Thermosetting resin composition, cured product, and molded article

Abstract

To provide a thermosetting resin composition capable of enhancing the heat resistance of the resulting cured product, a cured product having enhanced heat resistance, and a molded article including the cured product.SOLUTION: A thermosetting resin composition includes a monomer (A) having two carboxylic anhydride rings and a resin (B) having two or more amino groups.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a thermosetting resin composition, a cured product, and a molded article.

Background Art

[0002] As a molding material, for example, there is a phenolic resin composition.

[0003] As a technique related to a phenolic resin composition, for example, the technique described in Patent Document 1 can be mentioned. Patent Document 1 aims to provide a thermosetting resin composition and a friction material suitable for producing a friction material excellent in heat resistance, flexibility, and abrasion resistance. A triazine-modified resol-type phenolic resin (1) obtained by reacting bisphenol (a), triazine (b), aldehydes (c), and a novolak-type phenolic resin (e1) obtained with phenol (d) as essential constituent components, or a triazine-modified resol-type phenolic resin (2) obtained by reacting phenol (d), triazine (b), aldehydes (c), and a novolak-type phenolic resin (e2) obtained with bisphenol (a) as essential constituent components. A thermosetting resin composition containing the above is described, and the usage amount of bisphenol (a) and phenol (d) [bisphenol (a) / phenol (d)] is 0.4 to 1.0 in terms of molar conversion.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention provides a thermosetting resin composition capable of improving the heat resistance of the obtained cured product, a cured product with improved heat resistance, and a molded article including the above cured product.

Means for Solving the Problems

[0006] The inventors of the present invention have found that by including a monomer having two anhydrous carboxylic acid rings and a resin containing two or more amino groups, the heat resistance of the resulting cured product can be improved, and thus completed the present invention.

[0007] According to the present invention, there are provided a thermosetting resin composition, a cured product, and a molded article as described below.

[0008] [1] A thermosetting resin composition comprising a monomer (A) containing two anhydrous carboxylic acid rings and a resin (B) containing two or more amino groups. [2] The thermosetting resin composition according to [1] above, wherein the monomer (A) contains a compound represented by the following formula (1). [Chemical formula] (In the above formula (1), X represents a structure represented by the following formula (2) or (3).) [Chemical formula] (In the above formula (3), Y is a single bond or a divalent organic group.) [3] The thermosetting resin composition according to [1] or [2] above, wherein the molecular weight of the monomer (A) is 200 or more and 900 or less. [4] The thermosetting resin composition according to any one of [1] to [3] above, wherein the monomer (A) contains one or more selected from the group consisting of pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, and 3,3',4,4'-biphenyltetracarboxylic dianhydride. [5] The thermosetting resin composition according to any one of [1] to [4] above, wherein the content of the monomer (A) in the thermosetting resin composition is 1 part by mass or more and 150 parts by mass or less when the content of the resin (B) is 100 parts by mass. [6] The thermosetting resin composition according to any one of [1] to [5] above, which is in powder form. [7] The thermosetting resin composition according to any one of [1] to [5] above, which is in liquid form. [8] The thermosetting resin composition according to [7] above, which is a one-component resin composition or a two-component resin composition. [9] The thermosetting resin composition according to any one of [1] to [8] above, wherein the resin (B) contains one or more selected from the group consisting of aniline resins, melamine resins, and urea resins.

[10] The thermosetting resin composition according to [9] above, wherein the resin (B) contains an aniline formaldehyde resin.

[11] The thermosetting resin composition according to any one of [1] to

[10] above, wherein the polystyrene-reduced mass average molecular weight of the resin (B) is 500 or more and 20,000 or less.

[12] The thermosetting resin composition according to any one of [1] to

[11] above, wherein the content of the resin (B) in the thermosetting resin composition is 10% by mass or more and 99% by mass or less when the total amount of the components excluding the solvent of the thermosetting resin composition is 100% by mass.

[13] The thermosetting resin composition according to any one of [1] to

[12] above, wherein the extraction residue amount of the thermosetting resin composition by the following (Method 1) is 1.0% by mass or less when the total amount of the components excluding the solvent of the thermosetting resin composition is 100% by mass. (Method 1) The thermosetting resin composition is heated at 280°C for 1 hour to obtain a cured product of the thermosetting resin composition. Next, by the Soxhlet extraction method, the cured product is boiled with 100 g of acetone for 6 hours to extract unreacted components. After boiling, acetone is removed, and the residue is dried in a vacuum dryer at 80°C for 5 hours. Then, the residue is weighed, and the extraction residue amount is calculated based on the following formula (A). Extraction residue (mass %) = ((mass of cured product of thermosetting resin composition before boiling (g) - mass of residue (g)) / (mass of cured product of thermosetting resin composition before boiling (g))) × 100 ··· Formula (A)

[14] Regarding the cured product obtained by heating the above thermosetting resin composition at 280 °C for 1 hour, measured under the conditions of flowing gas: nitrogen, measurement temperature range: 25 °C to 500 °C, and heating rate: 10 °C / min in accordance with JIS K 7120:1987, the 10% mass loss temperature is 370 °C or higher, and the thermosetting resin composition according to any one of the above [1] to

[13] .

[15] The cured product of the thermosetting resin composition according to any one of the above [1] to

[14] .

[16] A molded article containing the cured product described in the above

[15] .

Advantages of the Invention

[0009] According to the present invention, it is possible to provide a thermosetting resin composition capable of improving the heat resistance of the obtained cured product, a cured product with improved heat resistance, and a molded article using the above cured product.

Modes for Carrying Out the Invention

[0010] Hereinafter, the present invention will be described based on embodiments. In this embodiment, "A to B" indicating a numerical range represents A or more and B or less unless otherwise specified.

[0011] <Thermosetting Resin Composition> The thermosetting resin composition of this embodiment contains a monomer (A) containing two anhydrous carboxylic acid rings and a resin (B) containing two or more amino groups.

[0012] According to the thermosetting resin composition of this embodiment, it is possible to provide a thermosetting resin composition capable of improving the heat resistance of the obtained cured product, a cured product with improved heat resistance, and a molded article using the above cured product. This is presumably because the monomer (A) containing two carboxylic anhydride rings crosslinks with the resin (B) containing two or more amino groups, generating a polyimide resin with improved heat resistance. Carboxylic anhydride itself has excellent heat resistance, and when the monomer containing two carboxylic anhydride rings crosslinks with the resin containing two or more amino groups to form a polyimide resin having a network structure, the heat resistance is considered to be improved.

[0013] [Monomer (A) containing two carboxylic anhydride rings] The thermosetting resin composition of this embodiment contains a monomer (A) containing two carboxylic anhydride rings (hereinafter also referred to as monomer (A)). From the viewpoint of further improving the heat resistance of the obtained cured product, the monomer (A) of this embodiment preferably contains a compound represented by the following formula (1).

[0014] [Chemical formula]

[0015] In the above formula (1), X represents a structure represented by the following formula (2) or (3).

[0016] [Chemical formula]

[0017] In the above formula (3), Y is a single bond or a divalent organic group.

[0018] From the viewpoint of further improving the heat resistance of the resulting cured product, the divalent organic group preferably contains one or more selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms, -O-, -CO-, -SO2-, -S-, -SO2-, -CONH-, -COO-, -OCO-, -C(CF3)2-, -COO-Z-OCO- and -O-Ph-C(CH3)2-Ph-O-, and more preferably contains -CO-. The above Z preferably contains one or more selected from the group consisting of -C6H4- and -(CH2) n - and -CH2-CH(-O-C(=O)-CH3)-CH2-. The above n is preferably an integer of 1 or more and 30 or less. In the divalent organic group, at least one hydrogen atom may be substituted with a substituent. The substituent preferably contains one or more selected from the group consisting of a hydroxy group, an aldehyde group, a carboxy group, a carbonyl group, a nitro group, an amino group, a sulfo group, an alkyl group, a vinyl group, an aryl group and a halogeno group.

[0019] From the viewpoint of further improving the heat resistance of the resulting cured product, the molecular weight of the monomer (A) in the present embodiment is preferably 200 or more, more preferably 210 or more, and preferably 900 or less, more preferably 850 or less, still more preferably 800 or less, still more preferably 750 or less, still more preferably 700 or less, still more preferably 650 or less, still more preferably 600 or less, still more preferably 550 or less, still more preferably 500 or less, still more preferably 450 or less, still more preferably 400 or less, still more preferably 350 or less. From the perspective of further improving the heat resistance of the resulting cured product, the molecular weight of the monomer (A) in this embodiment is preferably 200 or more and 900 or less, more preferably 200 or more and 850 or less, still more preferably 200 or more and 800 or less, still more preferably 200 or more and 750 or less, still more preferably 200 or more and 700 or less, still more preferably 200 or more and 650 or less, still more preferably 210 or more and 600 or less, still more preferably 210 or more and 550 or less, still more preferably 210 or more and 500 or less, still more preferably 210 or more and 450 or less, still more preferably 210 or more and 400 or less, still more preferably 210 or more and 350 or less.

[0020] From the perspective of further improving the heat resistance of the resulting cured product, the monomer (A) in this embodiment preferably contains one or more selected from the group consisting of pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, p-phenylene bis(trimellitic acid monoester anhydride), ethylene glycol bisanhydrotrimellitate, 4,4'-biphthalic anhydride, 3,4'-biphthalic anhydride, and naphthalene-1,4,5,8-tetracarboxylic dianhydride, and more preferably contains one or more selected from the group consisting of pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, and 3,3',4,4'-biphenyltetracarboxylic dianhydride.

[0021] From the viewpoint of further improving the heat resistance of the resulting cured product, the content of the monomer (A) in the thermosetting resin composition of the present embodiment, when the content of the resin (B) containing two or more amino groups is 100 parts by mass, is preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, still more preferably 25 parts by mass or more, and is preferably 150 parts by mass or less, more preferably 140 parts by mass or less, still more preferably 130 parts by mass or less, still more preferably 120 parts by mass or less, still more preferably 110 parts by mass or less, still more preferably 100 parts by mass or less, still more preferably 90 parts by mass or less. From the viewpoint of further improving the heat resistance of the resulting cured product, the content of the monomer (A) in the thermosetting resin composition of the present embodiment, when the content of the resin (B) containing two or more amino groups is 100 parts by mass, is preferably 1 part by mass or more and 150 parts by mass or less, more preferably 5 parts by mass or more and 140 parts by mass or less, still more preferably 10 parts by mass or more and 130 parts by mass or less, still more preferably 15 parts by mass or more and 120 parts by mass or less, still more preferably 20 parts by mass or more and 110 parts by mass or less, still more preferably 25 parts by mass or more and 100 parts by mass or less, still more preferably 25 parts by mass or more and 90 parts by mass or less.

[0022] [Resin (B) containing two or more amino groups] The thermosetting resin composition of the present embodiment contains a resin (B) containing two or more amino groups (hereinafter also referred to as resin (B)). Examples of the resin (B) of the present embodiment include polymers obtained by polycondensation of amino compounds and aldehydes, and specifically, resins obtained by polycondensing amino compounds and formaldehyde (aminoformaldehyde resins). From the viewpoint of further improving the heat resistance of the resulting cured product, the resin (B) of the present embodiment preferably contains one or more selected from the group consisting of aniline resins, melamine resins, and urea resins, more preferably contains one or more selected from the group consisting of aniline resins and melamine resins, and still more preferably contains an aniline resin.

[0023] Examples of the aniline resin include polymers obtained by polycondensation of aniline and aldehydes, and specifically, a resin obtained by polycondensing aniline and formaldehyde (aniline formaldehyde resin). Examples of the melamine resin include polymers obtained by polycondensation of melamine and aldehydes, and specifically, a resin obtained by polycondensing melamine and formaldehyde (melamine formaldehyde resin). Examples of the urea resin include polymers obtained by polycondensation of urea and aldehydes, and specifically, a resin obtained by polycondensing urea and formaldehyde (urea formaldehyde resin). Among these, from the viewpoint of further improving the heat resistance of the obtained cured product, the resin (B) of the present embodiment preferably contains an aniline formaldehyde resin.

[0024] The number of amino groups contained in the resin (B) of the present embodiment (hereinafter also referred to as the average amino group content) is 2 or more, preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, still more preferably 6 or more, still more preferably 8 or more, still more preferably 10 or more, from the viewpoint of further improving the heat resistance of the obtained cured product, and the higher the upper limit value, the more preferable it is. For example, it may be 1000 or less, 500 or less, 100 or less, 50 or less, 40 or less, or 30 or less. The number of amino groups contained in the resin (B) of the present embodiment is preferably 2 or more and 1000 or less, more preferably 3 or more and 1000 or less, still more preferably 4 or more and 500 or less, still more preferably 5 or more and 100 or less, still more preferably 6 or more and 50 or less, still more preferably 8 or more and 40 or less, still more preferably 10 or more and 30 or less, from the viewpoint of further improving the heat resistance of the obtained cured product.

[0025] The weight-average molecular weight in terms of polystyrene of the resin (B) in the present embodiment is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, still more preferably 800 or more, still more preferably 900 or more, still more preferably 1,000 or more, still more preferably 1,100 or more, still more preferably 1,200 or more, still more preferably 1,300 or more, still more preferably 1,400 or more, from the viewpoint of further improving the heat resistance of the obtained cured product, and is preferably 20,000 or less, more preferably 18,000 or less, still more preferably 15,000 or less, still more preferably 12,000 or less, still more preferably 10,000 or less, still more preferably 8,000 or less, still more preferably 5,000 or less, still more preferably 3,000 or less. The weight-average molecular weight in terms of polystyrene of the resin (B) in the present embodiment is preferably 500 or more and 20,000 or less, more preferably 600 or more and 20,000 or less, still more preferably 700 or more and 18,000 or less, still more preferably 800 or more and 18,000 or less, still more preferably 900 or more and 15,000 or less, still more preferably 1,000 or more and 12,000 or less, still more preferably 1,100 or more and 10,000 or less, still more preferably 1,200 or more and 8,000 or less, still more preferably 1,300 or more and 5,000 or less, still more preferably 1,400 or more and 3,000 or less, from the viewpoint of further improving the heat resistance of the obtained cured product.

[0026] Specifically, the method for measuring the weight-average molecular weight of the resin (B) in the present embodiment may include the GPC measurement method (gel permeation chromatography method). More specifically, the weight-average molecular weight of the resin (B) is measured based on the following <GPC measurement conditions>, and conversion is performed using the calibration curve of standard polystyrene. <GPC measurement conditions> The GPC device is composed of a pump, an injector, a guard column, a column, and a detector. For measurement, tetrahydrofuran (THF), for example, is used as the solvent. The flow rate of the pump is, for example, 0.5 ml / min. A commercially available guard column (for example, TSK GUARDCOLUMN HR-L manufactured by Tosoh Corporation: diameter 6.0 mm, tube length 40 mm) is used for the guard column, and for the column, for example, a plurality of commercially available polystyrene gel columns (TSK-GEL GMHHR-L manufactured by Tosoh Corporation: diameter 7.8 mm, tube length 30 mm) are connected in series. A differential refractometer (RI detector. For example, differential refractometer (RI) detector W2414 manufactured by WATERS) is used for the detector. As the sample, a THF solution of resin (B) adjusted to a concentration of 3 to 4 mg / ml is prepared, and about 50 to 150 μl of this is injected from the injector for measurement. In the analysis of the sample, a calibration curve prepared with a monodisperse polystyrene standard sample is used.

[0027] From the viewpoint of further improving the heat resistance of the obtained cured product, the melting point of the resin (B) in the present embodiment is preferably 60°C or higher, more preferably 63°C or higher, still more preferably 65°C or higher, still more preferably 68°C or higher, still more preferably 70°C or higher, and preferably 150°C or lower, more preferably 140°C or lower, still more preferably 130°C or lower, still more preferably 120°C or lower, still more preferably 110°C or lower. From the viewpoint of further improving the heat resistance of the obtained cured product, the melting point of the resin (B) in the present embodiment is preferably 60°C or higher and 150°C or lower, more preferably 63°C or higher and 140°C or lower, still more preferably 65°C or higher and 130°C or lower, still more preferably 68°C or higher and 120°C or lower, still more preferably 70°C or higher and 110°C or lower.

[0028] From the viewpoint of further improving the heat resistance of the resulting cured product, when the total amount of components excluding the solvent described later in the above thermosetting resin composition is taken as 100% by mass, the content of the resin (B) in the thermosetting resin composition of the present embodiment is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, still more preferably 25% by mass or more, still more preferably 30% by mass or more, still more preferably 35% by mass or more, still more preferably 40% by mass or more, still more preferably 45% by mass or more, still more preferably 50% by mass or more, and preferably 99% by mass or less, more preferably 97% by mass or less, still more preferably 95% by mass or less, still more preferably 93% by mass or less. From the viewpoint of further improving the heat resistance of the resulting cured product, when the total amount of components excluding the solvent described later in the above thermosetting resin composition is taken as 100% by mass, the content of the resin (B) in the thermosetting resin composition of the present embodiment is preferably 10% by mass or more and 99% by mass or less, more preferably 15% by mass or more and 99% by mass or less, still more preferably 20% by mass or more and 99% by mass or less, still more preferably 25% by mass or more and 97% by mass or less, still more preferably 30% by mass or more and 97% by mass or less, still more preferably 35% by mass or more and 95% by mass or less, still more preferably 40% by mass or more and 95% by mass or less, still more preferably 45% by mass or more and 93% by mass or less, still more preferably 50% by mass or more and 93% by mass or less.

[0029] From the viewpoint of further improving the heat resistance of the resulting cured product, when the total amount of components excluding the solvent described later in the above thermosetting resin composition is taken as 100% by mass, the total content of the monomer (A) and the resin (B) in the thermosetting resin composition of the present embodiment is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and the upper limit is not particularly limited, for example, it is 100% by mass or less.

[0030] [Physical properties] Regarding the extraction residue amount of the thermosetting resin composition of this embodiment by the following (Method 1), from the viewpoint of further improving the heat resistance of the obtained cured product, when the total amount of the components excluding the solvent of the thermosetting resin composition is 100% by mass, it is preferably 1.0% by mass or less, more preferably 0.9% by mass or less, still more preferably 0.8% by mass or less, still more preferably 0.7% by mass or less, still more preferably 0.6% by mass or less, still more preferably 0.5% by mass or less, still more preferably 0.4% by mass or less, still more preferably 0.3% by mass or less. And the lower limit value of the above extraction residue amount is not particularly limited, for example, it is 0.0% by mass or more.

[0031] (Method 1) By heating the above thermosetting resin composition at 280 °C for 1 hour, a cured product of the thermosetting resin composition is obtained. Next, by the Soxhlet extraction method, 5 g of the above cured product is boiled with 100 g of acetone for 6 hours to extract unreacted components. After boiling, acetone is removed, and the residue is dried in a vacuum dryer at 80 °C for 5 hours. Then, the residue is weighed, and the extraction residue amount is calculated based on the following formula (A). Extraction residue amount (% by mass) = (mass of the cured product of the thermosetting resin composition before boiling (g) - mass of the residue (g)) / (mass of the cured product of the thermosetting resin composition before boiling (g)) × 100 ··· Formula (A)

[0032] Regarding the cured product obtained by heating the thermosetting resin composition of this embodiment at 280 °C for 1 hour, in accordance with JIS K 7120:1987, the 10% mass loss temperature measured under the conditions of inlet gas: nitrogen, measurement temperature range: 25 °C to 500 °C, and heating rate: 10 °C / min is preferably 370 °C or higher, more preferably 400 °C or higher, still more preferably 430 °C or higher, still more preferably 460 °C or higher, still more preferably 490 °C or higher, still more preferably 500 °C or higher from the viewpoint of further improving the heat resistance of the obtained cured product. And the upper limit value of the above 10% mass loss temperature is not particularly limited, and the higher the temperature, the more preferable. For example, it may be 1000 °C or lower, 900 °C or lower, 800 °C or lower, 700 °C or lower, or 600 °C or lower. From the viewpoint of further improving the heat resistance of the resulting cured product, the 10% mass loss temperature of the thermosetting resin composition of this embodiment is preferably 370°C or higher and 1000°C or lower, more preferably 400°C or higher and 1000°C or lower, still more preferably 430°C or higher and 900°C or lower, still more preferably 460°C or higher and 800°C or lower, still more preferably 490°C or higher and 700°C or lower, and still more preferably 500°C or higher and 600°C or lower.

[0033] [Shape] From the viewpoints of suppressing curing unevenness of the resulting cured product and further improving the heat resistance of the resulting cured product, the thermosetting resin composition of this embodiment is preferably in powder form or liquid form. When the thermosetting resin composition of this embodiment is in liquid form, from the viewpoint of suppressing curing unevenness of the thermosetting resin composition, it is preferably a one-component resin composition or a two-component resin composition, and from the viewpoint of controlling the progress of curing of the thermosetting resin composition, it is more preferably a two-component resin composition. When the thermosetting resin composition of this embodiment is a two-component resin composition, it means a combination of resin composition 1 containing monomer (A) and resin composition 2 containing resin (B). When the thermosetting resin composition of this embodiment is a two-component resin composition, resin composition 1 and resin composition 2 can be mixed and used before use.

[0034] When the thermosetting resin composition of this embodiment is in powder form, it can be obtained by kneading the above-described respective components and then pulverizing them. Examples of the kneading method include methods using mechanical kneaders such as kneaders, kneading machines, and rolls. Examples of the pulverizing method include dry pulverizing apparatuses such as rod mills, ball mills, bead mills, jet mills, cyclone mills, roller mills, pin mills, and hammer mills; and methods using wet pulverizing apparatuses such as high-pressure homogenizers and bead mills. As the kneading method and the pulverizing method, one or a combination of two or more of the above specific examples can be used respectively.

[0035] When the thermosetting resin composition of the present embodiment is in a liquid state, it can be obtained by kneading the above-described respective components by the above-described kneading method and then adding a solvent to dissolve it in the solvent. Further, it can also be obtained by kneading the above-described respective components by the above-described kneading method, pulverizing them by the above-described pulverizing method, and then adding a solvent to dissolve and disperse them in the solvent.

[0036] The solvent preferably contains one or more selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve, carbitol, anisole, and N-methylpyrrolidone.

[0037] When the thermosetting resin composition of the present embodiment is in a liquid state, from the viewpoint of further improving the heat resistance and workability of the obtained cured product, the content of the solvent is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, still more preferably 25% by mass or more, still more preferably 30% by mass or more, still more preferably 35% by mass or more, still more preferably 40% by mass or more, still more preferably 45% by mass or more when the total amount of the thermosetting resin composition is 100% by mass, and is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, still more preferably 70% by mass or less, still more preferably 60% by mass or less, still more preferably 55% by mass or less.

[0038] <Cured product> The cured product of the present embodiment is a cured product obtained by curing the thermosetting resin composition of the present embodiment described above. Examples of the method for producing the cured product of the present embodiment include a method of heating the thermosetting resin composition of the present embodiment described above. Conditions such as the heating temperature and heating time when heating the thermosetting resin composition of the present embodiment can be appropriately adjusted according to the formulation of the thermosetting resin composition and the like.

[0039] From the perspective of improving the performance balance between the heat resistance and mechanical strength of the cured product, the heating temperature of the thermosetting resin composition of the present embodiment is preferably 150 °C or higher, more preferably 160 °C or higher, still more preferably 170 °C or higher. From the perspective of the production efficiency of the cured product, it is preferably 500 °C or lower, more preferably 450 °C or lower, still more preferably 400 °C or lower.

[0040] From the perspective of improving the performance balance between the heat resistance and mechanical strength of the cured product, the heating time of the thermosetting resin composition of the present embodiment is preferably 30 seconds or longer, more preferably 60 seconds or longer, still more preferably 300 seconds or longer. From the perspective of the production efficiency of the cured product, it is preferably 24 hours or shorter, more preferably 15 hours or shorter, still more preferably 10 hours or shorter.

[0041] <Molded article> The molded article of the present embodiment includes the cured product of the thermosetting resin composition of the present embodiment described above. Examples of the molding method for obtaining the molded article include injection molding, transfer molding, compression molding, etc. Regarding conditions such as the molding temperature and molding time when molding the thermosetting resin composition of the present embodiment, they can be appropriately adjusted according to the molding method, molding apparatus, or the formulation of the thermosetting resin composition, etc.

[0042] From the perspective of the production efficiency of the molded article, the molding temperature of the thermosetting resin composition of the present embodiment is preferably 100 °C or higher, more preferably 110 °C or higher, still more preferably 120 °C or higher. From the perspective of improving the performance balance between the heat resistance and mechanical strength of the molded article, it is preferably 500 °C or lower, more preferably 450 °C or lower, still more preferably 400 °C or lower.

[0043] From the perspective of improving the performance balance between the heat resistance and mechanical strength of the molded article, the molding time of the thermosetting resin composition of the present embodiment is preferably 30 seconds or longer, more preferably 60 seconds or longer, still more preferably 300 seconds or longer. From the perspective of the production efficiency of the molded article, it is preferably 10 hours or shorter, more preferably 5 hours or shorter, still more preferably 1 hour or shorter.

[0044] <Use> The thermosetting resin composition of this embodiment can be used, for example, in friction materials such as brake pads, brake linings, and clutch facings; substrate materials such as resin sheets and resin substrates; encapsulants for encapsulating electronic components; abrasives such as grinding wheels; printing materials such as 3D printers; carbon materials used in electrode materials, refractory materials, etc.

[0045] As described above, the embodiments of the present invention have been described, but these are examples of the present invention, and various configurations other than the above can be adopted. Further, the present invention is not limited to the above-described embodiments, and modifications, improvements, etc. within the scope capable of achieving the object of the present invention are included in the present invention.

Examples

[0046] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereby.

[0047] <Examples, Comparative Examples> (Preparation of Thermosetting Resin Composition) The thermosetting resin compositions of each example and each comparative example were obtained by uniformly mixing each component according to the formulation (parts by mass) shown in Table 1. Details of each component in Table 1 are as follows.

[0048] (Monomer (A) Containing Two Carboxylic Anhydride Rings) Monomer A1: Pyromellitic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) Monomer A2: 3,3’,4,4’-Benzophenone tetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) Monomer A3: 3,3’,4,4’-Biphenyltetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0049] (Resin (B) Containing Two or More Amino Groups) Resin B1: Aniline formaldehyde resin (manufactured by Sumitomo Bakelite Co., Ltd., mass average molecular weight: 1500, average number of amino groups contained: 15, melting point: 75 °C) Resin B2: Aniline formaldehyde resin (manufactured by Sumitomo Bakelite Co., Ltd., mass average molecular weight: 2500, average number of amino groups contained: 25, melting point: 106 °C)

[0050] (Phenolic resin) Phenolic resin 1: Novolak type phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd., product name: PR-50099)

[0051] <Evaluation> For each physical property of the thermosetting resin compositions of each example and each comparative example, evaluation was carried out by the following method. The results are shown in Table 1.

[0052] (Mass average molecular weight) The mass average molecular weight of the resin (B) used in each example and each comparative example was measured by the GPC measurement method (gel permeation chromatography method) based on the following <GPC measurement conditions>. <GPC measurement conditions> The GPC apparatus is composed of a pump, an injector, a guard column, columns, and a detector. For the measurement, tetrahydrofuran (THF) was used as the solvent. The flow rate of the pump was set to 0.5 ml / min. A commercially available guard column (TSK GUARDCOLUMN HR-L manufactured by Tosoh Corporation: diameter 6.0 mm, column length 40 mm) was used for the guard column, and a plurality of commercially available polystyrene gel columns (TSK-GEL GMHHR-L manufactured by Tosoh Corporation: diameter 7.8 mm, column length 30 mm) were connected in series for the columns. A differential refractive index meter (RI detector. Differential refractive index (RI) detector W2414 manufactured by WATERS) was used for the detector. For the sample, a THF solution of resin (B) adjusted to a concentration of 3 - 4 mg / ml was prepared, and about 50 - 150 μl of this was injected from the injector for measurement. For the analysis of the sample, a calibration curve prepared with a monodisperse polystyrene standard sample was used.

[0053] (10% mass loss start temperature) The thermosetting resin compositions of each example and each comparative example were heated at 280 °C for 1 hour to obtain cured products of the above thermosetting resin compositions. Next, 5 mg of the obtained cured product was set in a thermogravimetric-differential thermal analyzer (STA7200RV, manufactured by Hitachi High-Tech Science Corporation). Then, for the above cured product, in accordance with JIS K 7120:1987, thermogravimetric-differential thermal measurement was performed under the conditions of inlet gas: nitrogen, measurement temperature range: 25°C to 500°C, and heating rate: 10°C / min. At this time, the temperature at which a 10% mass reduction occurred with respect to the mass of the set cured product was read and defined as the 10% mass reduction start temperature.

[0054] (Extraction residue amount) The cured products of the thermosetting resin compositions of each example and each comparative example were obtained by heating at 280°C for 1 hour. Next, by the Soxhlet extraction method, 5 g of the above cured product was boiled for 6 hours using 100 g of acetone to extract unreacted components. After boiling, the acetone was removed, and the residue was dried in a vacuum dryer at 80°C for 5 hours. Then, the residue was weighed, and the extraction residue amount was calculated based on the following formula (A). Extraction residue amount (mass %) = (mass of the cured product of the thermosetting resin composition before boiling (g) - mass of the residue (g)) / (mass of the cured product of the thermosetting resin composition before boiling (g)) × 100... Formula (A)

[0055]

Table 1

[0056] In each example, it was shown that the heat resistance was improved compared to each comparative example.

Claims

1. A thermosetting resin composition comprising a monomer (A) containing two anhydrous carboxylic acid rings and a resin (B) containing two or more amino groups.

2. The thermosetting resin composition according to Claim 1, wherein the monomer (A) contains a compound represented by the following formula (1). 【Chemical Formula 1】 (In the formula (1), X represents a structure represented by the following formula (2) or (3).) 【Chemical Formula 2】 (In the formula (3), Y is a single bond or a divalent organic group.)

3. The thermosetting resin composition according to Claim 1 or 2, wherein the molecular weight of the monomer (A) is 200 or more and 900 or less.

4. The thermosetting resin composition according to Claim 1 or 2, wherein the monomer (A) contains one or more selected from the group consisting of pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, and 3,3',4,4'-biphenyltetracarboxylic dianhydride.

5. The thermosetting resin composition according to Claim 1 or 2, wherein the content of the monomer (A) in the thermosetting resin composition is 1 part by mass or more and 150 parts by mass or less when the content of the resin (B) is 100 parts by mass.

6. The thermosetting resin composition according to Claim 1 or 2, which is in powder form.

7. The thermosetting resin composition according to Claim 1 or 2, which is in liquid form.

8. The thermosetting resin composition according to Claim 7, which is a one-component resin composition or a two-component resin composition.

9. The thermosetting resin composition according to Claim 1 or 2, wherein the resin (B) contains one or more selected from the group consisting of aniline resins, melamine resins, and urea resins.

10. The thermosetting resin composition according to claim 9, wherein the resin (B) contains an aniline formaldehyde resin.

11. The thermosetting resin composition according to claim 1 or 2, wherein the mass average molecular weight of the resin (B) in terms of polystyrene is 500 or more and 20,000 or less.

12. The thermosetting resin composition according to claim 1 or 2, wherein the content of the resin (B) in the thermosetting resin composition is 10% by mass or more and 99% by mass or less when the total amount of components excluding the solvent of the thermosetting resin composition is 100% by mass.

13. The thermosetting resin composition according to claim 1 or 2, wherein the extraction residue amount of the thermosetting resin composition by the following (Method 1) is 1.0% by mass or less when the total amount of components excluding the solvent of the thermosetting resin composition is 100% by mass. (Method 1) The thermosetting resin composition is heated at 280 ° C for 1 hour to obtain a cured product of the thermosetting resin composition. Next, by the Soxhlet extraction method, 5 g of the cured product is boiled with 100 g of acetone for 6 hours to extract unreacted components. After boiling, acetone is removed, and the residue is dried in a vacuum dryer at 80 ° C for 5 hours. Then, the residue is weighed, and the extraction residue amount is calculated based on the following formula (A). Extraction residue amount (mass%) = (mass of cured product of thermosetting resin composition before boiling (g) - mass of residue (g)) / (mass of cured product of thermosetting resin composition before boiling (g)) × 100... Formula (A)

14. For the cured product obtained by heating the thermosetting resin composition at 280 ° C for 1 hour, in accordance with JIS K 7120: 1987, the 10% mass loss temperature measured under the conditions of inlet gas: nitrogen, measurement temperature range: 25 ° C to 500 ° C, heating rate: 10 ° C / min is 370 ° C or higher. The thermosetting resin composition according to claim 1 or 2.

15. The cured product of the thermosetting resin composition according to claim 1 or 2.

16. A molded article comprising the cured product according to claim 15.

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