Thermosetting resin composition, cured product and molded body

Abstract

To provide a thermosetting resin composition that is capable of yielding a cured product with improved heat resistance, a cured product having improved heat resistance, and a molded body including the cured product.SOLUTION: A thermosetting resin composition contains a resin (A) containing two or more anhydrous carboxylic acid rings, and a resin (B) containing 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 technology]

[0002] The molding material may be, for example, a phenolic resin composition.

[0003] As a technique relating to a phenolic resin composition, for example, the technique described in Patent Document 1 can be mentioned. Patent Document 1 describes a thermosetting resin composition suitable for producing a friction material having excellent heat resistance, flexibility, and abrasion resistance, and a friction material. The thermosetting resin composition contains a triazine-modified resol-type phenolic resin (1) obtained by reacting a novolac-type phenolic resin (e1) obtained by using bisphenol (a), triazine (b), aldehydes (c), and phenol (d) as essential components, or a triazine-modified resol-type phenolic resin (2) obtained by reacting phenol (d), triazine (b), aldehydes (c), and novolac-type phenolic resin (e2) obtained by using bisphenol (a) as essential components, and the amount of bisphenol (a) and phenol (d) used [bisphenol (a) / phenol (d)] is 0.4 to 1.0 in terms of moles. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2013-142142 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a thermosetting resin composition capable of improving the heat resistance of the resulting cured product, a cured product having improved heat resistance, and a molded article containing the cured product. [Means for solving the problem]

[0006] The present inventors discovered that the heat resistance of the resulting cured product can be improved by containing a resin (A) containing two or more carboxylic acid anhydride rings and a resin (B) containing two or more amino groups, and thus completed the present invention.

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

[0008] [1] A thermosetting resin composition comprising: a resin (A) having two or more carboxylic acid anhydride rings; and a resin (B) having two or more amino groups. [2] The thermosetting resin composition according to the above item [1], wherein the resin (A) contains one or more structural units selected from the group consisting of a structural unit (A1) represented by the following formula (1) and a structural unit (A2) represented by the following formula (2): [ka] [ka] (In the above formula (2), R a represents a direct bond or an alkylene group having 1 to 10 carbon atoms, the alkylene group may be linear or branched, and some of the hydrogen atoms in the alkylene group may be substituted with a substituent. [3] The thermosetting resin composition according to the above [1] or [2], wherein the resin (A) comprises a copolymer of an olefin monomer and maleic anhydride. [4] The thermosetting resin composition according to any one of the above [1] to [3], wherein the resin (A) contains one or more structural units selected from the group consisting of a structural unit (A3) represented by the following formula (3), a structural unit (A4) represented by the following formula (4), and a structural unit (A5) represented by the following formula (5): [ka] (In the above formula (3), n is 0, 1, or 2; R 1 ~R 4 are each independently a hydrogen atom or a substituted or unsubstituted, linear or branched alkyl group having 1 to 10 carbon atoms. [ka] (In the above formula (4), R 10 , R 11 and R 12 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, R 13 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms; R 13 may be bonded to each other to form a monocyclic ring. [ka] (In the above formula (5), R 20 is a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R 21 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms; R 20 and R 21 may be bonded to each other to form a monocyclic ring. [5] The thermosetting resin composition according to any one of the above [1] to [4], which is in a powder form. [6] The thermosetting resin composition according to any one of the above [1] to [4], which is liquid. [7] The thermosetting resin composition according to the above [6], which is a one-component resin composition or a two-component resin composition. [8] The thermosetting resin composition according to any one of the above [1] to [7], wherein the resin (A) has a polystyrene-equivalent weight average molecular weight of 500 or more and 50,000 or less. [9] The thermosetting resin composition according to any one of the above [1] to [8], wherein the content of the resin (A) in the thermosetting resin composition is 5 parts by mass or more and 150 parts by mass or less, when the content of the resin (B) is 100 parts by mass.

[10] The thermosetting resin composition according to any one of the above [1] to [9], wherein the resin (B) comprises one or more resins selected from the group consisting of aniline resins, melamine resins and urea resins.

[11] The thermosetting resin composition according to the above

[10] , wherein the resin (B) comprises an aniline formaldehyde resin.

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

[11] , wherein the resin (B) has a polystyrene-equivalent weight average molecular weight of 200 or more and 20,000 or less.

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

[12] , wherein the content of the resin (B) in the thermosetting resin composition is 40 mass% or more and 95 mass% or less, when the amount of all components of the thermosetting resin composition excluding the solvent is taken as 100 mass%.

[14] The thermosetting resin composition according to any one of the above [1] to

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

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

[14] , wherein the thermosetting resin composition has a 10% mass loss temperature of 370°C or higher, measured in accordance with JIS K 7120:1987 under the conditions of an inlet gas: nitrogen, a measurement temperature range: 25°C to 500°C, and a heating rate: 10°C / min.

[16] A cured product of the thermosetting resin composition according to any one of the above [1] to

[15] .

[17] A molded article comprising the cured product according to the above item

[16] . Effect 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 having improved heat resistance, and a molded article using the cured product. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0011] <Thermosetting resin composition> The thermosetting resin composition of the present embodiment contains a resin (A) containing two or more carboxylic acid anhydride rings and a resin (B) containing two or more amino groups.

[0012] According to the thermosetting resin composition of the present embodiment, it is possible to provide a thermosetting resin composition capable of improving the heat resistance of the obtained cured product, a cured product having improved heat resistance, and a molded article using the cured product. This is believed to be because a resin (A) containing two or more carboxylic anhydride rings and a resin (B) containing two or more amino groups are crosslinked to produce a polyimide resin having improved heat resistance. The carboxylic anhydride itself has excellent heat resistance, and it is believed that the heat resistance is improved by crosslinking a resin containing two or more carboxylic anhydride rings with a resin containing two or more amino groups to form a polyimide resin having a network structure.

[0013] [Resin containing two or more carboxylic acid anhydride rings (A)] The thermosetting resin composition of the present embodiment contains a resin (A) containing two or more carboxylic acid anhydride rings (hereinafter also referred to as resin (A)). From the viewpoint of further improving the heat resistance of the obtained cured product, the resin (A) of the present embodiment preferably contains one or more structural units selected from the group consisting of a structural unit (A1) represented by the following formula (1) and a structural unit (A2) represented by the following formula (2), and more preferably contains a structural unit (A1) represented by the following formula (1).

[0014] [ka]

[0015] [ka]

[0016] In the above formula (2), R a represents a direct bond or an alkylene group having 1 to 10 carbon atoms, the alkylene group may be linear or branched, and some of the hydrogen atoms in the alkylene group may be substituted with a substituent. a is preferably a direct bond or an alkylene group having 1 to 4 carbon atoms, more preferably a direct bond or an alkylene group having 1 to 2 carbon atoms, and even more preferably a direct bond or a methylene group.

[0017] The number of carboxylic acid anhydride rings contained in the resin (A) of the present embodiment (hereinafter also referred to as the average number of carboxylic acid anhydride rings) is 2 or more, preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more, from the viewpoint of further improving the heat resistance of the obtained cured product. The upper limit is not particularly limited, and may be, for example, 100 or less, 80 or less, or 60 or less.

[0018] The average number of carboxylic acid anhydride rings contained in the resin (A) of the present embodiment can be measured, for example, by the following method. 50 mg of resin (A) and 5 mg of dimethyl terephthalate as an internal standard were weighed and dissolved in DMSO-d6. This solution was analyzed using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). 1 H-NMR measurements are performed. 1 The amount of carboxylic acid anhydride rings is calculated from the integral value of the H peak (near 12.4 ppm) of the carboxyl group (-COOH) of resin (A) using the integral value of the 4H peak (near 8.1 ppm) of the phenyl group of dimethyl terephthalate, the internal standard for H-NMR measurement, as the standard.

[0019] From the viewpoint of further improving the heat resistance of the resulting cured product, the resin (A) of the present embodiment preferably contains a copolymer of an olefin monomer and maleic anhydride.

[0020] Examples of the olefin monomer of the present embodiment include linear olefins such as ethylene, propylene, butene, pentene, hexene, octene, decene, dodecene, tetradecene, hexadecene, octadecene, and eicosene; norbornene, norbornadiene, bicyclo[2.2.1]-2-heptene (common name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5-(2-propene), and the like. cyclic olefins such as 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethylidene-2-norbornene, 5-benzyl-2-norbornene, and 5-phenethyl-2-norbornene; olefins containing an indene skeleton or an acenaphthylene skeleton such as indene, 2-methylindene, 3-methylindene, and acenaphthylene; 1,5,9-cyclododecatriene, cis-trans-trans-1,5,9-cyclododecatriene, trans-trans-trans-1,5,9-cyclododecatriene, triphenylene, cyclohexane, cyclohexane-1,5,9-cyclohexane-1,5,9-cyclohexane-1 Olefins containing a triene structure, such as trans-cis-cis-1,5,9-cyclododecatriene and cis-cis-cis-1,5,9-cyclododecatriene; olefins containing a styrene skeleton, such as styrene, vinyltoluene, hydroxystyrene, acetoxystyrene, and α-methylstyrene; N-cycloalkylmaleimides, such as N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-norbornylmaleimide, N-cyclohexylmethylmaleimide, and N-cyclopentylmethylmaleimide; N-phenylmaleimide, N-chlorophenyl maleimide, N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide and other N-arylmaleimides; preferably, one or more selected from the group consisting of linear olefins, cyclic olefins, olefins containing a styrene skeleton, and olefins containing an indene skeleton or an acenaphthylene skeleton; and more preferably, bicyclo[2.2.1]-2-Heptene, styrene and indene are included as one or more selected from the group consisting of heptene, styrene and indene.

[0021] From the viewpoint of further improving the heat resistance of the obtained cured product, the resin (A) of the present embodiment preferably contains one or more structural units selected from the group consisting of a structural unit (A3) represented by the following formula (3), a structural unit (A4) represented by the following formula (4), and a structural unit (A5) represented by the following formula (5).

[0022] [ka]

[0023] In the above formula (3), n is 0, 1, or 2; R 1 ~R 4 are each independently a hydrogen atom or a substituted or unsubstituted, linear or branched alkyl group having 1 to 10 carbon atoms. 1 ~R 4 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and further preferably a hydrogen atom.

[0024] [ka]

[0025] In the above formula (4), R 10 , R 11 and R 12 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, R 13 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms; R 13 may be bonded to each other to form a monocyclic ring. 10 , R 11 and R 12 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a hydrogen atom.13 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, even more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0026] [ka]

[0027] In the above formula (5), R 20 is a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R 21 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms; R 20 and R 21 may be bonded to each other to form a monocyclic ring. 20 R is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, still more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom. 21 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, even more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

[0028] In the structural unit represented by the above formula (3), R 1 ~R 4 Examples of the alkyl group having 1 to 10 carbon atoms that can constitute the above group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

[0029] R 1 , R 2 , R 3 and R 4The hydrogen atom in the alkyl group having 1 to 10 carbon atoms may be substituted with any atomic group. For example, it may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group, etc. More specifically, R 1 , R 2 , R 3 and R 4 As the alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group or the like may be selected. In the structural unit represented by the above formula (3), n is preferably 0 or 1, and more preferably 0.

[0030] In the structural unit represented by the above formula (4), R 10 , R 11 and R 12 Examples of the organic group having 1 to 3 carbon atoms that can constitute R include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. 10 , R 11 and R 12 is preferably a hydrogen atom.

[0031] R in the above formula (4) 13 Examples of the organic group having 1 to 30 carbon atoms that can constitute the above group include substituted or unsubstituted, linear or branched organic groups having 1 to 30 carbon atoms, and more specific examples thereof include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups, heterocyclic groups, and carboxy groups.

[0032] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

[0033] Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group. The alkynyl group includes, for example, an ethynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group.

[0034] Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentyloxy group, a neopentyloxy group, and an n-hexyloxy group. Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

[0035] R in the structural unit represented by the above formula (4) 13 is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. In addition, R 13 The hydrogen atoms in the organic group having 1 to 30 carbon atoms may be substituted with any atomic group. For example, they may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group, or the like. More specifically, R 13 As the organic group having 1 to 30 carbon atoms, a fluorinated alkyl group or the like may be selected.

[0036] In the structural unit represented by the above formula (5), R 20 Examples of the organic group having 1 to 10 carbon atoms that can constitute the above group include substituted or unsubstituted, linear or branched organic groups having 1 to 10 carbon atoms, and more specific examples thereof include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups, heterocyclic groups, and carboxy groups.

[0037] In addition, in the structural unit represented by the above formula (5), R 21 Examples of the organic group having 1 to 30 carbon atoms that can constitute the above group include substituted or unsubstituted, linear or branched organic groups having 1 to 30 carbon atoms, and more specific examples thereof include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups, heterocyclic groups, and carboxy groups.

[0038] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

[0039] Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group. The alkynyl group includes, for example, an ethynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group.

[0040] Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentyloxy group, a neopentyloxy group, and an n-hexyloxy group. Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

[0041] In the structural unit represented by the above formula (5), R 20 and R 21 are preferably a hydrogen or an alkyl group, and more preferably hydrogen. Note that the hydrogen atoms in the organic group having 1 to 10 carbon atoms of R 20 and the hydrogen atoms in the organic group having 1 to 30 carbon atoms of R 21 may be substituted with any atomic group. For example, they may be substituted with a fluorine atom, a hydroxy group, a carboxy group, or the like. More specifically, as the organic group having 1 to 10 carbon atoms of R 20 and the organic group having 1 to 30 carbon atoms of R 21 , an alkyl fluoride group or the like may be selected.

[0042] From the viewpoint of further improving the heat resistance of the obtained cured product, the polystyrene-reduced mass average molecular weight of the resin (A) of the present embodiment is preferably 500 or more, more preferably 550 or more, still more preferably 600 or more, still more preferably 700 or more, still more preferably 800 or more, still more preferably 900 or more, and preferably 50,000 or less, more preferably 40,000 or less, still more preferably 30,000 or less, still more preferably 25,000 or less, still more preferably 20,000 or less, still more preferably 15,000 or less, still more preferably 13,000 or less.

[0043] Specifically, examples of the method for measuring the mass average molecular weight of the resin (A) of the present embodiment include the GPC measurement method (gel permeation chromatography method). More specifically, the mass average molecular weight of the resin (A) is measured based on the following <GPC measurement conditions>, and conversion is performed using a 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 example, tetrahydrofuran (THF) is used as a solvent for the measurement. The flow rate of the pump is, for example, 0.5 ml / min. The guard column is a commercially available guard column (for example, TSK GUARDCOLUMN HR-L manufactured by Tosoh Corporation: diameter 6.0 mm, tube length 40 mm), and the column is, for example, a commercially available polystyrene gel column (TSK-GEL GMHHR-L manufactured by Tosoh Corporation: diameter 7.8 mm, tube length 30 mm) connected in series in multiple pieces. The detector is a differential refractometer (RI detector, for example, WATERS differential refractive index (RI) detector W2414). For the sample, a THF solution of resin (A) 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 to perform the measurement. For the analysis of the sample, a calibration curve created with a monodisperse polystyrene standard sample is used.

[0044] From the viewpoint of further improving the heat resistance of the obtained cured product, the content of resin (A) in the thermosetting resin composition of this embodiment is, when the content of resin (B) is taken as 100 parts by mass, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, even more preferably 18 parts by mass or more, even more preferably 20 parts by mass or more, and is preferably 150 parts by mass or less, more preferably 140 parts by mass or less, even more preferably 130 parts by mass or less, even more preferably 120 parts by mass or less, even more preferably 110 parts by mass or less, even more preferably 105 parts by mass or less, and even more preferably 100 parts by mass or less.

[0045] [Resin containing two or more amino groups (B)] 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) in this embodiment include polymers obtained by polycondensation of an amino compound and an aldehyde, and specifically, resins obtained by polycondensation of an amino compound and formaldehyde (aminoformaldehyde resins). From the viewpoint of further improving the heat resistance of the obtained cured product, the resin (B) in the present embodiment preferably contains one or more resins selected from the group consisting of aniline resins, melamine resins, and urea resins, more preferably contains one or more resins selected from the group consisting of aniline resins and melamine resins, and even more preferably contains an aniline resin.

[0046] Examples of aniline resins include polymers obtained by polycondensation of aniline and aldehydes, and specifically, resins obtained by polycondensation of aniline and formaldehyde (aniline formaldehyde resins). Examples of melamine resins include polymers obtained by polycondensation of melamine and aldehydes, and specifically, resins obtained by polycondensation of melamine and formaldehyde (melamine formaldehyde resins). Examples of urea resins include polymers obtained by polycondensation of urea (urea) and aldehydes, and specifically, resins obtained by polycondensation of urea (urea) and formaldehyde (urea-formaldehyde resins). Among these, the resin (B) of the present embodiment preferably contains an aniline formaldehyde resin from the viewpoint of further improving the heat resistance of the resulting cured product.

[0047] The number of amino groups contained in the resin (B) of the present embodiment (hereinafter also referred to as the average number of amino groups) is, from the viewpoint of further improving the heat resistance of the obtained cured product, 2 or more, preferably 3 or more, more preferably 4 or more, even more preferably 5 or more, even more preferably 6 or more, even more preferably 8 or more, and even more preferably 10 or more, and the higher the upper limit value, the better, but it may be, for example, 1000 or less, 500 or less, 100 or less, 50 or less, 25 or less, or 20 or less.

[0048] The weight-average molecular weight in terms of polystyrene of the resin (B) in the present embodiment is preferably 200 or more, more preferably 250 or more, still more preferably 300 or more, still more preferably 500 or more, still more preferably 800 or more, still more preferably 900 or more, still more preferably 1000 or more, from the viewpoint of further improving the heat resistance of the resulting 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, still more preferably 2,000 or less.

[0049] Specific examples of the method for measuring the weight-average molecular weight of the resin (B) in the present embodiment 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 a calibration curve of standard polystyrene. <GPC measurement conditions> The GPC apparatus is composed of a pump, an injector, a guard column, columns, and a detector. For the measurement, for example, tetrahydrofuran (THF) is used as the solvent. The flow rate of the pump is, for example, 0.5 ml / min. As the guard column, a commercially available guard column (for example, TSK GUARDCOLUMN HR-L manufactured by Tosoh Corporation: diameter 6.0 mm, column length 40 mm) is used. For the columns, for example, a plurality of commercially available polystyrene gel columns (TSK-GEL GMHHR-L manufactured by Tosoh Corporation: diameter 7.8 mm, column length 30 mm) are connected in series. As the detector, a differential refractometer (RI detector. For example, differential refractometer (RI) detector W2414 manufactured by WATERS) is used. As the sample, a THF solution of the 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. For the analysis of the sample, a calibration curve prepared using a monodisperse polystyrene standard sample is used.

[0050] From the viewpoint of further improving the heat resistance of the obtained cured product, the melting point of the resin (B) in this embodiment is preferably 60°C or higher, more preferably 63°C or higher, even more preferably 65°C or higher, even more preferably 68°C or higher, and even more preferably 70°C or higher, and is preferably 150°C or lower, more preferably 130°C or lower, even more preferably 110°C or lower, even more preferably 100°C or lower, even more preferably 90°C or lower, and even more preferably 80°C or lower.

[0051] From the viewpoint of further improving the heat resistance of the obtained cured product, the content of resin (B) in the thermosetting resin composition of the present embodiment is, when the total amount of components in the thermosetting resin composition excluding the solvent described later is taken as 100 mass%, preferably 40 mass% or more, more preferably 42 mass% or more, even more preferably 44 mass% or more, even more preferably 46 mass% or more, even more preferably 48 mass% or more, even more preferably 50 mass% or more, and is preferably 95 mass% or less, more preferably 93 mass% or less, even more preferably 91 mass% or less, even more preferably 89 mass% or less, even more preferably 87 mass% or less, and even more preferably 85 mass% or less.

[0052] From the viewpoint of further improving the heat resistance of the obtained cured product, the total content of resin (A) and resin (B) in the thermosetting resin composition of the present embodiment is preferably 50 mass% or more, more preferably 60 mass% or more, even more preferably 70 mass% or more, even more preferably 80 mass% or more, even more preferably 90 mass% or more, and even more preferably 95 mass% or more, when the total amount of the components in the thermosetting resin composition excluding the solvent described later is taken as 100 mass%, and the upper limit value is not particularly limited, but is, for example, 100 mass% or less.

[0053] [Physical Properties] From the viewpoint of further improving the heat resistance of the obtained cured product, the amount of extraction residue of the thermosetting resin composition of this embodiment by the following (Method 1) is preferably 1.0 mass% or less, more preferably 0.9 mass% or less, even more preferably 0.8 mass% or less, even more preferably 0.7 mass% or less, even more preferably 0.6 mass% or less, even more preferably 0.5 mass% or less, even more preferably 0.4 mass% or less, and even more preferably 0.3 mass% or less, when the total amount of the components excluding the solvent of the thermosetting resin composition is taken as 100 mass%, and the lower limit of the extraction residue is not particularly limited, but is, for example, 0.0 mass% or more.

[0054] (Method 1) By the Soxhlet extraction method, 5 g of the cured product of the above thermosetting resin composition is boiled with 100 g of acetone for 6 hours to extract the unreacted components. After boiling, the acetone is removed and the residue is dried in a vacuum dryer at 80°C for 5 hours. The residue is then weighed and the amount of the extracted residue is calculated based on the following formula (A). Extraction residue (mass%)=(mass (g) of cured thermosetting resin composition before boiling−mass (g) of residue) / (mass (g) of cured thermosetting resin composition before boiling)×100 Formula (A)

[0055] The 10% mass loss temperature of the thermosetting resin composition of the present embodiment, measured in accordance with JIS K 7120:1987 under the conditions of inflow gas: nitrogen, measurement temperature range: 25°C to 500°C, and temperature rise rate: 10°C / min, is preferably 370°C or higher, more preferably 375°C or higher, even more preferably 380°C or higher, even more preferably 385°C or higher, even more preferably 390°C or higher, even more preferably 395°C or higher, and even more preferably 400°C or higher, from the viewpoint of further improving the heat resistance of the obtained cured product. The upper limit of the 10% mass loss temperature is not particularly limited, and a higher temperature is preferable, but it may be, for example, 1000°C or lower, 900°C or lower, 800°C or lower, 700°C or lower, 600°C or lower, or 500°C or lower.

[0056] [shape] The thermosetting resin composition of the present embodiment is preferably in a powder or liquid form from the viewpoint of suppressing uneven curing of the obtained cured product and further improving the heat resistance of the obtained cured product. When the thermosetting resin composition of the present embodiment is in a liquid form, it is preferably a one-liquid resin composition or a two-liquid resin composition from the viewpoint of suppressing uneven curing of the thermosetting resin composition, and more preferably a two-liquid resin composition from the viewpoint of controlling the progress of curing of the thermosetting resin composition. When the thermosetting resin composition of the present embodiment is a two-component resin composition, it means a combination of a resin composition 1 containing a resin (A) and a resin composition 2 containing a resin (B). When the thermosetting resin composition of the present embodiment is a two-component resin composition, the resin composition 1 and the resin composition 2 can be mixed before use.

[0057] When the thermosetting resin composition of the present embodiment is in the form of a powder, it can be obtained by kneading the above-mentioned components and then pulverizing them. Examples of the kneading method include a method using a mechanical kneader such as a kneader, a kneader, or a roll. Examples of the pulverizing method include a method using a dry pulverizing device such as a rod mill, a ball mill, a bead mill, a jet mill, a cyclone mill, a roller mill, a pin mill, or a hammer mill; and a wet pulverizing device such as a high-pressure homogenizer and a bead mill. As the kneading method and the pulverizing method, one or more of the above specific examples can be used in combination.

[0058] When the thermosetting resin composition of the present embodiment is liquid, it can be obtained by kneading the above-mentioned components by the above-mentioned kneading method, adding a solvent to dissolve the components in the solvent, or by kneading the above-mentioned components by the above-mentioned kneading method, pulverizing the components by the above-mentioned pulverizing method, and then adding a solvent to dissolve and disperse the components in the solvent.

[0059] Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethylsulfoxide, ethylene glycol, cellosolve, carbitol, anisole, and N-methylpyrrolidone. Among the above specific examples, one or more of the solvents can be used in combination.

[0060] When the thermosetting resin composition of the present embodiment is in a liquid state, the content of the solvent, when the total amount of the thermosetting resin composition is taken as 100 mass%, from the viewpoint of further improving the heat resistance of the obtained cured product and from the viewpoint of workability, is preferably 10 mass% or more, more preferably 15 mass% or more, even more preferably 20 mass% or more, even more preferably 25 mass% or more, even more preferably 30 mass% or more, even more preferably 35 mass% or more, even more preferably 40 mass% or more, even more preferably 45 mass% or more, and is preferably 90 mass% or less, more preferably 85 mass% or less, even more preferably 80 mass% or less, even more preferably 70 mass% or less, even more preferably 60 mass% or less, and even more preferably 55 mass% or less.

[0061] <Cured product> The cured product of this embodiment is a cured product obtained by curing the above-mentioned thermosetting resin composition of this embodiment. The method for producing the cured product of the present embodiment may be, for example, a method of heating the thermosetting resin composition of the present embodiment. The conditions for heating the thermosetting resin composition of the present embodiment, such as the heating temperature and heating time, can be appropriately adjusted depending on the formulation of the thermosetting resin composition.

[0062] The heating temperature of the thermosetting resin composition of the present embodiment is preferably 150° C. or higher, more preferably 160° C. or higher, and even more preferably 170° C. or higher, from the viewpoint of improving the performance balance of the heat resistance and mechanical strength of the cured product, and is preferably 500° C. or lower, more preferably 450° C. or lower, and even more preferably 400° C. or lower, from the viewpoint of production efficiency of the cured product.

[0063] The heating time for the thermosetting resin composition of the present embodiment is preferably 30 seconds or more, more preferably 60 seconds or more, and even more preferably 300 seconds or more, from the viewpoint of improving the performance balance of the heat resistance and mechanical strength of the cured product, and is preferably 24 hours or less, more preferably 15 hours or less, and even more preferably 10 hours or less, from the viewpoint of production efficiency of the cured product.

[0064] <Molded body> The molded article of the present embodiment includes a cured product of the thermosetting resin composition of the present embodiment described above. Examples of the molding method for obtaining a molded body include injection molding, transfer molding, compression molding, etc. Conditions such as molding temperature and molding time when molding the thermosetting resin composition of the present embodiment can be appropriately adjusted depending on the molding method, molding device, or compounding of the thermosetting resin composition.

[0065] The molding temperature of the thermosetting resin composition of the present embodiment is preferably 100° C. or higher, more preferably 110° C. or higher, and even more preferably 120° C. or higher from the viewpoint of production efficiency of the molded article, and is preferably 500° C. or lower, more preferably 450° C. or lower, and even more preferably 400° C. or lower from the viewpoint of improving the performance balance of the heat resistance and mechanical strength of the molded article.

[0066] The molding time of the thermosetting resin composition of the present embodiment is preferably 30 seconds or more, more preferably 60 seconds or more, and even more preferably 300 seconds or more, from the viewpoint of improving the performance balance of the heat resistance and mechanical strength of the molded article, and is preferably 10 hours or less, more preferably 5 hours or less, and even more preferably 1 hour or less, from the viewpoint of production efficiency of the molded article.

[0067] <Application> The thermosetting resin composition of the present embodiment can be used, for example, for friction materials such as brake pads, brake linings, and clutch facings; substrate materials such as resin sheets and resin substrates; sealing materials for sealing electronic components; abrasives such as grinding wheels; printing materials for 3D printers and the like; and carbon materials used in electrode materials, fire-resistant materials, and the like.

[0068] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of the present invention are included in the present invention. EXAMPLES

[0069] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0070] <Examples and Comparative Examples> (Preparation of Thermosetting Resin Composition) The thermosetting resin compositions of each of the Examples and Comparative Examples were obtained by uniformly mixing the components according to the formulation (parts by mass) shown in Table 1. Details of each component in Table 1 are as follows.

[0071] (Resin (A) containing two or more carboxylic acid anhydride rings) Resin A1: Alternating copolymer of maleic anhydride and 2-norbornene (manufactured by Sumitomo Bakelite Co., Ltd., mass average molecular weight: 10,000, average number of carboxylic acid anhydride rings: 50) Resin A2: Alternating copolymer of maleic anhydride and 2-norbornene (manufactured by Sumitomo Bakelite Co., Ltd., mass average molecular weight: 2,000, average number of carboxylic acid anhydride rings: 10) Resin A3: Alternating copolymer of maleic anhydride and styrene (mass average molecular weight: 6000, average number of carboxylic acid anhydride rings: 30) Resin A4: Alternating copolymer of maleic anhydride and styrene (mass average molecular weight: 1000, average number of carboxylic anhydride rings: 5) Resin A5: Alternating copolymer of maleic anhydride and indene (manufactured by Sumitomo Bakelite Co., Ltd., mass average molecular weight: 5,000, average number of carboxylic anhydride rings: 25)

[0072] (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: 15, melting point: 75 °C) Resin B2: Aniline formaldehyde resin (manufactured by Sumitomo Bakelite Co., Ltd., mass average molecular weight: 1100, average number of amino groups: 11, melting point: 71 °C)

[0073] (Phenolic resin) Phenolic resin 1: Novolak type phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd., product name: PR-50099)

[0074] (Solvent) Solvent 1: Methyl ethyl ketone

[0075] <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.

[0076] (Mass average molecular weight) The mass average molecular weights of Resin (A) and Resin (B) used in each example and each comparative example were measured by the GPC measurement method (gel permeation chromatography method) based on the following <GPC measurement conditions>. <GPC measurement conditions> The GPC device is composed of a pump, an injector, a guard column, a column, and a detector. Tetrahydrofuran (THF) was used as the solvent for the measurement. The flow rate of the pump was 0.5 ml / min. The guard column was a commercially available guard column (TSK GUARDCOLUMN HR-L, manufactured by Tosoh Corporation: diameter 6.0 mm, tube length 40 mm), and the column was a commercially available polystyrene gel column (TSK-GEL GMHHR-L, manufactured by Tosoh Corporation: diameter 7.8 mm, tube length 30 mm) connected in series. A differential refractometer (RI detector; WATERS differential refractive index (RI) detector W2414) was used as the detector. A THF solution of resin (A) or resin (B) adjusted to a concentration of 3 to 4 mg / ml was prepared as the sample, and about 50 to 150 μl of this was injected from the injector and the measurement was performed. A calibration curve created with a monodisperse polystyrene standard sample was used for the analysis of the sample.

[0077] (Average number of carboxylic acid anhydride rings) The average content of carboxylic acid anhydride rings in the resin (A) used in each of the Examples and Comparative Examples was measured by the following method. 50 mg of resin (A) and 5 mg of dimethyl terephthalate as an internal standard were weighed and dissolved in DMSO-d6. This solution was analyzed using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). 1 H-NMR measurements were carried out. 1 The amount of carboxylic acid anhydride rings was calculated from the integral value of the H peak (near 12.4 ppm) of the carboxyl group (-COOH) of resin (A) based on the integral value of the 4H peak (near 8.1 ppm) of the phenyl group of dimethyl terephthalate, the internal standard for H-NMR measurement.

[0078] (10% mass reduction start temperature) 5 mg of the obtained thermosetting resin composition of each Example and Comparative Example was set in a thermogravimetric / differential thermal analyzer (STA7200RV, manufactured by Hitachi High-Tech Science Corporation). Then, the thermosetting resin composition was subjected to thermogravimetric / differential thermal analysis in accordance with JIS K 7120:1987 under the conditions of inflow 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 thermosetting resin composition was read, and this was taken as the 10% mass reduction starting temperature.

[0079] (Extraction residual amount) By the Soxhlet extraction method, 5 g of the cured product of the thermosetting resin composition of each Example and Comparative Example was boiled with 100 g of acetone for 6 hours to extract the unreacted components. After boiling, the acetone was removed, and the residue was dried in a vacuum dryer at 80°C for 5 hours. The residue was then weighed, and the amount of the extracted residue was calculated based on the following formula (A). Extraction residue (mass%)=(mass (g) of cured thermosetting resin composition before boiling−mass (g) of residue) / (mass (g) of cured thermosetting resin composition before boiling)×100 Formula (A)

[0080] [Table 1]

[0081] Each of the examples showed improved heat resistance compared to each of the comparative examples.

Claims

1. A thermosetting resin composition comprising: a resin (A) having two or more carboxylic acid anhydride rings; and a resin (B) having two or more amino groups.

2. The thermosetting resin composition according to claim 1, wherein the resin (A) contains one or more structural units selected from the group consisting of a structural unit (A1) represented by the following formula (1) and a structural unit (A2) represented by the following formula (2): 【Chemistry 1】 【Chemistry 2】 (In the above formula (2), R ａ represents a direct bond or an alkylene group having 1 to 10 carbon atoms, the alkylene group may be linear or branched, and some of the hydrogen atoms in the alkylene group may be substituted with a substituent.

3. 3. The thermosetting resin composition of claim 1 or 2, wherein the resin (A) comprises a copolymer of an olefin monomer and maleic anhydride.

4. The thermosetting resin composition according to claim 1 or 2, wherein the resin (A) contains one or more structural units selected from the group consisting of a structural unit (A3) represented by the following formula (3), a structural unit (A4) represented by the following formula (4), and a structural unit (A5) represented by the following formula (5): 【Chemistry 3】 (In the formula (3), n is 0, 1, or 2; R １ ~R ４ are each independently a hydrogen atom or a substituted or unsubstituted, linear or branched alkyl group having 1 to 10 carbon atoms. 【Chemistry 4】 (In the above formula (4), R １０ , R １１ and R １２ are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms; R １３ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms; R １３ may be bonded to each other to form a monocyclic ring. 【Chemistry 5】 (In the above formula (5), R ２０ is a hydrogen atom or an organic group having 1 to 10 carbon atoms, R ２１ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms; R ２０ and R ２１ may be bonded to each other to form a monocyclic ring.

5. The thermosetting resin composition according to claim 1 or 2, which is in a powder form.

6. The thermosetting resin composition according to claim 1 or 2, which is in a liquid state.

7. The thermosetting resin composition according to claim 6, which is a one-component resin composition or a two-component resin composition.

8. The thermosetting resin composition according to claim 1 or 2, wherein the resin (A) has a polystyrene-equivalent mass average molecular weight of 500 or more and 50,000 or less.

9. 3. The thermosetting resin composition according to claim 1, wherein a content of the resin (A) in the thermosetting resin composition is 5 parts by mass or more and 150 parts by mass or less when a content of the resin (B) is 100 parts by mass.

10. 3. The thermosetting resin composition according to claim 1, wherein the resin (B) comprises one or more resins selected from the group consisting of aniline resins, melamine resins and urea resins.

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

12. The thermosetting resin composition according to claim 1 or 2, wherein the resin (B) has a polystyrene-equivalent mass average molecular weight of 200 or more and 20,000 or less.

13. 3. The thermosetting resin composition according to claim 1, wherein a content of the resin (B) in the thermosetting resin composition is 40% by mass or more and 95% by mass or less, when a total amount of components excluding a solvent in the thermosetting resin composition is taken as 100% by mass.

14. 3. The thermosetting resin composition according to claim 1, wherein an amount of the thermosetting resin composition remaining after extraction by the following (Method 1) is 1.0 mass% or less, when a total amount of components excluding the solvent of the thermosetting resin composition is taken as 100 mass%. (Method 1) By the Soxhlet extraction method, 5 g of the cured product of the thermosetting resin composition is boiled with 100 g of acetone for 6 hours to extract the unreacted components. After boiling, the acetone is removed, and the residue is dried in a vacuum dryer at 80° C. for 5 hours. The residue is then weighed, and the amount of the extracted residue is calculated based on the following formula (A). Extraction residue (mass %)=(mass (g) of cured thermosetting resin composition before boiling−mass (g) of residue) / (mass (g) of cured thermosetting resin composition before boiling)×100...Equation (A)

15. The thermosetting resin composition according to claim 1 or 2, wherein the 10% mass loss temperature of the thermosetting resin composition is 370°C or higher, as measured in accordance with JIS K 7120:1987 under the conditions of inflow gas: nitrogen, measurement temperature range: 25°C to 500°C, and temperature rise rate: 10°C / min.

16. A cured product of the thermosetting resin composition according to claim 1 or 2.

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

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