JP7095435B2 - Phenolic hydroxyl group-containing compounds, thermosetting compositions using them, and their cured products - Google Patents

Description

The present invention relates to a phenolic hydroxyl group-containing compound, a thermosetting composition using the same, and a cured product thereof.

Carbon fiber reinforced carbon composite materials are used in applications that require resistance to harsh temperature conditions and extremely high strength, such as rocket nozzles and brake materials for aircraft and competition automobiles. In addition, by utilizing its conductivity, it is also used for arms of transport appliances, fuel cell electrodes, etc. for static electricity elimination in the semiconductor industry.
It is known that it is useful to increase the residual carbon content in the carbonization treatment process as a means for obtaining heat resistance, chemical resistance, high strength, and high chemical resistance according to these application requirements. Normally, it is a common method to mold a prepreg sheet impregnated with a matrix resin such as phenol resin or furan resin into long carbon fiber or its woven fabric, and then carbonize it. There was a big problem that interlayer cracking due to blistering and curing shrinkage of the resin and voids due to sink marks occurred frequently.
As an improved method, a method of adding a filler to a matrix resin is generally used, and Patent Document 1 discloses a method of using a graphite powder filler as an added carbon source. Further, Patent Document 2 describes mesocarbon globules obtained by treating heavy petroleum oil, tar pitch, etc., and the carbides of the mesocarbon globules are 3 to 40% by weight, and carbon fiber is used. It is stated that the carbon content of the resin having a residual carbon content of 45% or more of 40 to 85% by weight should be adjusted to be in the range of 5 to 50% by weight after firing and carbonization.
However, in recent years, fullerenes, carbon nanotubes, graphene, etc. (Patent Documents 3 and 4) have been added as carbon source fillers for the purpose of further enhancing the performance, and the residual carbon ratio after firing is dramatically increased to improve the performance. Although the method is disclosed, nanocarbon materials such as fullerenes and carbon nanotubes have a big problem that their uses are limited because their industrial mass synthesis itself is expensive.

Japanese Unexamined Patent Publication No. 57-209883 Japanese Unexamined Patent Publication No. 2-9776 Japanese Unexamined Patent Publication No. 2013-193900 Japanese Unexamined Patent Publication No. 2009-144000

In order to solve these problems, the market is expected to develop a low-cost, high-residue carbon compound that can be industrially mass-synthesized using a general-purpose phenol compound.

An object of the present invention is to provide a low-cost, high-residue carbon compound that can be industrially synthesized in large quantities using a general-purpose phenol compound.

As a result of diligent studies to solve the above problems, the present inventors and others have found that a cage-type compound using an alkyl-substituted resorcinol compound and a polyaldehyde compound as reaction raw materials can be industrially mass-synthesized at low cost. We have found that it is useful as a high residual carbon compound, and have completed the present invention.

That is, the present invention relates to a cage-type compound containing an alkyl-substituted resorcinol compound (A) and a polyaldehyde compound (B) as essential reaction raw materials.

The present invention further relates to a carbon source filler containing the squirrel-cage compound and the solvent (C) included in the squirrel-cage compound.

The present invention further relates to a curable composition containing the carbon source filler and the matrix resin (D).

The present invention further relates to a cured product of the curable composition.

The present invention further relates to a fiber reinforced composite material containing the fiber material (F) and the curable composition.

According to the present invention, a cage-type compound useful as a low-cost high-residue carbon compound that can be synthesized in large quantities industrially, a carbon source filler using the same, a curable composition, a cured product thereof, and a fiber-reinforced composite material are provided. Can be provided.

FIG. 1 is a GPC chart of the squirrel-cage compound 1 obtained in Production Example 1. FIG. 2 is a 1H-NMR chart of the squirrel-cage compound 1 obtained in Production Example 1. FIG. 3 is a 13C-NMR chart of the squirrel-cage compound 1 obtained in Production Example 1. FIG. 4 is a MALDI-TOF-MAS spectrum of the cage compound 1 obtained in Production Example 1. FIG. 5 is a GPC chart of the squirrel-cage compound 2 obtained in Comparative Production Example 1.

Hereinafter, one embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications as long as the effects of the present invention are not impaired.

[Squirrel-cage compound]
The cage-type compound of the present invention contains an alkyl-substituted resorcinol compound (A) and a polyaldehyde compound (B) as essential reaction raw materials.
Here, the cage-type compound is defined as a compound having an isolated space in the molecule and the whole molecule is bonded by a chemical bond such as a carbon-carbon bond.

[Alkyl Substituted Resorcinol Compound (A)]
The alkyl-substituted resorcinol compound (A) used as a raw material for the cage-type compound according to the present invention may be any resorcinol substituted with an alkyl group and is not particularly limited. In one embodiment of the invention, the alkyl substituted resorcinol compound (A) is resorcinol substituted with an alkyl group having 1 to 9 carbon atoms, specifically, methylresorcinol, ethylresorcinol, propylresorcinol, butylresorcinol. , Pentyl resorcinol, hexyl resorcinol, heptyl resorcinol, octyl resorcinol and nonyl resorcinol. These alkyl-substituted resorcinol compounds (A) can be used alone or in combination of two or more.

[Polyaldehyde compound (B)]
The polyaldehyde compound (B) used as a raw material for the cage-type compound according to the present invention is not particularly limited as long as it is a compound having two or more aldehyde groups in the molecule. Specific examples of the polyaldehyde compound (B) include aliphatic dialdehydes such as glyoxal, malonaldehyde, succinaldehyde, glutaaldehyde, and adipaldehyde; aromatic dialdehydes such as phthalaldehyde, isophthalaldehyde, and terephthalaldehyde. An aliphatic trialdehyde such as triformylmethane; an aromatic trialdehyde such as benzenetrialdehyde can be used. In one embodiment of the present invention, the polyaldehyde compound (B) is preferably a dialdehyde compound or a trialdehyde compound, and more preferably a dialdehyde compound or a trialdehyde compound having 3 to 10 carbon atoms. Of these, glutaraldehyde, adipaldehyde, or terephthalaldehyde is preferable because it is easily available. The polyaldehyde compound (B) used as a raw material may be one kind of compound or may be used in combination of two or more kinds of compounds.

［式中ＲはＨを除く、炭素原子数１～９のアルキル基である。］
で表される、かご型化合物である。 In one embodiment of the present invention, the cage-type compound has the following structural formula (1).

[R in the formula is an alkyl group having 1 to 9 carbon atoms excluding H. ]
It is a cage-type compound represented by.

[Manufacturing method of cage compound]
The reaction between the alkyl-substituted resorcinol compound (A) and the polyaldehyde compound (B) can be carried out in the same manner as in a general method for producing a phenol resin. Specifically, the polyaldehyde compound (B) is 0.1 to 1.0 mol, preferably 0.1 to 0.5 mol, more preferably 0.1 to 1.0 mol, based on a total of 1 mol of the alkyl-substituted resorcinol compound (A). It can be used in the range of 0.2 to 0.4 mol, and a method of reacting under temperature conditions of 50 to 200 ° C., preferably 50 to 120 ° C., more preferably 60 to 90 ° C. can be mentioned.

[Carbon source filler]
The carbon source filler of the present invention contains the cage-type compound and the solvent (C) included in the cage-type compound.

[Subsumed solvent (C)]
The solvent (C) to be included is not particularly limited as long as it is included in the cage-type compound and serves as a carbon source. The included solvent includes aromatic hydrocarbon solvents such as benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, methylethylbenzene, ethylbenzene and diethylbenzene, and halogen-based solvents such as chloroform, methylene chloride, dichloromethane, chlorobenzene and dichlorobenzene. A solvent can be preferably used. These subsumed solvents (C) can be used alone or in combination of two or more.
The mixing ratio of the cage compound and the solvent (C) to be included is preferably 10: 1 to 1:20, more preferably 5: 1 to 1:10, and 2: 1 to 1: 5 in terms of molar ratio. More preferred.

[Cursable composition]
The curable composition of the present invention contains the cage-type compound, a solvent (C) included in the cage-type compound, and a matrix resin (D).

[Matrix resin (D)]
As the matrix resin, for example, a curable resin can be used. The curable resin includes functions in addition to thermosetting resins such as phenol resin, polyimide resin, polyamideimide resin, polyetherimide resin, bismaleimide resin, unsaturated polyester resin, epoxy resin, melamine resin, and urea resin. Thermoplastic resins such as polycarbonate resin, polyphenylene ether resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene resin, polypropylene resin, polyether sulfone resin, polyketone resin, polyether ketone resin, polyether ether ketone resin, etc. for the purpose of imparting sex. Can be used. Above all, a phenol resin can be preferably used. The phenol resin includes a resol resin, a novolak resin and the like. These matrix resins (D) can be used alone or in combination of two or more.

Examples of the resole resin include phenol, alkylphenols such as cresol and xylenol, bisphenols such as phenylphenol, resorcinol, biphenyl, bisphenol A and bisphenol F, phenolic hydroxyl group-containing compounds such as naphthol and dihydroxynaphthalene, and aldehyde compounds which are alkaline. Examples thereof include a polymer obtained by reacting under catalytic conditions.

As the novolak resin, phenol, alkylphenols such as cresol and xylenol, phenylphenols, resorcinols, biphenyls, bisphenols such as bisphenol A and bisphenol F, phenolic hydroxyl group-containing compounds such as naphthol and dihydroxynaphthalene, and aldehyde compounds are used as acidic catalyst conditions. Examples thereof include the polymer obtained by reacting below.

The blending amount of the carbon source filler and the matrix resin is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the solid content of the matrix resin, and is preferably 3 to 20 parts by mass. It is more preferable that the amount is 5 to 15 parts by mass, and the ratio is more preferably 5 to 15 parts by mass.

The curable composition of the present invention may further contain a curing agent (E1) and / or a curing catalyst (E2).

[Curing agent (E1)]
Examples of the curing agent (E1) include a melamine compound, a guanamine compound, a glycol uryl compound, a urea compound, a resol resin, and an epoxy compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group. , An isocyanate compound, an azido compound, a compound containing a double bond such as an alkenyl ether group, an acid anhydride, an oxazoline compound and the like. These curing agents (E1) may be used alone or in combination of two or more.

The melamine compound is, for example, a compound in which 1 to 6 methylol groups of hexamethylol melamine, hexamethoxymethyl melamine, and hexamethylol melamine are methoxymethylated, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, and methylol of hexamethylol melamine. Examples thereof include compounds in which 1 to 6 groups are asyloxymethylated.

The guanamine compound is, for example, a compound in which 1 to 4 methylol groups of tetramethylol guanamine, tetramethoxymethyl guanamine, tetramethoxymethylbenzoguanamine, and tetramethylol guanamine are methoxymethylated, tetramethoxyethyl guanamine, tetraacyloxyguanamine, and tetra. Examples thereof include a compound in which 1 to 4 methylol groups of methylolguanamine are acyloxymethylated.

The glycoluril compound is, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4,6-tetrakis (1,3,4,6-tetrakis). Hydroxymethyl) glycol uryl and the like can be mentioned.

Examples of the urea compound include 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea and 1,1,3,3-tetrakis (methoxymethyl) urea. Be done.

The resole resin is, for example, phenol, an alkylphenol such as cresol or xylenol, a phenylphenol, a resorcinol, a biphenyl, a bisphenol such as bisphenol A or bisphenol F, a phenolic hydroxyl group-containing compound such as naphthol or dihydroxynaphthalene, and an aldehyde compound which is alkaline. Examples thereof include a polymer obtained by reacting under catalytic conditions.

Examples of the epoxy compound include tris (2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, and trimethylolethane triglycidyl ether.

Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, cyclohexane diisocyanate and the like.

Examples of the azide compound include 1,1'-biphenyl-4,4'-bis azide, 4,4'-methylidene bis azide, 4,4'-oxybis azide and the like.

Examples of the compound containing a double bond such as an alkenyl ether group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, and tetramethylene glycol divinyl ether. , Neopentyl glycol divinyl ether, trimethylol propanetrivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropanetrivinyl ether. And so on.

The acid anhydride is, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, 4,4. Aromatic acid anhydrides such as'-(isopropyridene) diphthalic acid anhydride, 4,4'-(hexafluoroisopropyridene) diphthalic acid anhydride; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride , Anhydrous methylhexahydrophthalic acid, Endomethylenetetrahydrophthalic anhydride Dodecenylsuccinic anhydride, Trialkyltetrahydrophthalic anhydride and the like alicyclic carboxylic acid anhydrides and the like can be mentioned.

The blending amount of the curing agent in the curable composition of the present invention is preferably 0.1 to 50 parts by mass, and 0.2 to 30 parts by mass with respect to 100 parts by mass of the matrix resin. Is more preferable, and the ratio is more preferably 0.5 to 20 parts by mass.

[Curing catalyst (E2)]
As the curing catalyst (E2), for example, an inorganic acid such as phosphoric acid; an organic acid such as dodecylbenzenesulfonic acid or toluenesulfonic acid, or a substance obtained by blocking these with an amine or the like can be preferably used. These curing catalysts (E2) may be used alone or in combination of two or more. The blending amount of the curing catalyst in the curable composition of the present invention is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the matrix resin, and is preferably 1 to 20 parts by mass. It is more preferable, and it is further preferable that the ratio is 3 to 15 parts by mass.

Further, the viscosity of the curable resin is preferably in the range of 200 to 8000 mPa · s (25 ° C.) because the impregnation property into the fiber material is further improved.

[Fiber reinforced composite material]
The fiber-reinforced composite material of the present invention contains a fiber material (F), the cage-type compound, a solvent (C) included in the cage-type compound, and a matrix resin (D).
The fiber-reinforced composite material is a composite material in which the curable composition is impregnated into the fiber material, and as a method for obtaining the fiber-reinforced composite material, each component constituting the curable composition is uniformly mixed, and then this is used. Is impregnated into the fiber material (F) and then cured to produce the fiber material (F).

Specifically, the curing temperature at the time of curing is preferably in the temperature range of 50 to 250 ° C., and in particular, after curing at 50 to 100 ° C. to form a tack-free cured product, further 120 to 120 to It is preferable to treat at a temperature condition of 200 ° C.

Here, the fiber material (F) may be twisted yarn, untwisted yarn, untwisted yarn, or the like, but untwisted yarn or untwisted yarn is preferable because it has both impregnation property and mechanical strength of the curable composition. Further, as the form of the reinforcing fiber material (F), a material in which the fiber directions are aligned in one direction or a woven fabric can be used. For woven fabrics, plain weaves, satin weaves, and the like can be freely selected according to the part to be used and the intended use. Specific examples thereof include carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like because of their excellent mechanical strength and durability, and two or more of these can be used in combination. Among these, carbon fiber and glass fiber are particularly preferable because the strength of the molded product is good. Here, the amount of the fiber material used when the curable composition is impregnated into the fiber material to form a fiber-reinforced composite material is such that the volume content of the fiber material in the fiber-reinforced composite material is in the range of 25% to 85%. The amount is preferably in the range of 40 to 70% by mass, more preferably. If the fiber content is low, a high-strength molded product may not be obtained, and if the fiber content is high, the impregnation property of the curable composition into the fiber is insufficient, causing swelling of the molded product. After all, there is a possibility that a high-strength molded product cannot be obtained.

As components of the carbon fiber reinforced carbon composite material of the present invention, for example, a polymerization inhibitor, a curing accelerator, a filler, a low shrinkage agent, a release agent, a thickener, a thickener, a pigment, an antioxidant, a plasticizer. , A flame retardant, an antibacterial agent, an ultraviolet stabilizer, a reinforcing material, a photocuring agent and the like can be further contained.

[Carbon fiber reinforced carbon composite material]
In one embodiment of the present invention, the carbon fiber material (F1) can be used as the fiber material (F).
As the carbon fiber material (F1), carbon fibers cut to a length of 2.5 to 50 mm are preferably used, but the fluidity in the mold at the time of molding, the appearance of the molded product, and the mechanical properties are more favorable. Carbon fibers cut to 5 to 40 mm are more preferable because of the improvement.

As the carbon fiber material (F1), various materials such as polyacrylonitrile-based, pitch-based, and rayon-based materials can be used. Among these, polyacrylonitrile-based materials can be easily obtained because high-strength carbon fibers can be easily obtained. Those are preferable.

The number of filaments of the fiber bundle used as the carbon fiber material (F1) is preferably 1000 to 60,000 because the impregnation property and the mechanical properties of the molded product are further improved.

Further, the carbon fiber material (F1) in the carbon fiber reinforced carbon composite material of the present invention is impregnated with a resin in a state where the fiber directions are random.

[Glass fiber reinforced carbon composite material]
In one embodiment of the present invention, the glass fiber material (F2) can be used as the fiber material (F).
The glass fiber material (F2) is not particularly limited, but it is preferable to use a glass fiber material having a fiber diameter of 50 nm to 2 μm, and more preferably a glass fiber material (F2) having a fiber diameter of 100 nm to 900 nm.

[Fiber reinforced molded product]
The fiber-reinforced molded product of the present invention contains a fiber material (F) and a curable composition containing the cage-type compound, the solvent (C) included in the cage-type compound, and the matrix resin (D).
The fiber-reinforced molded product of the present invention is a molded product in which the curable composition is impregnated with the fiber material (F), and as a method for obtaining the fiber-reinforced molded product, a fiber aggregate is laid in a mold and the curability is obtained. Using either the hand lay-up method, the spray-up method, or the male type or the female type, in which the compositions are laminated in multiple layers, the fiber material (F) is impregnated with the curable composition and stacked to form and pressurize. A vacuum bag method in which a flexible mold that can act on a molded product is covered and the airtightly sealed material is vacuum (decompressed) molded. The fiber material (F) is impregnated with the curable composition in advance to form a sheet. A prepreg in which the fiber material (F) is impregnated with the curable composition is manufactured by an SMC press method in which the fibers are compression-molded with a mold, an RTM method in which the curable composition is injected into a combined mold in which fibers are spread, and the like. , There is a method of baking this in a large autoclave. The fiber-reinforced molded product obtained above is a molded product having the fiber material (F) and the cured product of the curable composition.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples do not limit the interpretation of the present invention. The number average molecular weight (Mn), weight average molecular weight (Mw), and polydispersity (Mw / Mn) of the synthesized compound were measured under the following GPC measurement conditions.
[GPC measurement conditions]
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation
Column: Showa Denko Corporation "Shodex KF802" (8.0 mmφ x 300 mm) + Showa Denko Co., Ltd. "Shodex KF803" (8.0 mmφ x 300 mm) + "Shodex KF804" (8.0 mmφ x 300 mm)
Column temperature: 40 ° C
Detector: RI (Differential Refractometer)
Data processing: "GPC-8020 Model II Version 4.30" manufactured by Tosoh Corporation
Developing solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Sample: Tetrahydrofuran solution of 0.5% by mass in terms of resin solid content filtered through a microfilter Injection volume: 0.1 mL
Standard sample: The following monodisperse polystyrene (standard sample: monodisperse polystyrene)
Tosoh Corporation "A-500"
Tosoh Corporation "A-2500"
Tosoh Corporation "A-5000"
Tosoh Corporation "F-1"
Tosoh Corporation "F-2"
Tosoh Corporation "F-4"
Tosoh Corporation "F-10"
Tosoh Co., Ltd. "F-20"

1 For the measurement of the ¹ H-NMR spectrum, "AL-400" manufactured by JEOL Ltd. was used, and the DMSO _- d6 solution of the sample was analyzed for structural analysis. The measurement conditions of ¹ H-NMR spectrum are shown below.
[ ^{1 1} H-NMR spectrum measurement conditions]
Measurement mode: SGNNE (1H complete decoupling method for NOE elimination)
Pulse angle: 45 ° C pulse Sample concentration: 30 wt%
Accumulation number: 10,000 times

For the measurement of the ¹³ C-NMR spectrum, "AL-400" manufactured by JEOL Ltd. was used, and the DMSO _- d6 solution of the sample was analyzed for structural analysis. The measurement conditions of the ¹³ C-NMR spectrum are shown below.
[ ¹³ C-NMR spectrum measurement conditions]
Measurement mode: SGNNE (1H complete decoupling method for NOE elimination)
Pulse angle: 45 ° C pulse Sample concentration: 30 wt%
Accumulation number: 10,000 times

For the measurement of the MALDI-TOF-MS spectrum, "AXIMA TOF2" manufactured by Shimadzu Corporation was used, and the sample was analyzed using disanol as the matrix and sodium trifluoroacetate as the cationizing agent to perform molecular weight analysis.
Measurement mode: Linear mode Sample preparation: Sample / Dislanol / Sodium trifluoroacetate / THF = 10/10/1/1

[Production Example 1 Synthesis of Squirrel-cage Compound 1 (2MeNoria)]
25 g (0.2 mol) of 2-methylresorcinol and 10 g (0.05 mol) of a 50% glutaraldehyde aqueous solution were put into a 500 ml three-necked eggplant-shaped flask equipped with a Jimroth condenser and a thermometer, and dissolved in 50 ml of industrial ethanol. While stirring, 20 ml of 37% hydrochloric acid was added dropwise over 10 minutes in an ice bath, and after confirming that the temperature of the contents did not rise, the reaction was carried out by reflux stirring at 80 ° C. for 48 hours in an oil bath. After completion of the reaction, the contents of the flask were added dropwise to 1000 ml of water to perform a reprecipitation operation, and the precipitate was separated by filtration. The separated precipitate was dried in a vacuum dryer at 100 ° C. for 24 hours, redissolved in 50 ml of industrial ethanol, and added dropwise to 500 ml of diethyl ether to perform a reprecipitation operation. The obtained precipitate was separated by filtration, washed 10 times with 50 ml of diethyl ether, and dried in a vacuum dryer at 120 ° C. for 24 hours to obtain 8.6 g of the yellow powder of the cage compound 1 in a yield of 49. Obtained at 3%. Compounds were identified by gel permeation chromatography (GPC), ¹ H-NMR, ¹³ C-NMR, and MALDI-TOF-MS. The results are shown in FIGS. 1 to 4, respectively. In GPC, Mn1,745, Mw1,787, and Mw / Mn1.02 were observed as sharp single peaks (Fig. 1), and in MALDI-TOF-MS, 1,897 peaks indicating the formation of cage compound 1 were observed. (Fig. 4).

[Comparative Production Example 1 Synthesis of Squirrel-cage Compound 2 (Noria)]
44 g (0.4 mol) of resorcinol and 20 g (0.1 mol) of a 50% glutaraldehyde aqueous solution were put into a 500 ml three-necked eggplant-shaped flask equipped with a Jimroth condenser and a thermometer, and dissolved in 90 ml of industrial ethanol. While stirring, 60 ml of 37% hydrochloric acid was added dropwise over 30 minutes in an ice bath, and after confirming that the temperature of the contents did not rise, the reaction was carried out by reflux stirring at 80 ° C. for 48 hours in an oil bath. After completion of the reaction, the contents of the flask were added dropwise to 1000 ml of methanol to perform a reprecipitation operation, and the precipitate was separated by filtration. The separated precipitate was dried in a vacuum dryer at 100 ° C. for 24 hours, redissolved in 50 ml of industrial ethanol, and added dropwise to 500 ml of diethyl ether to perform a reprecipitation operation. The obtained precipitate was separated by filtration, washed 10 times with 50 ml of diethyl ether, and dried in a vacuum dryer at 100 ° C. for 24 hours to obtain 22.4 g of a yellow powder of cage-type compound 2 in a yield of 78. Obtained at 9%. Identification was performed by GPC, and it was observed as a single peak of Mn1,578, Mw1,672, and Mw / Mn1.06 (FIG. 5).

[Synthesis Example 1 Synthesis of Matrix Resin]
462 g of phenol, 639 g of 42% formalin aqueous solution, and 15 g of triethylamine were charged in a 2000 ml 4-neck flask provided with a cooling tube, and heated in an oil bath at 70 ° C. for 2 hours, stirred and reacted. The temperature was lowered to 50 ° C. with dehydration under reduced pressure to obtain 1200 g of an aqueous resin solution. The resin pH was 8.2, and the non-volatile content at 135 ° C. was 72%. A reprecipitation operation was performed by dropping 200 ml of the obtained resin solution onto 2000 ml of diethyl ether. The obtained precipitate was separated by filtration, washed 10 times with 500 ml of diethyl ether, and dried in a vacuum dryer at 60 ° C. for 72 hours to obtain 104 g of a brown powder of phenol resin. Similarly, the operations of reprecipitation and drying were repeated to obtain 507 g of matrix resin powder.

[Examples 1 and 2 and Comparative Examples 1 and 2]
The cage-type compound 1, the cage-type compound 2, and the matrix resin obtained in Production Example 1 and Comparative Production Example 1 were evaluated in the following manner.

Production of Aggregates 10 g of a 20 mass% ethanol solution of cage compound 1, cage compound 2 or matrix resin was added to 100 parts by mass of toluene or dichloromethane, and a reprecipitation operation was performed. The precipitate was separated by filtration, and the obtained precipitate was dried in a vacuum dryer at 120 ° C. for 24 hours to remove volatile components adhering to the surface to obtain an aggregate.

Composition ratio of agglomerates ^{1 1} H-NMR of the obtained agglomerates was measured, and the value of the encapsulated solvent when 1 molecule of each compound was set to 1 was calculated from the area ratio of the peak.

Measurement of residual carbonization rate The residual carbonization rate is evaluated by using a differential thermal weight simultaneous measurement device (TG / DTA) and when the temperature of the cage compound 1, cage compound 2 or matrix resin is raised at a constant rate under the following conditions. The weight loss was measured, and the value of the carbonization rate at 600 ° C. was taken as the residual coal rate.
Measuring equipment: TG / DTA 6200 manufactured by Seiko Instruments
Measurement range: RT-600 ° C
Temperature rise rate: 10 ° C / min Atmosphere: Nitrogen

[Examples 3 and 4 and Comparative Examples 3 and 4]
Further, the aggregates obtained in Examples 1 and 2 and Comparative Example 1 were evaluated in the following manner.

Production of Curable Composition The aggregates obtained in Examples 1 and 2 and Comparative Example 1 were mixed with a matrix resin, diethylene glycol (DEG) and ethanol to obtain a curable composition (Examples 3 and 4, respectively). And Comparative Example 3). Further, as Comparative Example 4, a product not mixed with aggregates was prepared.

Measurement of bending characteristics (bending strength, elongation and elastic modulus) ^Two 50 × 50 mm glass mats with a basis weight of 300 g / m were placed on a glass plate, and the curable compositions of Examples 3 and 4 and Comparative Examples 3 and 4 were placed. Was applied with a roller so as to be 72 g / m ² . After curing the applied sample at room temperature for 48 hours, the test piece was dried and cured in a constant temperature dryer under the conditions of 110 ° C. x 5 minutes + 170 ° C. x 10 minutes, and then the obtained cured product was subjected to JIS K7017 A method. The bending characteristics were measured according to the above.

From the above, the cage-type compound of the present invention can be used as a carbon source filler because the residual carbon ratio increases by incorporating the solvent as a carbon source by utilizing the inclusion behavior in which the cage-type compound takes in the solvent. It turned out to be useful.
Further, the cured product of the curable composition using the cage-type compound of the present invention has bending characteristics equal to or higher than those using the nanocarbon material, and is useful as an impregnating composition of the fiber-reinforced composite material. It became clear that.
Furthermore, compared to nanocarbon materials such as fullerenes and carbon nanotubes used as additives, industrial mass synthesis is possible and the cost is low, so it has high industrial superiority and usefulness. Is.

Claims (7)

A fiber-reinforced composite material containing a carbon source filler, a matrix resin (D), and a fiber material (F).
The carbon source filler contains a cage-type compound and a solvent (C) included in the cage-type compound.
The cage-type compound is a fiber-reinforced composite material which is a cage-type compound containing an alkyl-substituted resorcinol compound (A) and a polyaldehyde compound (B) as essential reaction raw materials . The fiber-reinforced composite material according to claim 1, wherein the alkyl-substituted resorcinol compound (A) is resorcinol substituted with an alkyl group having 1 to 9 carbon atoms. The fiber-reinforced composite material according to claim 1 or 2, wherein the polyaldehyde compound (B) is a dialdehyde compound or a trialdehyde compound having 3 to 10 carbon atoms. The fiber-reinforced composite material according to any one of claims 1 to 3, wherein the polyaldehyde compound (B) is glutaraldehyde, adipaldehyde or terephthalaldehyde. The cage-type compound has the following structural formula (1).

[R in the formula is an alkyl group having 1 to 9 carbon atoms. ]
The fiber-reinforced composite material according to any one of claims 1 to 4, which is represented by. The fiber-reinforced composite material according to any one of claims 1 to 5 , further comprising a curing agent (E1) and / or a curing catalyst (E2). The fiber-reinforced composite material according to any one of claims 1 to 6 , wherein the fiber material is a carbon fiber material or a glass fiber material.

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