TG-DTA analysis results of the char residue of the heat-resistant resin material 2C (cured product 2C) obtained by curing the curable composition 2B according to one embodiment of the present invention. Detailed Implementation

[0074] The present invention will now be described in detail.

[0075] [Curing composition] The curable composition of the present invention, which contains a specific compound having an acetylene group, contains the formula (A1). [Chemistry 18]

[0076] The curable composition of the compound represented by the compound having an acetylene group.

[0077] The present invention relates to a curable composition containing a compound having an acetylene group as represented by formula (A1), wherein the main curing reaction is a cross-linking reaction in which the acetylene group in the compound having an acetylene group as represented by formula (A1) undergoes cyclic trimerization. The cross-linking reaction in which the acetylene group undergoes cyclic trimerization is a reaction that forms a benzene ring, and is a reaction in which low molecular weight compound components are not produced or removed during the cross-linking reaction.

[0078] <Compounds containing an acetylene group as represented by formula (A1)> The compounds with an acetylene group represented by formula (A1) are shown below.

[0079] [Chemistry 19]

[0080] Z in equation (A1) 11 Selected from Ar 11 , [Chemistry 20]

[0081] -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 11 -、-P(=O)(OR 12 )-、-NR 13 CO-, -COO-, -NR 14 - and n-valent aromatic organic groups consisting of one or more groups in direct bonding. Ar 11 Ar 13 Ar 14 and Ar 16 Each is an aromatic ring with a valence of more than one valence that can independently have substituents. Ar 12 It can be a divalent or higher aromatic ring that has substituents. Ar 15 It can be an aromatic ring with a valence of 4 or more and have substituents. -X 11 -C≡CH and Ar 11 ~Ar 16 Any one of the bonds in, R 11 ~R 14 Each is independently a hydrogen or monovalent organic group. Z 11 Medium, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R11 -、-P(=O)(OR 12 )-、-NR 13 CO-, -COO- and -NR 14 - They are not directly bonded to each other.

[0082] -X 11 - is selected from -C (=O)-, -S (=O)-, -S (=O)2-, -P (=O)R 15 - and -P (=O) (OR 16 The divalent group in )- R 15 R 16 Each is an organic group that is either hydrogen or monovalent.

[0083] n 11 Integers greater than or equal to 1.

[0084] Ar 11 ~Ar 16 R 11 ~R 16 -X 11 When there are multiple, they can be the same as each other or different from each other.

[0085] In the curable composition of the present invention containing a specific acetylene-containing compound, n represents the acetylene-containing compound represented by formula (A1). 11 =2, -X 11 - is -C (=O)-, Z 11 for, [Chemistry 21]

[0086] At that time, 2 -X 11 -C≡CH is preferably located in the adjacent or intermediate position.

[0087] In the curable compositions of the present invention containing specific acetylene-containing compounds, with regard to the acetylene-containing compounds represented by formula (A1), n 11 =2, -X 11 - is -C (=O)-, Z 11 for, [Chemistry 22]

[0088] At that time, 2 -X 11 -C≡CH is preferably located in the adjacent or intermediate position.

[0089] In the curable compositions of the present invention containing specific acetylene-containing compounds, with regard to the acetylene-containing compounds represented by formula (A1), n 11 =2, -X 11 - is -C (=O)-, Z 11 for, [Chemistry 23]

[0090] At least one -X 11 -C≡CH is preferably located in the adjacent or intermediate position relative to N.

[0091] Z in the constructive formula (A1) 11 Ar 11 ~Ar 16 Aromatic rings can include hydrocarbon aromatic rings and heteroaromatic rings. These can be either monocyclic or polycyclic. They can be rings that are aromatic in themselves, or rings fused with aromatic rings, or rings formed by multiple bonds of these rings.

[0092] Examples of aromatic rings in hydrocarbons include benzene rings, naphthalene rings, anthracene rings, tetraphenylene rings, pyrene rings, spirodifluorene rings, phenanthrene rings, and perylene rings.

[0093] Examples of heteroaromatic rings include pyridine rings, pyrazine rings, pyrimidine rings, triazine rings, pyridazine rings, pyrrole rings, imidazole rings, oxazole rings, oxadiazole rings, thiadiazole rings, thiazolium rings, phenoxazine rings, isoquinoline rings, benzopyran rings, indole rings, pyridoline rings, acridine rings, quinoline rings, carbazole rings, quinoxaline rings, furan rings, benzofuran rings, dibenzofuran rings, dibenzodioxin rings, thiophene rings, benzothiophene rings, thioene rings, phenothiazine rings, thiophene-thiophene rings, dithiophene-thiophene rings, pyrazole rings, phosphaticyclopentadiene rings, dibenzophosphaticyclopentadiene rings, dibenzosiloxane pentadiene rings, and dibenzoborane pentadiene rings.

[0094] Z in equation (A1) 11 As Ar 11 Ar 13 Ar 14 and Ar 16 The term "aromatic ring with a valence of 1 or higher" can be exemplified by removing one or more hydrogen atoms directly bonded to the carbon atom or heteroatom (nitrogen atom, sulfur atom, etc.) constituting the aromatic ring, and by forming one or more aromatic rings with a valence of 1 or higher formed by bonding two or more such aromatic rings.

[0095] Z in equation (A1) 11 As Ar 12The term "aromatic ring with a valence of 2 or higher" can be exemplified by removing two or more hydrogen atoms directly bonded to the carbon or heteroatoms (nitrogen, sulfur, etc.) constituting the aromatic ring, and by forming one or more aromatic rings with a valence of 2 or higher formed by bonding two or more aromatic rings with a valence of 1 or higher.

[0096] Z in equation (A1) 11 As Ar 15 The term "aromatic ring with a valence of 4 or higher" can be exemplified by removing 4 or more hydrogen atoms directly bonded to the carbon or heteroatoms (nitrogen, sulfur, etc.) constituting the aromatic ring, and by forming one or more aromatic rings with a valence of 4 or higher formed by the bonding of 2 or more aromatic rings with a valence of 1 or higher.

[0097] Z in equation (A1) 11 Ar 11 ~Ar 16 The substituents that can be present, as long as they do not interfere with -X 11 The acetylene group in the -C≡CH group can be subjected to a cross-linking reaction based on cyclic trimerization, and there are no particular limitations. For example, one or more of the following can be selected: fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, cyanate ester group (-OCN group), alkyl group with 1 to 20 carbon atoms, haloalkyl group with 1 to 20 carbon atoms, aryl group with 6 to 30 carbon atoms, alkoxy group with 1 to 20 carbon atoms, aryloxy group with 6 to 30 carbon atoms, ketal alkyl group with 2 to 20 carbon atoms, ketal aryl group with 7 to 30 carbon atoms, amino group, alkylamino group with 1 to 20 carbon atoms, dialkylamino group with 2 to 40 carbon atoms, carboxyl group, hydroxyl group, alkyl ester group of carboxylic acid with 1 to 21 carbon atoms, alkenyl group with 2 to 20 carbon atoms, and alkyne group with 2 to 20 carbon atoms.

[0098] Z in equation (A1) 11 Ar 11 ~Ar 16 There is no particular limit to the number of substituents it can have, but it can be more than zero.

[0099] Z in equation (A1) 11 R in 11 ~R 14 and X 11 As R 15 ~R 16 A monovalent organic group, as long as it does not interfere with -X 11 The acetylene group in the -C≡CH group can be subjected to a cross-linking reaction based on cyclic trimerization, and there are no particular limitations. For example, one or more of the following can be listed: alkyl groups with 1 to 20 carbon atoms, haloalkyl groups with 1 to 20 carbon atoms, and aryl groups with 6 to 30 carbon atoms.

[0100] n in equation (A1) 11n is an integer greater than or equal to 1, representing the total number of units in the curable composition. 11 The average (apparent n) 11 For example, it is 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, 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.

[0101] In the curable composition of the present invention, the compound having an acetylene group represented by the above formula (A1) can be used with n 11 A mixture of compounds with different values.

[0102] When the total amount of n in the cured composition 11 When the average value of n in the curing composition is small, the molecular weight of the cured product obtained from the curing composition is difficult to increase, the degree of crosslinking of the cured product is insufficient, and there is a risk of problems with heat resistance or mechanical properties. 11 If the average value is too high, the curing property of the curing composition is too high, which may cause problems in terms of storage stability or operability. In addition, there is a risk that the cured product will become brittle.

[0103] Here, "n in the curing composition as a whole" 11 "Average" refers to the average of each n in formula (A1) in the curable composition. 11 The sum of the products of the value and the proportion of the corresponding compound can be obtained by the following formula.

[0104] [n in the curing composition as a whole] 11 The average] = {1 × [n 11 The proportion of compounds with a value of 1 (mol%) + 2 × [n 11 The proportion of compounds with a concentration of 2 (mol%) +n×[n 11 [Proportion of compounds with value n (mol%)] / 100 In a curable composition containing a specific acetylene-containing compound of the present invention, the acetylene-containing compound represented by formula (A1) is preferably the acetylene-containing compound represented by formula (A2) below. [Chemistry 24]

[0105] (In formula (A2), Ar) 21 ~Ar 23 Each independently selected from Ar 24 , [Chemistry 25]

[0106] An n-valent aromatic organic group consisting of one or more groups. Ar 24 Ar 26 Ar 27 and Ar 29 Each is an aromatic ring with a valence of more than one valence that can independently have substituents. Ar 25 It can be a divalent or higher aromatic ring that has substituents. Ar 28 It can be an aromatic ring with a valence of 4 or more and have substituents. Q 21 and Q 22 Each is independently selected from -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 21 -、-P(=O)(OR 22 )-、-NR 23 CO-, -COO-, -NR 24 - and groups in direct bonding. R 21 ~R 24 Each is an organic group that is either hydrogen or monovalent.

[0107] -X 21 -~-X 23 - Each is independently selected from -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 25 - and -P (=O) (OR 26 The divalent group in )- R 25 R 26 Each is an organic group that is either hydrogen or monovalent.

[0108] n 21 ~n 24 n is an integer greater than or equal to 0 or 1. 25 n is an integer greater than or equal to 1. 24 When n is 0, 25 Integers greater than 2 n 24 n is an integer greater than or equal to 1 and 23 When n is 0, 21 +n 25 Integers greater than 2 n 23 and n 24 When n is an integer greater than or equal to 1, 21 +n 22 +n25 Integers greater than or equal to 2.

[0109] Ar 21 ~Ar 29 -X 21 -~-X 23 -、R 21 ~R 26 When there are multiple instances, they can be the same as each other or different from each other. n 24 =0, n 25 =2, -X 23 - is -C (=O)-, -Ar 23 -for, [Chemistry 26]

[0110] At that time, 2 -X 23 -C≡CH is located in the adjacent or intermediate position.

[0111] n 21 For 1, n 23 =0, n 24 =1, -X 21 -and-X 23 - is -C (=O)-, -Ar 21 -Q 22 -Ar 23 -for, [Chemistry 27]

[0112] At least one -X 11 -C≡CH is adjacent or intermediate with respect to N. Ar in formula (A2) 21 ~Ar 29 The aromatic ring and Z in the formula (A1) 11 Ar 11 ~Ar 16 They have the same aromatic rings.

[0113] Ar in formula (A2) 21 ~Ar 29 The substituents that can be present and Z in formula (A1) 11 Ar 11 ~Ar 16 They can have the same substituents.

[0114] Q in equation (A2) 21 and Q 22 R in 11 ~R 14 and -X 21 -~-X23 - as R 15 ~R 16 The monovalent organic group, and Z in formula (A1) 11 R in 11 ~R 14 and -X 21 -~-X 23 - as R 15 ~R 16 The monovalent organic groups are the same.

[0115] In the curable composition of the present invention containing a specific compound having an acetylene group, the compound having an acetylene group represented by the above formula (A2) is more preferably the compound having an acetylene group represented by the following formula (A3); [Chemistry 28]

[0116] (In formula (A3), Q) 21 and Q 22 Each is independently selected from -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 21 -、-P(=O)(OR 22 )-、-NR 23 CO-, -COO-, -NR 24 - and groups in direct bonding. R 21 ~R 24 Each is an organic group that is either hydrogen or monovalent.

[0117] -X 21 -~-X 23 - Each is independently selected from -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 25 - and -P (=O) (OR 26 The divalent group in )- R 25 R 26 Each is an organic group that is either hydrogen or monovalent.

[0118] n 21 ~n 24 n is an integer greater than or equal to 0 or 1. 25 n is an integer greater than or equal to 1. 24 When n is 0, 25 Integers greater than 2 n 24 n is an integer greater than or equal to 1 and 23 When n is 0, 21 +n 25Integers greater than 2 n 23 and n 24 When n is an integer greater than or equal to 1, 21 +n 22 +n 25 Integers greater than or equal to 2.

[0119] -X 21 -~-X 23 -、R 21 ~R 26 When there are multiple instances, they can be the same as each other or different from each other.

[0120] n 24 =0, n 25 =2, -X 23 When - is -C (=O)-, there are 2 -X. 23 -C≡CH is located in the adjacent or intermediate position.

[0121] n 21 n 24 and n 25 For 1, n 23 =0, -X 21 -and-X 23 - is -C (=O)-, Q 22 For NR 24 R 24 When it is phenyl, -X 21 -C≡CH is adjacent or intermediate with respect to N. In the curable composition of the present invention, the compound containing the acetylene group represented by formula (A1) is used as -X 11 - is a compound of -C (=O)-, for example, the following compounds (Aa1)~(Aa98) can be listed.

[0122] [Chemistry 29]

[0123] [Chemistry 30]

[0124] [Chemistry 31]

[0125] [Chemistry 32]

[0126] [Chemistry 33]

[0127] [Chemistry 34]

[0128] In the curable composition of the present invention, the compound containing the acetylene group represented by formula (A1) is used as -X 11 Compounds that are -S (=O)-, such as the following compounds (Ab1) to (Ab35).

[0129] [Chemistry 35]

[0130] [Chemistry 36]

[0131] In the curable composition of the present invention, the compound containing the acetylene group represented by formula (A1) is used as -X 11 - is a compound of -S (=O)2-, for example, the following compounds (Ac1)~(Ac35) can be listed.

[0132] [Chemistry 37]

[0133] [Chemistry 38]

[0134] In the curable composition of the present invention, the compound containing the acetylene group represented by formula (A1) is used as -X 11 -for-P(=O)R 15 - compounds, for example, the following compounds (Ad1) ~ (Ad64) can be listed.

[0135] [Chemistry 39]

[0136] [Chemistry 40]

[0137] [Chemistry 41]

[0138] In the curable composition of the present invention, the compound containing the acetylene group represented by formula (A1) is used as -X 11 - is -P (=O) (OR) 16 Compounds of type )-, for example, the following compounds (Ae1)~(Ae32) can be listed.

[0139] [Chemistry 42]

[0140] [Chemistry 43]

[0141] Among the compounds containing an acetylene group represented by formula (A1) in the curable composition of the present invention, As X 11 Compounds having a -C (=O)- motif are preferred, especially those represented by (Aa1), (Aa4)~(Aa6), and (Aa8)~(Aa95) above. As X 11 - is a compound of -S (=O)-, preferably a compound represented by (Ab1)~(Ab2) and (Aa5)~(Ab34) above. As X 11 - is a compound of -S (=O)2-, preferably a compound represented by (Ac1)~(Ac2) and (Ac5)~(Ac34) above. As X 11 -for-P(=O)R 15 The compounds of - are preferably those represented by (Ad1)~(Ad2), (Ad5)~(Ad34), and (Ad37)~(Ad63) above. As X 11 - is -P (=O) (OR) 16 The compounds of (Ae1) to (Ae2) and (Ae5) to (Ae34) are preferred.

[0142] Among these, from the perspective of the reactivity of compounds containing an acetylene group, -X is more preferred. 11 - is selected from one or more of -C(=O)-, -S(=O)- and -S(=O)2-.

[0143] Further optimization of -X 11 - is a compound of -C (=O)- or -S (=O)2-.

[0144] More preferably -X 11 The compounds represented by (Aa1), (Aa4)~(Aa6), (Aa8)~(Aa95) above, which are of the form -C (=O)-, are particularly preferred to have -X. 11 - is the compound represented by (Ac1)~(Aa35) above for -S(=O)2-.

[0145] In the curable composition of the present invention, the compound containing an acetylene group represented by formula (A1) is used as n 11Compounds with a value of 1 include, for example, compounds selected from (Aa1) to (Aa95) with only one -C(=O)-C≡CH, compounds selected from (Ab1) to (Ab35) with only one -S(=O)-C≡CH, compounds selected from (Ac1) to (Ac35) with only one -S(=O)2-C≡CH, and compounds selected from (Ad1) to (Ad64) with only one -P(=O)R 15 Compounds with only one -C≡CH group, and compounds from (Ae1) to (Ae32) above, where -P (=O) (OR) 16 One or more of the following compounds: )-C≡CH with only one molecule.

[0146] <The content of compounds containing acetylene groups as represented by formula (A1)> In the curable composition containing a compound having an acetylene group as represented by formula (A1) according to the present invention, the content of the compound having an acetylene group as represented by formula (A1) is not particularly limited. It can be appropriately adjusted according to the intended use or desired properties.

[0147] For example, the total amount of a curable composition may be a compound having an acetylene group as represented by formula (A1).

[0148] For example, the total amount of the curable composition may be less than 100% by mass, preferably less than 99.7% by mass, more preferably less than 99.5% by mass, for example more than 10% by mass, more preferably more than 30% by mass, and more preferably more than 50% by mass of the compound represented by formula (A1) having an acetylene group.

[0149] <Additives> The present invention relates to a curable composition containing a compound having an acetylene group as represented by formula (A1). In addition to the compound having an acetylene group as represented by formula (A1), one or more additives selected from the following can be formulated as needed: curable components, curing accelerators, fillers, fibers, flame retardants, solvents, antioxidants, light stabilizers, ultraviolet absorbers, resins, coupling agents, conductive material colorants, release agents, dispersants, adhesion promoters, tackifiers, anti-sagging agents, thixotropic agents, pore-forming materials, foaming agents, emulsifiers, plasticizers, etc.

[0150] (The curing components other than those represented by formula (A1) which contain an acetylene group) The curable component other than the compound with an acetylene group represented by formula (A1) is not particularly limited as long as it is a component that reacts with the compound with an acetylene group represented by formula (A1) or a component that can form an interpenetrating polymer network structure (IPN structure) when the curable composition containing the compound with an acetylene group represented by formula (A1) of the present invention is cured.

[0151] Examples include compounds containing an acetylenic group other than those represented by formula (A1), compounds having vinyl, allyl, (meth)acryloyloxy, maleimide, or other vinyl unsaturated groups, and compounds having one or more reactive groups selected from cyanate (-OCN), hydroxyl, epoxy, isocyanate, amino, mercapto, carboxyl, hydrolyzable silyl, etc.

[0152] Other than the compounds containing an acetylene group represented by formula (A1), examples of curing agents include compounds selected from those represented by (C) below. [Chemistry 44]

[0153] (where Z) 41 For Z in equation (A1) 11 Different groups, X 41 For X in equation (A1) 11 Same or different groups, n 41 (Integers greater than or equal to 1.) Terephthaloylacetylene, N,N'-bis(4-ethynylcarbonylphenylene aniline), compounds containing an ethynyl group other than those represented by formula (A1) and 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 acid compounds having one or more (meth)acryloyloxy groups in the molecule, maleimide compounds having one or more maleimide groups in the molecule, cyanate compounds having one or more cyanate groups (-OCN groups) in the molecule, polyhydroxy compounds, epoxy resins, polyisocyanate compounds, polyamine compounds, polythiols, polycarboxylic acid compounds, hydrolyzable silicon compounds, phenolic resins, reactive ester compounds, unsaturated polyester resins, polybutadiene resins, benzoxazine resins, etc.

[0154] The content of curing components other than the acetylene-containing compound represented by formula (A1) is not particularly limited. It can be adjusted appropriately according to the application or the desired properties. For example, as a percentage of 100% by mass of the total curing composition, it may contain 90% by mass or less of the curing components other than the acetylene-containing compound represented by formula (A1), preferably 70% by mass or less, more preferably 50% by mass or less, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more.

[0155] (Curing accelerator) The curing accelerator is any compound that can promote the curing of the following components, without any particular limitation: a compound having an acetylene group as represented by formula (A1), a component that reacts with a compound having an acetylene group as represented by formula (A1), and a component that can form an interpenetrating polymer network structure (IPN structure) when the curable composition containing a compound having an acetylene group as represented by formula (A1) is cured.

[0156] For example, one or more of the following can be listed: amine compounds (primary amines, secondary amines, tertiary amines, guanidines, aminosilanes, amino acids, ketimines, etc.), imidazole compounds, organic peroxides, organophosphorus compounds, azo compounds, organic acid metal salts, organometallic compounds, etc.

[0157] Examples of 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, (dimethylaminomethyl)phenol, 2,4,6- Tris(dimethylaminomethyl)phenol, tripropylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), guanidine, phenylguanidine, diphenylguanidine, butyl biguanide, 1-o-tolyl biguanide, 1-phenyl biguanide, dicyandiamide, DL-alanine, γ-aminobutyric acid, δ-aminovaleric acid, L-glutamic acid, glutamine, glycine, L-theanine, glycylglycine, γ-aminohexanoic acid, L-glutamine, aspartic acid, asparagine, L-citrulline, L-arginine, L-leucine, L-serine and other amino acid compounds, compounds containing ketone imine groups, and salts of these amine compounds, etc., are one or more of the following.

[0158] Examples of imidazole compounds include, for instance, one or more selected from imidazole, 2-methylimidazolium, 2-ethylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 2-undecylimidazolium, 1-benzyl-2-methylimidazolium, 2-heptadecylimidazolium, 4,5-diphenylimidazolium, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazolium, 2,4-dimethylimidazolium, 2-phenyl-4-methylimidazolium, 2-ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, and 2-phenyl-4-methylimidazoline. Imidazole compounds can also be masked using masking agents such as acrylonitrile, phenyl diisocyanate, toluene diisocyanate, naphthalene diisocyanate, methylene diphenyl isocyanate, and melamine acrylate.

[0159] Examples of organic peroxides include, for example, one or more selected from dicumyl peroxide, benzoyl peroxide, cumyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxide)-3-hexyne, di-tert-butyl peroxide, tert-butylcumyl peroxide, tert-butyl hydroperoxide, α,α'-di(tert-butylperoxide)dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane, di-tert-butyl isophthalate peroxide, tert-butyl peroxide, 2,2-bis(tert-butylperoxide)butane, 2,2-bis(tert-butylperoxide)octane, 2,5-dimethyl-2,5-di(benzoylperoxide)hexane, di(trimethylsilyl)peroxide, trimethylsilyltriphenylsilyl peroxide, dodecyl peroxide, methyl ethyl ketone peroxide, etc.

[0160] As an organophosphorus compound, examples include one or more selected from ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine / triphenylborane complex, tetraphenylphosphine tetraphenylboronic acid, etc.

[0161] Examples of azo compounds include 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile), 2,2'-azobis(2-amidinylpropane) dihydrochloride, 2,2'-azobis(2,4-dimethylpentanonitrile), 2,2'-azobis(isobutyronitrile), 2,2'-azobis-2-methylbutyronitrile, 1,1-azobis(1-cyclohexanecarboxylonitrile), 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(methyl isobutyrate), and azobisisobutyronitrile.

[0162] As metal salts of organic acids, examples include metal salts of one or more fatty acids selected from aliphatic carboxylic acids (octanoic acid, lauric acid, stearic acid, neodecanoic acid, oleic acid, etc.) with carbon 6 to 18 (benzoic acid, naphthoic acid, etc.) and aromatic carboxylic acids (benzoic acid, naphthoic acid, etc.) with carbon 6 to 18 (selected from one or more 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.).

[0163] As organometallic compounds, metal chelate compounds preferably have one or more of β-diketones (acetylacetone, benzoylacetone, stearoylbenzoylmethane, dibenzoylmethane, ethyl acetoacetate, dehydroacetic acid, etc.) as chelating components. Examples of metals include one or more selected from magnesium, calcium, zinc, cobalt, nickel, tin, barium, iron, aluminum, copper, manganese, zirconium, titanium, indium, lead, etc.

[0164] In the curable composition of the present invention containing a compound having an acetylene group as represented by formula (A1), an amine compound is preferably used as a curing accelerator.

[0165] The curable compositions of the present invention containing compounds having an acetylene group as represented by formula (A1) can promote curing without the use of metal components such as organic acid metal salts or organometallic compounds.

[0166] The content of the curing accelerator is not particularly limited. It can be appropriately adjusted according to the reactivity of the curing component in the curing composition or the curing conditions. For example, it is 0.01 parts by mass or more, preferably 0.05 parts by mass or more, for example 5.0 parts by mass or less, and preferably 1.0 parts by mass or less, relative to 100 parts by mass of the compound having an acetylene group as represented by formula (A1).

[0167] (Filling material) As filler materials, one or more can be selected from oxides, hydroxides, sulfates, carbonates, borates, phosphates, titanates, nitrides, carbides, etc. For example, one or more of the following can be listed: silica (amorphous silica, crystalline silica, fused silica, spherical silica, precipitated silica, anhydrous silica, hydrated silica, etc.), alumina, titanium dioxide, magnesium oxide, 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, Neunburg silica, silicon nitride, aluminum nitride, boron nitride, aluminum borate, carbon black, iron oxide, resin powder (styrene resin powder, acrylic resin powder, vinyl chloride resin powder, olefin resin powder, polyurethane resin powder, polyamide resin powder, polyester resin powder, etc.), glass microspheres, volcanic ash microspheres, etc.

[0168] There are no particular restrictions on the shape of the filler material. For example, it can be spherical, amorphous (crushed), fibrous, etc.

[0169] There is no particular limitation on the volume average particle size of the filler material. For example, it is 0.01 μm or more, preferably 0.1 μm or more, for example 100 μm or less, preferably 50 μm or less.

[0170] The filler material may also be surface-treated. Surface treatment agents used for surface treatment of the filler material may include, for example, one or more selected from silane coupling agents such as epoxy silane, vinyl silane, (meth)propylene silane, amino silane, alkoxy silane, and titanium coupling agents.

[0171] The content of the filler material is not particularly limited. It can be adjusted appropriately according to the application or desired characteristics. For example, relative to 100 parts by mass of the compound with an acetylene group represented by formula (A1), the filler material is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, for example, 1200 parts by mass or less, preferably 1000 parts by mass or less.

[0172] (fiber) The fiber can be any type of twisted, untwisted, or untwisted yarn. When forming fiber-reinforced composite materials, untwisted or untwisted yarns are preferred from the perspective of formability. Furthermore, materials or fabrics with unidirectional fiber orientation can be used. As the fabric, plain weave, satin weave, and other similar fabrics can be used.

[0173] As a fiber, for example, one or more can be selected from carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber, potassium titanate fiber, etc.

[0174] There is no particular limitation on the fiber diameter. For example, it is 0.01 μm or more, preferably 0.1 μm or more, for example, 100 mm or less, preferably 50 mm or less.

[0175] The fibers may also be surface treated. Surface treatment agents used for surface treatment of fibers may include, for example, one or more selected from silane coupling agents such as epoxy silane, vinyl silane, (meth)propylene silane, amino silane, alkoxy silane, and titanium coupling agents.

[0176] The fiber content is not particularly limited. It can be adjusted appropriately according to the intended use or desired properties. For example, relative to 100 parts by mass of the compound containing an acetylene group as represented by formula (A1), the fiber content is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, for example, 1200 parts by mass or less, preferably 1000 parts by mass or less.

[0177] (Flame retardant) As a flame retardant, there are no particular limitations as long as it can impart flame retardancy to the curing composition and / or the cured product of the curing composition. For example, one or more flame retardants selected from halogenated flame retardants (bromine-based flame retardants (pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A and hexabromocyclododecane, etc.), chlorinated flame retardants (chlorinated paraffins, etc.)) and phosphorus-based flame retardants (condensed phosphate esters, cyclic phosphate esters and other phosphate ester compounds, cyclic phosphazenes and other phosphazene compounds, dialkylphosphinate aluminum salts and other phosphinate salts flame retardants, melamine phosphates, melamine polyphosphates and other melamine phosphate compounds, phosphine oxide compounds having diphenylphosphine oxide groups, etc.) can be listed.

[0178] There is no particular limitation on the content of flame retardant. A quantity that does not impair the properties and imparts the necessary flame retardancy may be used relative to the curing composition and / or the cured product of the curing composition.

[0179] (solvent) The curable composition may, as needed, contain a solvent capable of dissolving or dispersing the acetylene group represented by formula (A1) without reacting with the acetylene group represented by formula (A1). There are no particular limitations on the solvent, and examples include one or more selected from 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.

[0180] There is no particular limitation on the amount of solvent. When impregnating fibers or coating articles with the curable composition, an amount that imparts impregnation or coating properties may be used.

[0181] (Antioxidants) As an antioxidant, it is not particularly limited as long as it can impart antioxidant properties (anti-aging properties) and weather resistance to the curable composition and / or the cured product of the curable composition. For example, one or more of the following can be listed: hindered phenolic antioxidants, monophenolic antioxidants, bisphenolic antioxidants, polyphenolic antioxidants, etc.

[0182] (Light stabilizer) As a light stabilizer, it 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 selected from benzotriazole light stabilizers, hindered amine light stabilizers, benzoate ester light stabilizers, etc. can be listed.

[0183] (UV absorber) As a UV absorber, it is not particularly limited as long as it can impart UV resistance stability (surface weather resistance) to the curable composition and / or the cured product of the curable composition. For example, one or more of the following can be listed: benzophenone-based UV absorbers, benzotriazole-based UV absorbers, salicylate-based UV absorbers, substituted acrylonitrile-based UV absorbers, and metal chelate-based UV absorbers.

[0184] (Resin) As a resin, any resin with a weight-average molecular weight of 500 or higher is acceptable, without any particular limitation. For example, one or more of the following can be listed: polyimide resin, polyamide resin, polybenzimidazole resin, polybenzoxazole resin, polyester resin, polyurethane resin, phenolic resin, polyetheretherketone resin, polyetherketone resin, polyethersulfone resin, polyphenylene ether resin, polyether resin, polyketone resin, acetal resin, polyolefin resin, polystyrene resin, vinyl chloride resin, fluororesin, vinyl ester resin, vinyl alcohol resin, vinyl alcohol acetal resin, acrylic resin, synthetic rubber, diene resin, grafted resin, core-shell resin, block resin, etc.

[0185] (Coupled agent) As coupling agents, examples include one or more selected from silane coupling agents such as epoxy silane, vinyl silane, (meth)propylene silane, amino silane, alkoxy silane, titanium coupling agents, phosphorus coupling agents, aluminum coupling agents, boron coupling agents, zirconium coupling agents, etc.

[0186] (Conductive materials) As a conductive material, there are no particular limitations as long as it is a material that can impart conductivity to the curable composition. For example, one or more of the following can be listed: metal powder, metal-coated particles, metal vapor-deposited materials, conductive polymers, etc.

[0187] <Morphology of Curable Compositions> The form of the curable composition of the present invention containing the acetylene group represented by formula (A1) is not particularly limited. For example, it can be prepared as a powder, solution, or dispersion. When it is in solution form, it can be a single-liquid form or a multi-liquid form (e.g., a two-liquid form).

[0188] <Weight Loss in TG-DTA (Thermogravimetric-Differential Thermal Analysis) Determination> The curable composition of the present invention comprising a compound having an acetylene group as represented by formula (A1) can be the above-mentioned curable composition that satisfies the requirements of (I) and / or (II) below; (I) In the TG-DTA (thermogravimetric-differential calorimetry) determination of the above-mentioned curable composition, the weight loss when heated from 30°C to 300°C at a heating rate of 10°C / min under a nitrogen atmosphere is less than 10%. (II) In the TG-DTA (thermogravimetric-differential thermal analysis) determination of the cured product of the above-mentioned curable composition obtained by heating at a temperature of 50°C to 250°C and for 48 hours or less, the weight loss when heated from 30°C to 300°C at a heating rate of 10°C / min under a nitrogen atmosphere is less than 10%.

[0189] The curable compositions of the present invention containing a compound having an acetylene group as represented by formula (A1) preferably satisfy the requirements of (I) and / or (II).

[0190] Requirement (I) refers to the behavior of the "curable composition" in a TG-DTA (thermogravimetric-differential calorimetry) determination, wherein the weight loss during TG-DTA determination, when heated from 30°C to 300°C at a heating rate of 10°C / min under a nitrogen atmosphere, 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 used to determine the 5% weight loss temperature described in the examples described later.

[0191] Requirement (II) refers to the behavior of the cured product of the above-described curable composition obtained by heating at a temperature of 50°C to 250°C for 48 hours or less in a TG-DTA (thermogravimetric-differential calorimetry) test, wherein the weight loss during the TG-DTA test, when heated from 30°C to 300°C at a heating rate of 10°C / min under a nitrogen atmosphere, is 10% or less, preferably 7% or less, and more preferably 5% or less. Requirement (II) can be confirmed, for example, by the same method used to determine the 5% weight loss temperature described in the examples described later.

[0192] In requirement (II), the lower limit of the heating time under conditions of 50°C to 250°C is the time required for the curing of the curable composition to complete and form a cured product, and is not particularly limited as long as it is 48 hours or less. For example, it can be set to 15 minutes or more, preferably 1 hour or more, more preferably 2 hours or more, and even more preferably 4 hours or more.

[0193] As for the conditions for obtaining "the cured product of the above-mentioned curable composition obtained by heating at a temperature of 50°C to 250°C and for 48 hours or less", for example, the same method used in the determination of the 5% weight loss temperature described in the following examples can be used to produce the cured product.

[0194] <Solvent-insoluble components> The present invention relates to a curable composition containing a compound having an acetylene group as represented by formula (A1), which is a curable composition that satisfies the requirement that when a cured product obtained by heating the above-mentioned curable composition at a temperature of 50°C to 250°C for 48 hours or less is impregnated in boiling tetrahydrofuran for 2 hours, subjected to solvent replacement in acetone at 25°C ± 5°C for 6 hours or more, and dried under a reduced pressure of -0.1 MPa at 80°C for 1 hour until no change in mass is observed for 3 hours or more, the insoluble component is 70% or more.

[0195] The solvent-insoluble component mentioned above is preferably 75% or more, more preferably 85% or more, and even more preferably 90% or more. A cured product whose solvent-insoluble component still exceeds 70% even after being impregnated in boiling tetrahydrofuran for 2 hours can be called a cured product with excellent solvent resistance to various solvents.

[0196] The conditions for obtaining "the cured product of the above-mentioned curable composition obtained by heating at a temperature of 50°C to 250°C for 48 hours or less" can be the same as those in the above-mentioned <weight loss in TG-DTA (thermogravimetric-differential thermal analysis) determination>. For example, the same method as the curing method for determining the 5% weight loss temperature described in the following examples can be used.

[0197] <Exothermic onset temperature (Tonset (°C)) and exothermic peak temperature (Tpeak (°C))> The exothermic onset temperature (Tonset (°C)) of the curable composition containing a compound having an acetylene group as represented by formula (A1) involved in this invention is below 250°C, for example below 200°C, preferably below 170°C, and more preferably below 120°C. When the exothermic onset temperature (Tonset (°C)) is below 250°C, for example below 200°C, a curable composition with excellent low-temperature curing properties can be prepared.

[0198] As a method for determining the exothermic onset temperature (Tonset (°C)) and the exothermic peak temperature (Tpeak (°C)), for example, the same method used for determining the exothermic onset temperature (Tonset (°C)) and the exothermic peak temperature (Tpeak (°C)) described in the embodiments described later can be used.

[0199] <Glass transition temperature> The cured product of the curable composition containing a compound having an acetylene group as represented by formula (A1) according to the present invention preferably has a glass transition temperature of 300°C or higher, as determined by dynamic viscoelasticity measurement. More preferably, the glass transition temperature is 330°C or higher. When the glass transition temperature of the cured product of the curable composition is 300°C or higher, it can be described as a cured product with excellent heat resistance.

[0200] As a method for determining the glass transition temperature obtained by dynamic viscoelasticity measurement, for example, the same method as the method for determining the glass transition temperature obtained by dynamic viscoelasticity measurement described in the following embodiments can be used.

[0201] <Residual Carbon Rate> The present invention relates to a curable composition containing a compound having an acetylene group as represented by formula (A1). The cured product obtained by heating the curable composition at 50°C to 250°C for 48 hours or less, and then heating it in TG-DTA at 100°C to 800°C under a nitrogen atmosphere and holding it at 800°C for 1 hour, preferably has a char residue (residual mass) of 60% by mass or more. More preferably, the char residue is 63% by mass or more, and even more preferably 65% ​​by mass or more. A char residue of 60% by mass or more indicates a cured product with excellent heat resistance, especially flame retardancy.

[0202] The char residue was determined by heating the cured material from 100°C to 800°C at a rate of 10°C / min in a non-oxidizing atmosphere, and calculating the mass fraction remaining after holding at 800°C for 1 hour, with the mass fraction of the cured material at 100°C as 100. For example, the same method as described in the examples below can be used to determine the char residue.

[0203] <Method for manufacturing curable compositions> The method for manufacturing the curable composition containing a compound having an acetylene group as represented by formula (A1) according to the present invention is not particularly limited. For example, it can be prepared by mixing the compound having an acetylene group as represented by formula (A1) with additives formulated as needed. During mixing, for example, methods such as using an extruder, kneader, roller mixer or other mixer to mix thoroughly until homogeneous can be included.

[0204] <Uses> The curable compositions containing acetylene groups represented by formula (A1) involved in this invention can be used for a wide variety of applications. Examples include adhesives, sealants, potting compounds, encapsulation materials, carbon material raw materials, prepregs, circuit connection materials, conductive compositions, molded articles, insulating materials, coatings, laminates, cured prepregs, fiber-reinforced composites, automotive parts, electrical and electronic materials, civil engineering materials, structural materials, and films.

[0205] [Compound] <The compound represented by formula (B)> A compound having an acetylene group, characterized by being represented by formula (B); [Chemistry 45]

[0206] (In formula (B), Z) 31 Selected from Ar 31 , [Chemistry 46]

[0207] -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 31 -、-P(=O)(OR 32 )-、-NR 33 CO-, -COO-, -NR 34 - and n-valent aromatic organic groups consisting of one or more groups in direct bonding. Ar 31 Ar 33 Ar 34 and Ar 36 Each is an aromatic ring with a valence of more than one valence that can independently have substituents. Ar 32 It can be a divalent or higher aromatic ring that has substituents. Ar 35 It can be an aromatic ring with a valence of 4 or more and have substituents. -X 31 -C≡CH and Ar 31 ~Ar 36 Any one of the bonds in, R 31 ~R 34 Each is independently a hydrogen or monovalent organic group. Z 31 Medium, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 31 -、-P(=O)(OR 32 )-、-NR 33 CO-, -COO- and -NR 34 - They are not directly bonded to each other.

[0208] -X 31 - is selected from -C (=O)-, -S (=O)-, -S (=O)2-, -P (=O)R 35 - and -P (=O) (OR 36 The divalent group of )- R 35 R 36 Each is an organic group that is either hydrogen or monovalent.

[0209] n 31 Integers greater than or equal to 2.

[0210] Ar 31 ~Ar 36 R 31 ~R 36 -X 31 When there are multiple, they can be the same as each other or different from each other.

[0211] -X 31 - is -C (=O) -, Z 31 When n is a phenyl ring without substituents, 31 It is an integer between 3 and 6.

[0212] n 31 =2, -X 31 - is -C (=O)-, Z 31 for, [Chemistry 47]

[0213] At least one -X 31 -C≡CH is adjacent to N, or two -XC≡CH are opposite and interpositional relative to N.

[0214] n 31 =2, -X 31 - is -C (=O)- or -S (=O)2-, Z 31 for, [Chemistry 48]

[0215] At least one -X 31 -C≡CH is located in the adjacent or intermediate position relative to O.

[0216] n 31 =2, -X 31 - is -C (=O)-, Z 31 for, [Chemistry 49]

[0217] At least one -X 31 -C≡CH is located in the ortho or meta position relative to the amide bond.

[0218] n 31 =2, -X 31 - is -C (=O)-, Z 31 for [Transformation 50]

[0219] At least one -X 31-C≡CH is located in the ortho or para position relative to the amide bond. Z in equation (B) 31 X 31 and n 31 respectively with Z in equation (A1) 11 X 11 and n 11 The same. Furthermore, Z in equation (B) 31 Ar 31 ~Ar 36 R 31 ~R 34 Aromatic rings and monovalent organic groups, X 31 R in 35 ~R 36 and the monovalent organogroups respectively react with Z in formula (A1) 11 Ar 11 ~Ar 16 R 11 ~R 14 Aromatic rings and monovalent organic groups, X 11 R in 15 ~R 16 It is the same as the monovalent organic group.

[0220] As a compound having an acetylene group as represented by formula (B) of the present invention, for example, the compound represented by formula (A2) in the above-described [curable composition] can be listed.

[0221] Furthermore, as compounds containing an acetylene group represented by formula (B) of the present invention, compounds represented by formula (A3) in the above-mentioned [curable composition] can be listed as examples.

[0222] In the compound having an acetylene group represented by formula (B) of the present invention, as -X 31 - is a compound of -C (=O)-, for example, the compounds (Aa2)~(Aa19) and (Aa21)~(Aa95) mentioned above.

[0223] In the compound having an acetylene group represented by formula (B) of the present invention, as -X 31 -For compounds with -S (=O)-, for example, the compounds (Ab1) to (Ab35) mentioned above can be listed.

[0224] In the compound having an acetylene group represented by formula (B) of the present invention, as -X 31 - is a compound of -S (=O)2-, for example, the compounds (Ac1)~(Ac13) and (Ac15)~(Ac35) mentioned above.

[0225] In the compound having an acetylene group represented by formula (B) of the present invention, as -X31 -for-P(=O)R 35 - compounds, for example, can be listed as (Ad1) to (Ad64) above.

[0226] In the compound having an acetylene group represented by formula (B) of the present invention, as -X 31 - is -P (=O) (OR) 36 Compounds of type )-, for example, can be listed as compounds (Ae1)~(Ae32) mentioned above.

[0227] In the compound having an acetylene group represented by formula (B) of the present invention, As X 31 Compounds with -C (=O)- are preferred, especially those represented by (Aa4)~(Aa19) and (Aa21)~(Aa95) above. As X 31 Compounds of -S (=O)- are preferred, especially those represented by (Ab1)~(Ab2) and (Ab5)~(Ab34) above. As X 31 Compounds of -S(=O)2- are preferred, especially those represented by (Ac1)~(Ac2) and (Ac5)~(Ac34) above. As X 31 -for-P(=O)R 35 The compounds of - are preferred, especially those represented by (Ad1)~(Ad2), (Ad5)~(Ad34), and (Ad37)~(Ad64) above. As X 31 - is -P (=O) (OR) 36 The compounds of (Ae1) to (Ae2) and (Ae5) to (Ae32) are preferred.

[0228] Among these, from the perspective of the reactivity of compounds containing an acetylene group, -X is more preferred. 31 - is selected from one or more of -C (=O)- and -S (=O)2-.

[0229] Further optimization of -X 31 - is a compound of -C (=O)- or -S (=O)2-.

[0230] More preferably, -X is particularly preferred. 31 - refers to the compounds represented by (Aa4)~(Aa18), (Aa21)~(Aa38), (Aa41)~(Aa95) above for -C(=O)-.

[0231] <Method for manufacturing the compound with an acetylene group represented by formula (B)> The compound containing an acetylene group represented by formula (B) of the present invention can be manufactured by an industrial synthetic method.

[0232] For example, the reactions described in (i) or (ii) below can be listed.

[0233] (i) [Chemistry 51]

[0234] Make Z 31 -(X) 31 -Hal 31 )n 31 (where Z) 31 X 31 and n 31 respectively with Z in equation (B) 31 X 31 and n 31 Same, Hal 31 (where is a halogen atom.) The acid halide represented by CH≡CM 31 -Hal 32 (where M) 31 Alkali earth metals, alkali metals, manganese, palladium, titanium, zinc, aluminum, bismuth, indium, germanium, silicon, and samarium, Hal 31 (where is a halogen atom.) represents the reaction of organometallic compounds in the presence of organic solvents and bases.

[0235] (ii) [Chemistry 52]

[0236] (S1) makes Z 31 -(X) 31 -Hal 31 )n 31 (where Z) 31 X 31 and n 31 respectively with Z in equation (B) 31 X 31 and n 31 Same, Hal 31 (where is a halogen atom.) represents the reaction of an acid halide with bis(trialkylsilyl)acetylene in the presence of an organic solvent and a Lewis acid catalyst, (S2), followed by the removal of the trialkylsilyl group in the presence of an organic solvent and a base.

[0237] As the organic solvent in the reactions (i) and (ii) above, one or more may be selected from hydrocarbon solvents (benzene, toluene, xylene, etc.), halogenated hydrocarbon solvents (chlorobenzene, dichlorobenzene, dichloromethane, 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.).

[0238] As the base in reactions (i) and (ii) above, one or more bases from various types, such as inorganic bases and organic bases, can be listed. For example, one or more bases selected from metal carbonates (sodium carbonate, sodium bicarbonate, etc.), metal carboxylic acid salts (sodium acetate, calcium acetate, etc.), metal hydroxides (sodium hydroxide, calcium hydroxide, etc.), metal borates (sodium borate, etc.), amines (ammonia, triethylamine, triisopropylamine, tributylamine, methylamine, benzylamine, N,N-dimethylaniline, piperazine, pyridine, etc., primary amines, secondary amines, tertiary amines, etc.) can be listed.

[0239] The Lewis acid used in reactions (i) and (ii) above may be one or more of the following: aluminum chloride, chromium oxide, aluminum oxide, silicon aluminum, zeolite, boron trifluoride, tin tetrachloride, titanium tetrachloride, phosphorus pentafluoride, phosphorus pentachloride, antimony pentafluoride, etc.

[0240] In this invention, since the above-mentioned reaction (i) is simple and advantageous in terms of reaction yield, the above-mentioned reaction (i) is preferred.

[0241] Furthermore, the (meth)acrylate esterification reaction can be carried out in the presence of a polymerization inhibitor (thermal polymerization inhibitor) as needed. Examples of polymerization inhibitors include hydroquinone compounds, catechol compounds, amine compounds, 2,2-diphenyl-1-picrylhydrazine, and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxo radicals. Examples of hydroquinone compounds include hydroquinone; hydroquinone monomethyl ethers (methoxyquinone) and other hydroquinone monoalkyl ethers. Examples of catechol compounds include alkyl catechols such as tert-butylcatechol. Examples of amine compounds include diphenylamine. These polymerization inhibitors can be used alone or in combination of two or more.

[0242] There are no particular limitations on the reaction conditions for the preparation of the compound with an acetylene group represented by formula (B). The reaction can be carried out under cooling or heating, or at room temperature (25℃±5℃). The reaction can be carried out under pressure or reduced pressure.

[0243] When manufacturing the compound with an acetylene group represented by formula (B), after the reaction is complete, operations such as neutralization, washing with water, concentration, crystallization, and filtration may be performed as needed. Further purification can be achieved through operations such as recrystallization, distillation, adsorption, and column chromatography.

[0244] [Heat-resistant resin materials] The heat-resistant resin material of the present invention is a heat-resistant resin material obtained by curing a curable composition containing a compound having an acetylene group as represented by formula (A1) or a compound having an acetylene group as represented by formula (B). The heat-resistant resin material can be a fully cured product obtained by completely curing the curable composition containing a compound having an acetylene group as represented by formula (A1) or a compound having an acetylene group as represented by formula (B), or a partially cured product. For example, it can be obtained by heating the curable composition containing a compound having an acetylene group as represented by formula (A1) or the compound having an acetylene group as represented by formula (B) under conditions of 50°C to 250°C and for 48 hours or less. Examples of heating temperatures include 50°C or higher, for example 60°C or higher, preferably 70°C or higher, more preferably 100°C or higher, and 250°C or lower, for example 200°C or lower, preferably 180°C or lower, more preferably 150°C or lower. Examples of heating times in heating conditions include 48 hours or less, preferably 36 hours or less, more preferably 24 hours or less, preferably 15 minutes or more, preferably 1 hour or more, more preferably 2 hours or more, and even more preferably 4 hours or more.

[0245] The heat-resistant resin material (cured product of the curable composition) is obtained by curing the curable composition containing a compound having an acetylene group as represented by formula (A1) or a compound having an acetylene group as represented by formula (B), as disclosed in this invention. The cured product obtained therefrom preferably satisfies the requirements of (II) below. (II) In the TG-DTA (thermogravimetric-differential thermal analysis) determination of the cured product of the above-mentioned curable composition obtained by heating at a temperature of 50°C to 250°C and for 48 hours or less, the weight loss when heated from 30°C to 300°C at a heating rate of 10°C / min under a nitrogen atmosphere is less than 10%.

[0246] [Adhesive] The adhesive of the present invention comprises a curable composition containing a compound having an acetylene group as represented by formula (A1) above, or an adhesive containing a compound having an acetylene group as represented by formula (B) above. Any component may also be used as an additive as needed. When the acetylene group of the compound having an acetylene group as represented by formula (A1) or the compound having an acetylene group as represented by formula (B) undergoes a cyclization reaction, it can exhibit strong adhesive strength. The curable composition containing a compound having an acetylene group as represented by formula (A1) or the adhesive containing a compound having an acetylene group as represented by formula (B) of 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.

[0247] [Sealing material] The sealing material of the present invention comprises a curable composition containing a compound having an acetylene group as represented by formula (A1) or a sealing material containing a compound having an acetylene group as represented by formula (B). Any component may also be used as an additive as needed. When the acetylene group of the compound having an acetylene group as represented by formula (A1) or the compound having an acetylene group as represented by formula (B) undergoes a cyclization reaction, it can exhibit a strong sealing effect. The sealing material of the present invention, comprising a curable composition containing a compound having an acetylene group as represented by formula (A1) or a sealing material containing a compound having an acetylene group as represented by formula (B), can be used as a sealing material for civil engineering, a sealing material for various structures, a heat-resistant sealing material for aerospace, etc.

[0248] [Potting Material] The potting material of the present invention comprises a curable composition containing a compound having an acetylene group as represented by formula (A1) or a potting material containing a compound having an acetylene group as represented by formula (B). Any component may also be used as an additive as needed. When the acetylene group of the compound having an acetylene group as represented by formula (A1) or the compound having an acetylene group as represented by formula (B) undergoes a cyclization reaction, it can exhibit strong functionality as a potting material. The curable composition containing a compound having an acetylene group as represented by formula (A1) or the potting material containing a compound having an acetylene group as represented by formula (B) of the present invention can be used as an insulating material for electrical components, electronic components, motor components, battery components, etc., or as a material for protecting electrical components, electronic components, motor components, battery components from thermal shock or mechanical shock.

[0249] [Encapsulation Materials] The encapsulation material of the present invention comprises a curable composition containing a compound having an acetylene group as represented by formula (A1) or an encapsulation material containing a compound having an acetylene group as represented by formula (B). Any component may also be used as an additive as needed. When the acetylene group of the compound having an acetylene group as represented by formula (A1) or the compound having an acetylene group as represented by formula (B) undergoes a cyclization reaction, it can exhibit strong functionality as an encapsulation material. The encapsulation material of the present invention, comprising a curable composition containing a compound having an acetylene group as represented by formula (A1) or an encapsulation material containing a compound having an acetylene group as represented by formula (B), can be used as an encapsulation material for electrical components, electronic components, motor components, battery components, etc., and especially for electronic components such as semiconductors.

[0250] [Carbon Materials] The carbon material involved in this invention is of formula (A): [Chemistry 53]

[0251] (In formula (A), -X- is selected from -C (=O)-, -S (=O)-, -S (=O)2-, -P (=O)R a - and -P (=O) (OR b When there are multiple divalent groups (-X-) in the - group, they can be the same as or different from each other. R a R is a hydrogen or monovalent organic group. a When there are multiple instances, they can be the same as each other or different from each other. R b R is a hydrogen or monovalent organic group. b When there are multiple instances, they can be the same as each other or different from each other. Z is an n-valent organic group. (n is an integer greater than or equal to 1.) The carbon material obtained by calcining the compound containing an acetylene group, the cured product of the compound containing an acetylene group represented by formula (A) above, a curable composition containing the compound containing an acetylene group represented by formula (A) above, or a cured product of the above curable composition. Examples of the obtained carbon materials include glassy carbon, graphene, carbon fibers, carbon sheets, carbon molded products, porous carbon materials, and carbon particles. Furthermore, it can also be used as a raw material for these materials.

[0252] The n-valent organic group in Z in formula (A) can be, for example, an n-valent aromatic group, an n-valent alicyclic group, or an n-valent aliphatic group.

[0253] When the n-valent organic group in Z in formula (A) is an n-valent aromatic group, the compound represented by formula (A1) described in the above [curable composition] can be used as the compound having an acetylene group represented by formula (A).

[0254] When the n-valent organic group Z in formula (A) is an n-valent alicyclic group, it can be any ring consisting only of carbon and having a structure other than a conjugated unsaturated ring (aromatic ring), i.e., an n-valent alicyclic group, without any particular limitation. Examples of alicyclic groups include cycloalkyl rings with 3 to 20 carbon atoms (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.), cycloalkenyl rings with 3 to 20 carbon atoms (e.g., cyclopentene, cyclohexene, cyclopentadiene, etc.), fused rings with 8 to 30 carbon atoms (e.g., bicyclic alkanes), and bridged rings with 6 to 30 carbon atoms (e.g., tricyclic [5.2.1.02, 6]decane, norbornene, norbornane, adamantane, etc.).

[0255] When the n-valent organic group in Z in formula (A) is an n-valent aliphatic group, the aliphatic group can be any saturated or unsaturated n-valent aliphatic hydrocarbon group with 2 to 30 carbon atoms, and there is no particular limitation. Examples include groups with alkyl groups having 1 to 20 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, etc.) forming an n-valent group; groups with 1 to 24 carbon atoms, preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8 carbon atoms (e.g., vinyl, propynyl, butenyl, pentenyl, hexenyl, octenyl, etc.) forming an n-valent group; and groups with 1 to 24 carbon atoms, preferably 1 to 18, more preferably 1 to 12, and even more preferably 1 to 8 carbon atoms (e.g., ethynyl, propynyl, butynyl, pentynyl, hexynyl, ocynyl, etc.) forming an n-valent group.

[0256] In formula (A), n is an integer greater than or equal to 1. In this invention, compounds containing an acetylene group with n greater than or equal to 2 are preferably used.

[0257] When using compounds containing acetylene groups represented by multiple formulas (A), the average value 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, 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. The average value of n can be calculated using the same method as described above for "the average value of n in the overall curable composition".

[0258] In the carbon material of the present invention, the compounds containing acetylene groups represented by formula (A) can be listed, for example, the above-mentioned compounds (Aa1)~(Aa98), (Ab1)~(Ab35), (Ac1)~(Ac35), (Ad1)~(Ad64) and (Ae1)~(Ae32) and the following compounds (Aa99)~(Aa111), (Ab36)~(Ab52), (Ac36)~(Ac52), (Ad65)~(Ad98) and (Ae33)~(Ae49).

[0259] [Chemistry 54]

[0260] [Chemistry 55]

[0261] [Chemistry 56]

[0262] [Chemistry 57]

[0263] [Chem.58]

[0264] [Chemistry 59]

[0265] [Prepreg] The prepreg involved in this invention is a prepreg containing a compound with an acetylene group as represented by formula (A) and a fibrous reinforcing material: [Transformation 60]

[0266] (In formula (A), -X- is selected from -C (=O)-, -S (=O)-, -S (=O)2-, -P (=O)R a - and -P (=O) (OR b When there are multiple divalent groups (-X-) in the - group, they can be the same as or different from each other. R a R is a hydrogen or monovalent organic group. a When there are multiple instances, they can be the same as each other or different from each other. R b R is a hydrogen or monovalent organic group. b When there are multiple instances, they can be the same as each other or different from each other. Z is an n-valent organic group. (n is an integer greater than or equal to 1.) The prepreg of this invention refers to a material obtained by applying a compound having an acetylene group or a composition containing a compound having an acetylene group to a fibrous reinforcing material through prepreg, coating or other means.

[0267] As compounds containing an acetylene group as represented by formula (A), compounds containing an acetylene group described in the above [Carbon Materials] section can be listed.

[0268] As a fibrous reinforcing material, one or more of the following can be listed: 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; examples include fabrics, nonwoven fabrics, rovings, chopped strand mats, and surface mats. As a fabric, plain weave fabrics, square plain weave fabrics, and twill weave fabrics can be used.

[0269] The fibrous reinforcement material can be made of materials that have undergone fiber splitting or surface treatment with silane coupling agents, as needed.

[0270] As needed, the prepreg can be cured by heating in a temperature range of, for example, 50°C to 250°C or 50°C to 200°C after molding to obtain a fiber-reinforced material.

[0271] Example The following examples illustrate the present invention in more detail, but these examples are merely illustrative and should not be construed as limiting the present invention.

[0272] {Synthesis of compounds represented by formula (A1) / (B)} [Example 1A] <Synthesis of 1-(3-(4-propioloylphenoxy)phenyl)prop-2-yn-1-one> (Step 1: Synthesis of 3-(4-formylphenoxy)benzaldehyde) [Chemistry 61]

[0273] Under an argon atmosphere, 4-fluorobenzaldehyde (4.96 g, 40.0 mmol) was dissolved in 20 mL of anhydrous dimethyl sulfoxide. 3-Hydroxybenzaldehyde (4.44 g, 20.0 mmol) and potassium carbonate (5.53 g, 40.0 mmol) were added, and the mixture was heated and stirred at 110 °C for 43 hours. The solution was allowed to cool naturally to room temperature (25 °C), and 200 mL of water was added. The mixture was then extracted three times with 200 mL of a mixed solvent (hexane:ethyl acetate = 4:1, v / v). The solvent was removed from the resulting organic phase by vacuum distillation and drying under vacuum. 3-(4-formylphenoxy)benzaldehyde (4.24 g, 18.7 mmol) was thus obtained in 93.6% yield as a pale yellow liquid.

[0274] (Step 2: Synthesis of 1-(3-(4-propioloylphenoxy)phenyl)prop-2-yn-1-one) [Chemistry 62]

[0275] 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 ethynyl magnesium chloride was added dropwise over 30 minutes. The solution was then heated to room temperature (25 °C) and stirred for 19 hours. 200 mL of a saturated ammonium chloride aqueous solution 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 vacuum distillation, and the product was dried under vacuum to obtain the crude product. The 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 for 1 hour at room temperature (25 °C). The solution was filtered, and the solvent was removed from the organic phase by vacuum distillation, and the product was dried under vacuum. The product was purified by column chromatography using a hexane:ethyl acetate mixture (v / v) of 4:1. Thus, 1-(3-(4-Propioloylphenoxy)phenyl)prop-2-yn-1-one (2.68 g, 9.77 mmol) was given as a pale yellow solid in 65.2% yield.

[0276] <Synthesis of 1,1'-(1,3-phenylene)bis(prop-2-yn-1-one)> [Chemistry 63]

[0277] Isophthaldialdehyde (3.35 g, 25.0 mmol) was dissolved in 250 mL of anhydrous tetrahydrofuran under an argon atmosphere. After cooling to 0 °C, 200 mL (100 mmol) of a 0.5 M tetrahydrofuran solution of acetylenyl magnesium chloride was added dropwise over 30 minutes. The solution was then heated to room temperature (25 °C) and stirred for 19 hours. 200 mL of a saturated ammonium chloride aqueous solution was added to the solution, and the mixture was extracted three times with 50 mL of dichloromethane each time. The solvent was removed from the organic phase by vacuum distillation, and the product was dried under vacuum to obtain the crude product. The 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 for 1 hour at room temperature (25 °C). The solution was filtered, and the solvent was removed from the organic phase by vacuum distillation, and the product was dried under vacuum. The product was purified by column chromatography using a hexane:ethyl acetate mixture (v / v) of 4:1. Thus, 1,1'-(1,3-phenylene)bis(prop-2-yn-1-one) (2.26 g, 12.4 mmol) in red solid was obtained in 49.6% yield.

[0278] [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)) [Chemistry 64]

[0279] 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 naturally to room temperature (25 °C), and 20 mL of water was added. The solution was then extracted three times with 20 mL of a mixed solvent of hexane and ethyl acetate (v / v ratio 4:1). The solvent was removed from the resulting organic phase by vacuum distillation and the solution was dried under vacuum. 2,2'-(1,2-phenylenebis(oxy))Bis(benzaldehyde) (1.41 g, 4.43 mmol) was thus obtained as a pale yellow liquid in 88.6% yield.

[0280] (Step 2: Synthesis of 1,1'-((1,2-phenylenebis(oxy))bis(2,1-phenylene))bis(prop-2-yn-1-one)) [Chemistry 65]

[0281] 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 acetylenyl magnesium chloride was added dropwise over 30 minutes. The solution was then heated to room temperature (25 °C) and stirred at room temperature (25 °C) for 19 hours. 200 mL of a saturated ammonium chloride aqueous solution 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 vacuum distillation, and the product was dried under vacuum to obtain the crude product. The crude product was dissolved in 150 mL of dichloromethane under an air atmosphere, 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 vacuum distillation, and the product was dried under vacuum. Purification was performed by column chromatography using a mixed solvent of hexane and ethyl acetate in a volume ratio of 4:1. This yielded 1,1'-((1,2-phenylenebis(oxy))bis(2,1-phenylene))bis(prop-2-yn-1-one) (0.500 g, 1.36 mmol) as a pale yellow solid in 34.1% yield.

[0282] [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)) [Chemistry 66]

[0283] Under an argon atmosphere, 4-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 naturally to room temperature (25 °C), and 20 mL of water was added. The solution was then extracted three times with 20 mL of a mixed solvent of hexane and ethyl acetate (v / v ratio 4:1). The solvent was removed from the resulting organic phase by vacuum distillation and drying under vacuum. 4,4'-(1,2-phenylenebis(oxy))bis(benzaldehyde) (1.44 g, 4.53 mmol) was thus obtained as a pale yellow solid in 90.6% yield.

[0284] (Step 2: Synthesis of 1,1'-((1,2-phenylenebis(oxy))bis(4,1-phenylene))bis(prop-2-yn-1-one)) [Chemistry 67]

[0285] 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 acetylenyl magnesium chloride was added dropwise over 30 minutes. The solution was then heated to room temperature (25 °C) and stirred at room temperature (25 °C) for 19 hours. 200 mL of a saturated ammonium chloride aqueous solution 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 vacuum distillation, and the product was dried under vacuum to obtain the crude product. The crude product was dissolved in 45 mL of dichloromethane under an air atmosphere, 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 vacuum distillation, and the product was dried under vacuum. Purification was performed by column chromatography using a mixed solvent of hexane and ethyl acetate in a volume ratio of 4:1. This yielded 1,1'-((1,2-phenylenebis(oxy))bis(4,1-phenylene))bis(prop-2-yn-1-one) as a pale yellow solid (1.11 g, 3.03 mmol) in 67.0% yield.

[0286] [Example 4A] <Synthesis of 4,4'-oxybis((ethynylsulfonyl)benzene)> (Step 1: Synthesis of 4,4'-oxydibenzenethiol) [Chemistry 68]

[0287] Under an argon atmosphere, 4,4'-oxydibenzenesulfonyl chloride (5.51 g, 15.0 mmol) was dissolved in 30 mL of anhydrous 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 naturally 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 vacuum distillation and the solution was dried under vacuum. The resulting pale yellow solid was dissolved in 400 mL of a 10% (w / w) aqueous solution of sodium hydroxide and neutralized with 1.0 L of 1 M hydrochloric acid. The precipitated pale yellow solid was separated by filtration, washed with 100 mL of water, and dried under vacuum. 4,4'-oxydibenzenesulfonyl chloride (3.24 g, 13.8 mmol) was thus obtained as a pale yellow solid in 92.1% yield.

[0288] (Step 2: Synthesis of 1,1'-((oxybis(4,1-phenylene))bis(sulfanediyl))bis(pyrrolidine-2,5-dione)) [Chemistry 69]

[0289] 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 min. 40 mL (22.0 mmol) of 0.55 M triethylamine dichloromethane solution was added dropwise, and the mixture was further stirred at 0 °C for 2 h. After adding 20 mL of water, the mixture was extracted three times with 30 mL of dichloromethane. The solvent was removed from the resulting organic phase by vacuum distillation and the phase was dried under vacuum. Purification was performed by column chromatography using a methanol:dichloromethane mixture (v / v) of 1:50. This yielded a quantitative amount of 1,1'-((oxybis(4,1-phenylene))bis(sulfanediyl))bis(pyrrolidine-2,5-dione) (4.30 g, 10.0 mmol) as a colorless, transparent solid.

[0290] (Step 3: Synthesis of (((oxybis(4,1-phenylene))bis(sulfanediyl))bis(ethyne-2,1-diyl))bis(trimethylsilane)) [Chemistry 70]

[0291] 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 2.69 M n-Butyllithium tetrahydrofuran solution was added dropwise, and the mixture was stirred at -78 °C for 30 min. 20 mL (10.0 mmol) of 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 heated to room temperature (25 °C) and stirred for 2 h. 100 mL of saturated sodium bicarbonate aqueous 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 vacuum distillation and the phase was dried under vacuum. Purification was performed by column chromatography using a hexane:ethyl acetate mixture (v / v) of 50:1. Thus, a pale yellow solid of (((oxybis(4,1-phenylene))bis(sulfanediyl))bis(ethyne-2,1-diyl))bis(trimethylsilane) (3.71 g, 8.72 mmol) was obtained in 87.2% yield.

[0292] (Step 4: Synthesis of 4,4'-oxybis((ethynylsulfonyl)benzene)) [Chemistry 71]

[0293] 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. Then, m-chloroperoxybenzoic acid (containing approximately 30% water) (9.69 g, 39.3 mmol) was added, and the mixture was stirred at room temperature (25 °C) for 27 hours. After adding 100 mL of a 10% (w / w) sodium thiosulfate aqueous solution, the mixture was extracted three times with 40 mL of dichloromethane. The resulting organic phase was further washed with 40 mL of saturated sodium bicarbonate aqueous solution. The solvent was removed from the resulting organic phase by vacuum distillation, and the mixture was dried under vacuum to obtain the crude product. The crude product was dissolved in 125 mL of ethanol, and 12 mL of a 1.64 M sodium fluoride aqueous solution was added. The mixture was stirred at room temperature (25 °C) for 30 minutes. The mixture was extracted three times with 40 mL of dichloromethane after adding 20 mL of water. The solvent was removed from the resulting organic phase by vacuum distillation and the mixture was dried under vacuum. The organic phase was then purified by column chromatography with a mixed solvent of hexane and ethyl acetate in a volume ratio of 2:1. This yielded a colorless, transparent solid of 4,4'-oxybis((ethynylsulfonyl)benzene) (1.47 g, 4.25 mmol) in 64.9% yield.

[0294] [Example 5A] <Synthesis of 1,1'-(oxydi-1,4-phenylene)bis(prop-2-yn-1-one)> [Chemistry 72]

[0295] 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 the mixture was 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 vacuum distillation, and the mixture was dried under vacuum to obtain the crude product. The crude product was dissolved in 500 mL of dry tetrahydrofuran, and 50.5 mL (0.505 mmol) of 0.0100 M borax aqueous solution 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 vacuum distillation and the mixture was dried under vacuum. The organic phase was then purified by column chromatography with a hexane:ethyl acetate mixture of 1:1 (v / v). 1,1'-(oxydi-1,4-phenylene)bis(prop-2-yn-1-one) (9.36 g, 34.1 mmol) was thus obtained in 48.7% yield as a pale yellow solid.

[0296] [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)) [Chemistry 73]

[0297] Under an argon atmosphere, 4-Fluorobenzaldehyde (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 naturally to room temperature (25 °C), and 20 mL of water was added. The solution was then extracted three times with 20 mL of a mixed solvent of hexane and ethyl acetate (v / v ratio 4:1). The solvent was removed from the resulting organic phase by vacuum distillation and the solution was dried under vacuum. 4,4'-(1,4-Phenylenebis(oxy))bis(benzaldehyde) (1.25 g, 3.93 mmol) was thus obtained as a pale yellow solid in 78.4% yield.

[0298] (Step 2: Synthesis of 1,1'-((1,4-phenylenebis(oxy))bis(4,1-phenylene))bis(prop-2-yn-1-one)) [Chemistry 74]

[0299] Under an argon atmosphere, 4,4'-(1,4-Phenylenebis(oxy))bis(benzaldehyde) (0.934 g, 2.94 mmol) was dissolved in 30 mL of dry tetrahydrofuran. After cooling to 0 °C, 23.6 mL (11.8 mmol) of a 0.5 M tetrahydrofuran solution of ethynyl magnesium chloride was added dropwise over 30 minutes. The solution was then heated to room temperature (25 °C) and stirred for 1 hour. 200 mL of a saturated ammonium chloride aqueous solution 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 vacuum distillation, and the product was dried under vacuum to obtain the crude product. The crude product was dissolved in 30 mL of dichloromethane under an air atmosphere, and manganese dioxide (10.2 g, 118 mmol) was added. The mixture was stirred for 2 hours at room temperature (25 °C). The solution was filtered, and the solvent was removed from the organic phase by vacuum distillation, and the product was dried under vacuum. Purification was performed by column chromatography using a mixed solvent of hexane and ethyl acetate in a volume ratio of 4:1. This yielded 1,1'-((1,4-phenylenebis(oxy))bis(4,1-phenylene))bis(prop-2-yn-1-one) as a pale yellow solid (0.962 g, 2.62 mmol) in 89.1% yield.

[0300] {Preparation of Curable Composition} [Example 1B] <Preparation of Curable Composition 1B> Weigh 16.4644 g (60 mmol) of 1-(3-(4-propioloylphenoxy)phenyl)prop-2-yn-1-one and add 0.1292 g (1.50 mmol) of piperazine. Grind and mix in a mortar for 30 minutes to obtain 16.5936 g of cured composition 1B.

[0301] [Example 2B] <Preparation of Curable Composition 2B> 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, the same as in Example 1B, yielded 11.0612 g of cured composition 2B.

[0302] [Example 3B] <Preparation of Curable Composition 3B> Weigh 16.4640 g (60 mmol) of 1-(3-(4-propioloylphenoxy)phenyl)prop-2-yn-1-one, pulverize and mix it in a mortar for 30 minutes to obtain 16.4640 g of cured composition 3B.

[0303] [Example 4B] <Preparation of Curable Composition 4B> 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, the same curable composition 4B as in Example 3B was obtained.

[0304] [Example 5B] <Preparation of Curable Composition 5B> Weigh 0.080600 g (0.22 mmol) of 1,1'-((1,2-phenylenebis(oxy))bis(2,1-phenylene))bis(prop-2-yn-1-one), and add 0.000474 g (0.00550 mmol) of piperazine. Grind and mix in a mortar for 30 minutes to obtain 0.081074 g of cured composition 5B.

[0305] [Example 6B] <Preparation of Curable Composition 6B> Except for the use of 0.080600 g (0.22 mmol) of 1,1'-((1,2-phenylenebis(oxy))bis(2,1-phenylene))bis(prop-2-yn-1-one) instead of 1,1'-((1,2-phenylenebis(oxy))bis(4,1-phenylene))bis(prop-2-yn-1-one), a curable composition 6B of 0.081074 g was obtained, similar to Example 5B.

[0306] [Example 7B] <Preparation of Curable Composition 7B> Weigh 0.06920 g (0.20 mmol) of 4,4'-oxybis((ethynylsulfonyl)benzene) and add 0.00431 g (0.00500 mmol) of piperazine. Grind and mix in a mortar for 30 minutes to obtain 0.07351 g of cured composition 7B.

[0307] [Example 8B] <Preparation of Curable Composition 8B> 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, 16.5936 g of curable composition 8B was obtained in the same manner as in Example 1B.

[0308] [Example 9B] <Preparation of Curable Composition 9B> Except for the use of 0.080600 g (0.22 mmol) of 1,1'-((1,4-phenylenebis(oxy))bis(4,1-phenylene))bis(prop-2-yn-1-one) instead of 1,1'-((1,2-phenylenebis(oxy))bis(4,1-phenylene))bis(prop-2-yn-1-one), a curable composition 9B of 0.081074 g was obtained, similar to Example 5B.

[0309] {Determination of properties of curable compositions and cured products} [5% weight loss temperature of the curing composition] <Determination of 5% weight loss temperature of curing composition 1B> 7.8 mg of curable composition 1B was weighed into a platinum pan, which was then placed in a thermogravimetric analyzer (Hitachi Advanced Scientific Corporation "STA7200"). Under a nitrogen atmosphere, the cured composition 1B weighed in the platinum pan was heated from 30°C to 800°C at a heating rate of 10°C / min. TG-DTA analysis was performed, and the 5% weight loss temperature Td5 was determined, yielding a result of 475°C. Figure 1 The TG-DTA analysis results of the curable composition 1B are shown.

[0310] <Determination of 5% weight loss temperature of curing composition 2B> The 5% weight loss temperature Td5 of curable composition 2B was determined using the same method as that used for <Determination of 5% weight loss temperature of curable composition 1B>, and the result was 419°C. Figure 2 The TG-DTA analysis results of the curable composition 2B are shown.

[0311] <Determination of 5% weight loss temperature of curing composition 3B> The 5% weight loss temperature Td5 of curable composition 3B was determined using the same method as that used for <Determination of 5% weight loss temperature of curable composition 1B>, and the result was 397°C. Figure 3 The TG-DTA analysis results of the curable composition 3B are shown.

[0312] <Determination of 5% weight loss temperature of curing composition 4B> The 5% weight loss temperature Td5 of curing composition 4B was determined by the same method as that for <Determination of 5% weight loss temperature of curing composition 1B>, and the result was 155°C. Figure 4 The TG-DTA analysis results of the curable composition 4B are shown.

[0313] <Determination of 5% weight loss temperature of curable composition 5B> The 5% weight loss temperature Td5 of curable composition 5B was determined using the same method as that used for <Determination of 5% weight loss temperature of curable composition 1B>, and the result was 342°C. Figure 5 The TG-DTA analysis results of the curable composition 5B are shown.

[0314] <Determination of 5% weight loss temperature of curing composition 6B> The 5% weight loss temperature Td5 of curable composition 6B was determined using the same method as that used for <Determination of 5% weight loss temperature of curable composition 1B>, and the result was 481°C. Figure 6The TG-DTA analysis results of the curable composition 6B are shown.

[0315] <Determination of 5% weight loss temperature of curable composition 8B> The 5% weight loss temperature Td5 of curable composition 8B was determined using the same method as that used for <Determination of 5% weight loss temperature of curable composition 1B>, and the result was 437°C. Figure 7 The TG-DTA analysis results of the curable composition 8B are shown.

[0316] <Determination of 5% weight loss temperature of curing composition 9B> The 5% weight loss temperature Td5 of curable composition 9B was determined using the same method as that used for <Determination of 5% weight loss temperature of curable composition 1B>, and the result was 418°C. Figure 8 The TG-DTA analysis results of the curable composition 9B are shown.

[0317] [5% weight loss temperature of the heat-resistant resin material obtained by curing the curing composition] <Determination of 5% weight loss temperature of 1Ca in heat-resistant resin materials (cured products)> 65.0 mg of curable composition 1B was melted at 120°C and poured into a 1 cm × 2 cm aluminum mold. The mold was then heated in an oven at 120°C for 6 hours in air to obtain heat-resistant resin material (cured product) 1Ca. 5.7 mg of the obtained heat-resistant resin material (cured product) 1Ca was weighed and placed in a platinum pan, which was then placed in a thermogravimetric analyzer (Hitachi Advanced Scientific Corporation "STA7200"). Under a nitrogen atmosphere, the heat-resistant resin material (cured product) 1Ca in the platinum pan was heated from 100°C to 800°C at a heating rate of 10°C / min. TG-DTA analysis was performed, and the 5% weight loss temperature Td5 was determined, which was 480°C. Figure 9 The results of TG-DTA analysis are shown.

[0318] <Determination of 5% weight loss temperature at 2C for heat-resistant resin materials (cured products)> 65.0 mg of curable composition 2B was melted at 130°C and poured into a 1 cm × 2 cm aluminum mold. The mold was then heated in an oven under air atmosphere 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 determined using the same method as described above for <Determination of the 5% weight loss temperature of heat-resistant resin material (cured product) 1Ca>, and the result was 427°C. Figure 10 The results of TG-DTA analysis are shown.

[0319] <Determination of 5% weight loss temperature of heat-resistant resin materials (cured products) at 3C> 65.2 mg of the curable composition 3B was melted at 120°C and poured into a 1 cm × 2 cm aluminum mold. The mold was then subjected to staged heating in an oven under air atmosphere at 120°C for 1 hour, 150°C for 2 hours, and 180°C for 2 hours to obtain the heat-resistant resin material (cured product) 3C. The 5% weight loss temperature Td5 of the heat-resistant resin material (cured product) 3C was determined using the same method as described above for the determination of the 5% weight loss temperature of the heat-resistant resin material (cured product) 1C, and the result was 436°C. Figure 11 The results of TG-DTA analysis are shown.

[0320] <Determination of 5% weight loss temperature of heat-resistant resin materials (cured products) at 4C> 65.0 mg of the curable composition 4B was melted at 130°C and poured into a 1 cm × 2 cm aluminum mold. The mold was then subjected to staged heating in an oven under air atmosphere at 130°C for 1 hour, 150°C for 2 hours, and 180°C for 2 hours to obtain the heat-resistant resin material (cured product) 4C. The 5% weight loss temperature Td5 of the heat-resistant resin material (cured product) 4C was determined using the same method as described above for the determination of the 5% weight loss temperature of the heat-resistant resin material (cured product) 1C, and the result was 398°C. Figure 12 The results of TG-DTA analysis are shown.

[0321] <Determination of 5% weight loss temperature at 5°C for heat-resistant resin materials (cured products)> 65.0 mg of the curable composition 5B was melted at 120°C and poured into a 1 cm × 2 cm aluminum mold. The mold was then heated in an oven at 120°C for 6 hours in air to obtain the heat-resistant resin material (cured product) 5C. The 5% weight loss temperature Td5 of the heat-resistant resin material (cured product) 5C was determined using the same method as described above for <Determination of the 5% weight loss temperature of the heat-resistant resin material (cured product) 1Ca>, and the result was 341°C. Figure 13 The results of TG-DTA analysis are shown.

[0322] <Determination of 5% weight loss temperature of heat-resistant resin materials (cured products) at 6°C> 65.0 mg of the curable composition 6B was melted at 120°C and poured into a 1 cm × 2 cm aluminum mold. The mold was then heated in an oven at 120°C for 6 hours in air to obtain the heat-resistant resin material (cured product) 6C. The 5% weight loss temperature Td5 of the heat-resistant resin material (cured product) 6C was determined using the same method as described above for <Determination of the 5% weight loss temperature of the heat-resistant resin material (cured product) 1Ca>, and the result was 458°C. Figure 14 The results of TG-DTA analysis are shown.

[0323] <Determination of 5% weight loss temperature at 7°C for heat-resistant resin materials (cured products)> 65.0 mg of the curable composition 7B was melted at 150°C and poured into a 1 cm × 2 cm aluminum mold. The mold was then heated in an oven under air atmosphere at 150°C for 1 hour, further at 160°C for 1 hour, and further at 180°C for 2 hours to obtain the heat-resistant resin material (cured product) 7C. The 5% weight loss temperature Td5 of the heat-resistant resin material (cured product) 7C was determined using the same method as described above for <Determination of the 5% weight loss temperature of the heat-resistant resin material (cured product) 1Ca>, and the result was 292°C. Figure 15 The results of TG-DTA analysis are shown.

[0324] <Determination of 5% weight loss temperature at 8°C for heat-resistant resin materials (cured products)> 65.0 mg of the curable composition 8B was heated at 120°C and placed on a 1 cm × 2 cm aluminum mold. The mixture was then heated in an oven under air atmosphere at 120°C for 2 hours, then at 150°C for 2 hours, and further heated at 180°C for 2 hours to obtain the heat-resistant resin material (cured product) 8C. The 5% weight loss temperature Td5 of the heat-resistant resin material (cured product) 8C was determined using the same method as described above for <Determination of the 5% weight loss temperature of the heat-resistant resin material (cured product) 1Ca>, and the result was 401°C. Figure 16 The results of TG-DTA analysis are shown.

[0325] <Determination of 5% weight loss temperature of heat-resistant resin materials (cured products) at 9C> 65.0 mg of the curable composition 9B was heated at 120°C and placed on a 1 cm × 2 cm aluminum mold. The mixture was then heated in an oven under air atmosphere at 120°C for 2 hours, then at 150°C for 2 hours, and further heated at 180°C for 2 hours to obtain the heat-resistant resin material (cured product) 9C. The 5% weight loss temperature Td5 of the heat-resistant resin material (cured product) 9C was determined using the same method as described above for the determination of the 5% weight loss temperature of the heat-resistant resin material (cured product) 1Ca, and the result was 420°C. Figure 17 The results of TG-DTA analysis are shown.

[0326] [The glass transition temperature (Tg) of the heat-resistant resin material obtained by curing the curable composition] <Determination of the glass transition temperature (Tg) of heat-resistant resin materials (cured products) 1Cb> 163 mg of curable composition 1B was melted at 120°C and injected into an 8 mm × 50 mm aluminum mold. The mold was then subjected to staged heating in an oven under air atmosphere at 120°C for 1 hour, 150°C for 2 hours, and 180°C for 2 hours to obtain a heat-resistant resin material (cured product) 1Cb with a thickness of 290 μm. The obtained heat-resistant resin material (cured product) 1Cb was placed in a dynamic viscoelasticity measuring apparatus (Hitachi Advanced Technology Scientific Co., Ltd. "DMA7100"). The dynamic viscoelasticity of the heat-resistant resin material (cured product) 1Cb was measured by heating it from 30°C to 450°C at a heating rate of 10°C / min under air atmosphere. The glass transition temperature (Tg) of the heat-resistant resin material (cured product) 1Cb was determined to be 351°C from the peak of Tanδ. Figure 18 The DMA measurement results are shown.

[0327] <Determination of the glass transition temperature (Tg) of heat-resistant resin materials (cured products) at 2C> 163.3 mg of curable composition 2B was melted at 130°C and injected into an 8 mm × 50 mm aluminum mold. The mold was then heated in an oven at 130°C for 8 hours in air to obtain a heat-resistant resin material (cured product) 2C with a thickness of 360 μm. The obtained heat-resistant resin material (cured product) 2C was placed in a dynamic viscoelasticity measuring apparatus (Hitachi Advanced Technology Scientific Co., Ltd. "DMA7100"). The dynamic viscoelasticity of the heat-resistant resin material (cured product) 2C was measured by heating it from 30°C to 400°C at a heating rate of 10°C / min in air. No Tanδ peak was observed, and the glass transition temperature (Tg) exceeded 400°C. Figure 19 The DMA measurement results are shown.

[0328] [Exothermic onset temperature (Tonset (°C) and exothermic peak temperature (Tpeak (°C)) of the curing composition] <Determination of the exothermic onset temperature and exothermic peak temperature of curable composition 1B> 7.1 mg of curable composition 1B was weighed into an aluminum dish, and the dish was placed in a differential scanning calorimeter (DSC7020, manufactured by Hitachi Advanced Scientific Corporation). Under a nitrogen atmosphere, the temperature was increased from 30°C to 300°C at a rate of 5°C / min to obtain an exothermic spectrum. The exothermic onset temperature (Tonset (°C)) and exothermic peak temperature (Tpeak (°C)) were measured. In this invention, the exothermic onset temperature (Tonset (°C)) refers to the temperature at the intersection of the tangent line at the point of maximum slope at the peak in the DSC exothermic spectrum and the baseline, and the exothermic peak temperature (Tpeak (°C)) refers to the peak temperature in the DES exothermic spectrum. The exothermic onset temperature (Tonset (°C)) of curable composition 1B was 94.4°C, and the exothermic peak temperature (Tpeak (°C)) was 158°C.

[0329] <Determination of the 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 determined using the same method as described above for the determination of the 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.

[0330] <Determination of the 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 determined using the same method as described above for the determination of the 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.

[0331] <Determination of the 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 determined using the same method as described above for the determination of the 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.

[0332] [Percentage of insoluble components in the heat-resistant resin material obtained by curing the curable composition] <Determination of the insoluble component percentage of heat-resistant resin materials (cured products) at 1C> 65 mg of curable composition 1B was placed in a 1 cm × 2 cm mold and heated in an oven at 120 °C for 6 hours under air atmosphere 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 impregnated in boiling tetrahydrofuran for 2 hours, followed by solvent replacement in acetone at room temperature (25 ± 5 °C) for 20 hours. The mass was measured every hour under reduced pressure (-0.1 MPa) at 80 °C until no mass change was observed for more than 3 hours (6 hours). Drying was then performed, and the insoluble component percentage was calculated using the following formula. The insoluble component percentage of heat-resistant resin material (cured product) 1C was 100%.

[0333] Insoluble component percentage = (Mass of the dried sample / Mass of the sample before extraction) × 100 <Determination of the insoluble component percentage of 2C in heat-resistant resin materials (cured products)> Curing composition 2B is used instead of curing composition 1B, and heat-resistant resin material (cured product) 2C is obtained by the same method as in <Determination of the insoluble component percentage of heat-resistant resin material (cured product) 1C>. The insoluble component percentage of heat-resistant resin material (cured product) 2C is determined by the same method as in <Determination of the insoluble component percentage of heat-resistant resin material (cured product) 1C> described above. The insoluble component percentage of heat-resistant resin material (cured product) 2C is 99.5%.

[0334] <Determination of the Insoluble Component Ratio of 3C in Heat-Resistant Resin Materials (Cures)> Curing composition 3B was used instead of curing composition 1B, and heat-resistant resin material (cured product) 3C was obtained by the same method as in <Determination of the insoluble component percentage of heat-resistant resin material (cured product) 1C>. The insoluble component percentage of heat-resistant resin material (cured product) 3C was determined by the same method as in <Determination of the insoluble component percentage of heat-resistant resin material (cured product) 1C> described above. The insoluble component percentage of heat-resistant resin material (cured product) 3C was 99.0%.

[0335] <Determination of the insoluble component percentage of 4C in heat-resistant resin materials (cured products)> Curing composition 4B was used instead of curing composition 1B, and heat-resistant resin material (cured product) 4C was obtained by the same method as in <Determination of the insoluble component percentage of heat-resistant resin material (cured product) 1C>. The insoluble component percentage of heat-resistant resin material (cured product) 4C was determined by the same method as in <Determination of the insoluble component percentage of heat-resistant resin material (cured product) 1C> described above. The insoluble component percentage of heat-resistant resin material (cured product) 4C was 98.5%.

[0336] [Carbon residue of the cured heat-resistant resin material obtained by curing a curable composition] <Determination of char residue of heat-resistant resin materials (cured products) at 1C> 65.1 mg of curable composition 1B was melted at 120°C and poured into a 1 cm × 2 cm aluminum mold. The mold was then heated in an oven at 120°C for 6 hours in air to obtain heat-resistant resin material (cured product) 1C. 8.5 mg of heat-resistant resin material (cured product) 1C was placed in a platinum pan, which was then placed in a thermogravimetric analyzer (Hitachi High Technology Scientific Co., Ltd. "STA7200"). Under a nitrogen atmosphere, the heat-resistant resin material (cured product) 1C in the platinum pan was held at 100°C for 30 minutes, then 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. When the mass fraction of the heat-resistant resin material (cured product) 1C after being held at 100°C for 30 minutes is taken as 100, the mass fraction after being heated at 800°C for 1 hour is taken as the carbon residue, and the carbon residue is calculated. The result is 66.1%. Figure 20 The results of TG-DTA analysis are shown.

[0337] <Determination of char residue of heat-resistant resin materials (cured products) 2C> 65.0 mg of the curable composition 2B was melted at 130°C and poured into a 1 cm × 2 cm aluminum mold. The mold was then heated in an oven under air atmosphere at 130°C for 6 hours to obtain a heat-resistant resin material (cured product) 2C. The obtained heat-resistant resin material (cured product) 2C was heated using the same method as described above for <Determination of the char residue of heat-resistant resin material (cured product) 1C> to obtain carbon material 2D. The char residue of the obtained heat-resistant resin material (cured product) 2C was determined using the same method as described above for <Determination of the char residue of heat-resistant resin material (cured product) 1C>, and the result was 65.8%. Figure 21 The results of TG-DTA analysis are shown.

[0338] The embodiments and examples of the present invention have been described above, but the embodiments and examples described above do not limit the scope of the invention as defined in the claims. Furthermore, it should be noted that the combinations of features described in the embodiments and examples are not necessarily all necessary for the method to solve the problem of the invention, and various modifications can be made as long as they do not depart from the technical spirit of the present invention.

Claims

1. A curable composition, characterized in that, Compounds containing the acetylene group represented by formula (A1); [Chemistry 1] In formula (A1), Z 11 Selected from Ar 11 , [Chemistry 2] -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 11 -、-P(=O)(OR 12 )-、-NR 13 CO-, -COO-, -NR 14 - and n-valent aromatic organic groups consisting of one or more groups in direct bonding. Ar 11 Ar 13 Ar 14 and Ar 16 Each is an aromatic ring with a valence of more than one valence that can independently have substituents. Ar 12 It can be a divalent or higher aromatic ring that has substituents. Ar 15 It can be an aromatic ring with a valence of 4 or more and have substituents. -X 11 -C≡CH and Ar 11 ~Ar 16 Any one of the bonds in, R 11 ~R 14 Each is independently a hydrogen or monovalent organic group. Z 11 Medium, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 11 -、-P(=O)(OR 12 )-、-NR 13 CO-, -COO- and -NR 14 - They are not directly bonded to each other. -X 11 - is selected from -C (=O)-, -S (=O)-, -S (=O)2-, -P (=O)R 15 - and -P (=O) (OR 16 The divalent group in )- R 15 R 16 Each is independently a hydrogen or monovalent organic group. n 11 Integers greater than or equal to 1 Ar 11 ~Ar 16 R 11 ~R 16 -X 11 When there are multiple, they can be the same as each other or different from each other.

2. The curable composition according to claim 1, characterized in that, In the aforementioned formula (A1), n 11 =2, -X 11 - is -C (=O)-, Z 11 for, [Chemistry 3] At that time, 2 -X 11 -C≡CH is located in the adjacent or intermediate position. n 11 =2, -X 11 - is -C (=O)-, Z 11 for, [Chemistry 4] At least one -X 11 -C≡CH is located adjacent to or between N.

3. The curable composition according to claim 1 or 2, characterized in that, The compound with an acetylene group represented by formula (A1) contains n 11 For compounds that are integers greater than or equal to 2, the total number of n in the curing composition is... 11 The average is above 1.

5.

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

5. The curable composition according to claim 1 or 2, characterized in that, For the cured product obtained by heating the curing composition at a temperature of 50°C to 250°C for 48 hours or less, after impregnation in boiling tetrahydrofuran for 2 hours, solvent replacement is carried out in acetone at 25°C ± 5°C for 6 hours or more, and drying is carried out under reduced pressure of -0.1 MPa at 80°C. The mass is measured every hour until no mass change is observed after 3 hours or more. At this time, the insoluble component is more than 70%.

6. The curable composition according to claim 1 or 2, characterized in that, The compound containing an acetylene group represented by formula (A1) is the compound containing an acetylene group represented by formula (A2) below; [Chemistry 5] In formula (A2), Ar 21 ~Ar 23 Each independently selected from Ar 24 , [Chemistry 6] An n-valent aromatic organic group consisting of one or more groups. Ar 24 Ar 26 Ar 27 and Ar 29 Each is an aromatic ring with a valence of more than one valence that can independently have substituents. Ar 25 It can be a divalent or higher aromatic ring that has substituents. Ar 28 It can be an aromatic ring with a valence of 4 or more and have substituents. Q 21 and Q 22 Each is independently selected from -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 21 -、-P(=O)(OR 22 )-、-NR 23 CO-, -COO-, -NR 24 - and groups in direct bonding. R 21 ~R 24 Each is independently a hydrogen or monovalent organic group. -X 21 -~-X 23 - Each is independently selected from -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 25 - and -P (=O) (OR 26 The divalent group in ) R 25 R 26 Each is independently a hydrogen or monovalent organic group. n 21 ~n 24 n is an integer greater than or equal to 0 or 1. 25 n is an integer greater than or equal to 1. 24 When n is 0, 25 Integers greater than 2 n 24 n is an integer greater than or equal to 1, and n 23 When n is 0, 21 +n 25 Integers greater than 2 n 23 and n 24 When n is an integer greater than or equal to 1, 21 +n 22 +n 25 Integers greater than 2 Ar 21 ~Ar 29 -X 21 -~-X 23 -、R 21 ~R 26 When there are multiple instances, they can be the same as each other or different from each other. n 24 =0, n 25 =2, -X 23 - is -C (=O)-, -Ar 23 -for, [Chemistry 7] At that time, 2 -X 23 -C≡CH is located in the adjacent or intermediate position. n 21 For 1, n 23 =0, n 24 =1, -X 21 -and-X 23 - is -C (=O)-, -Ar 21 -Q 22 -Ar 23 -for, [Chemistry 8] At least one -X 23 -C≡CH is located adjacent to or between N.

7. The curable composition according to claim 6, characterized in that, The compound with an acetylene group represented by formula (A2) is the compound with an acetylene group represented by formula (A3) below; [Chemistry 9] In equation (A3), Q 21 and Q 22 Each is independently selected from -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 21 -、-P(=O)(OR 22 )-、-NR 23 CO-, -COO-, -NR 24 - and groups in direct bonding. R 21 ~R 24 Each is independently a hydrogen or monovalent organic group. -X 21 -~-X 23 - Each is independently selected from -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 25 - and -P (=O) (OR 26 The divalent group in )- R 25 R 26 Each is independently a hydrogen or monovalent organic group. n 21 ~n 24 n is an integer greater than or equal to 0 or 1. 25 n is an integer greater than or equal to 1. 24 When n is 0, 25 Integers greater than 2 n 24 n is an integer greater than or equal to 1 and 23 When n is 0, 21 +n 25 Integers greater than 2 n 23 and n 24 When n is an integer greater than or equal to 1, 21 +n 22 +n 25 Integers greater than 2 -X 21 -~-X 23 -、R 21 ~R 26 When there are multiple instances, they can be the same as each other or different from each other. n 24 =0, n 25 =2, -X 23 When - is -C (=O)-, there are 2 -X. 23 -C≡CH is located in the adjacent or intermediate position. n 21 n 24 and n 25 For 1, n 23 =0, -X 21 -and-X 23 - is -C (=O)-, Q 22 For NR 24 R 24 When it is phenyl, -X 21 -C≡CH is located adjacent to or between N.

8. The curable composition according to claim 1 or 2, characterized in that, It can be a single-liquid or multi-liquid type.

9. A compound having an acetylene group, characterized in that, Represented by equation (B); [Chemistry 10] In equation (B), Z 31 Selected from Ar 31 , [Chemistry 11] -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 31 -、-P(=O)(OR 32 )-、-NR 33 CO-, -COO-, -NR 34 - and n-valent aromatic organic groups consisting of one or more groups in direct bonding. Ar 31 Ar 33 Ar 34 and Ar 36 Each is an aromatic ring with a valence of more than one valence that can independently have substituents. Ar 32 It can be a divalent or higher aromatic ring that has substituents. Ar 35 It can be an aromatic ring with a valence of 4 or more and have substituents. -X 31 -C≡CH and Ar 31 ~Ar 36 Any one of the bonds in, R 31 ~R 34 Each is independently a hydrogen or monovalent organic group. Z 31 Medium, -O-, -S-, -C(=O)-, -S(=O)-, -S(=O)2-, -P(=O)R 31 -、-P(=O)(OR 32 )-、-NR 33 CO-, -COO- and -NR 34 - They are not directly bonded to each other. -X 31 - is selected from -C (=O)-, -S (=O)-, -S (=O)2-, -P (=O)R 35 - and -P (=O) (OR 36 The divalent base in )- R 35 R 36 Each is independently a hydrogen or monovalent organic group. n 31 Integers greater than 2 Ar 31 ~Ar 36 R 31 ~R 36 -X 31 When there are multiple instances, they can be the same as each other or different from each other. -X 31 - is -C (=O)-, Z 31 When n is a phenyl ring without substituents, 31 Integers between 3 and 6 n 31 =2, -X 31 - is -C (=O)-, Z 31 for, [Chemistry 12] At least one -X 31 -C≡CH is adjacent to N, or two -X 31 -C≡CH is located in the anti- and meta positions relative to N. n 31 =2, -X 31 - is -C (=O)- or -S (=O)2-, Z 31 for, [Chemistry 13] At least one -X 31 -C≡CH is located adjacent to or between O. n 31 =2, -X 31 - is -C (=O)-, Z 31 for, [Chemistry 14] At least one -X 31 -C≡CH is located in the ortho or meta position relative to the amide bond. n 31 =2, -X 31 - is -C (=O)-, Z 31 for, [Chemistry 15] At least one -X 31 -C≡CH is located in the ortho or para position relative to the amide bond.

10. A heat-resistant resin material, characterized in that, It is obtained by curing the curable composition of claim 1 or the compound of claim 9.

11. An adhesive, characterized in that, Contains the curable composition of claim 1 or the compound of claim 9.

12. A sealing material, characterized in that, Contains the curable composition of claim 1 or the compound of claim 9.

13. A potting compound, characterized in that, Contains the curable composition of claim 1 or the compound of claim 9.

14. An encapsulation material, characterized in that, Contains the curable composition of claim 1 or the compound of claim 9.

15. A carbon material, characterized in that, It is obtained by calcining a curable composition or its cured product containing a compound having an acetylene group as represented by formula (A). [Chemistry 16] In formula (A), -X- is selected from -C (=O)-, -S (=O)-, -S (=O)2-, -P (=O)R a - and -P (=O) (OR b When there are multiple divalent groups (-X-) in the - group, they can be the same as or different from each other. R a R is a hydrogen or monovalent organic group. a When there are multiple instances, they can be the same as each other or different from each other. R b R is a hydrogen or monovalent organic group. b When there are multiple instances, they can be the same as each other or different from each other. Z is an n-valent organic group. n is an integer greater than or equal to 1.

16. A prepreg, characterized in that, Contains a compound with an acetylene group as represented by formula (A) and a fibrous reinforcing material. [Chemistry 17] In formula (A), -X- is selected from -C (=O)-, -S (=O)-, -S (=O)2-, -P (=O)R a - and -P (=O) (OR b When there are multiple divalent groups (-X-) in the - group, they can be the same as or different from each other. R a R is a hydrogen or monovalent organic group. a When there are multiple instances, they can be the same as each other or different from each other. R b R is a hydrogen or monovalent organic group. b When there are multiple instances, they can be the same as each other or different from each other. Z is an n-valent organic group. n is an integer greater than or equal to 1.

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