Thermosetting resin composition and cured product

Abstract

The present disclosure provides a thermosetting resin composition and the like in which the toughness of a cured product is further improved. The present disclosure relates to a thermosetting resin composition having a first resin as a thermosetting resin, and resin particles containing a second resin having an amide bond, the second resin including one or more second functional groups selected from the group consisting of an amino group, a carboxyl group, an isocyanate group, and a carboxylic acid anhydride group, the first resin contains a first functional group capable of reacting with the second functional group, the second resin contains 25-190 mmol / kg of the second functional group, and the relative viscosity of the second resin is 1.50-2.50.

Description

Technical Field

[0001] The present disclosure relates to a thermosetting resin composition and a cured product. Background Art

[0002] Cured products obtained by curing epoxy resin compositions have been used as materials for aircraft fuselages, golf club shafts, fishing rods, and the like (for example, Patent Document 1).

[0003] In addition, from the viewpoint of improving the toughness of a cured product obtained by curing the epoxy resin composition, an epoxy resin composition having resin particles containing an epoxy resin and a polyamide resin has been used (for example, Patent Document 2).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 61-103922

[0007] Patent Document 2: International Publication No. 2015 / 019965 Summary of the invention

[0008] Problems to be solved by the invention

[0009] However, there may be a demand for a cured product having further improved toughness.

[0010] However, sufficient research has not yet been conducted on thermosetting resin compositions having further improved toughness of cured products.

[0011] Therefore, an object of the present disclosure is to provide a thermosetting resin composition having a cured product with further improved toughness, and a cured product obtained by thermally curing the thermosetting resin composition.

[0012] Solution to the problem

[0013] A first aspect of the present disclosure relates to a thermosetting resin composition comprising a first resin as a thermosetting resin and resin particles comprising a second resin having an amide bond, wherein:

[0014] The second resin comprises one or more second functional groups selected from an amino group, a carboxyl group, an isocyanate group, and a carboxylic anhydride group,

[0015] The first resin includes a first functional group capable of reacting with the second functional group.

[0016] The second resin contains 25 to 190 mmol / kg of the second functional group.

[0017] The relative viscosity of the second resin is 1.50 to 2.50.

[0018] A second aspect of the present disclosure relates to a cured product obtained by thermally curing the thermosetting resin composition.

[0019] A third aspect of the present disclosure relates to a prepreg obtained by impregnating or injecting the above-mentioned thermosetting resin composition into an aggregate of reinforcing fibers.

[0020] A fourth aspect of the present disclosure relates to a molded article formed of the above-mentioned cured product.

[0021] A fifth aspect of the present disclosure relates to a fiber-reinforced plastic including the above-mentioned cured product and reinforcing fibers.

[0022] Effects of the Invention

[0023] According to the present disclosure, a thermosetting resin composition having a further improved toughness of a cured product can be provided. In addition, according to the present disclosure, a cured product obtained by heat curing the thermosetting resin composition can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a SEM image of the resin particles used in Example 3.

[0025] Figure 2 This is a SEM image of a cross section of a cured product obtained by thermally curing the thermosetting resin composition of Example 3. DETAILED DESCRIPTION

[0026] Hereinafter, one embodiment of the present disclosure will be described.

[0027] It should be noted that the various configurations and their combinations in the various embodiments are merely examples, and additions, omissions, substitutions, and other changes to the configurations may be appropriately made without departing from the spirit of the present disclosure. The present disclosure is not limited to the embodiments, but only to the claims.

[0028] Furthermore, each aspect disclosed in this specification may be combined with any other feature disclosed in this specification.

[0029] <Thermosetting resin composition>

[0030] First, the thermosetting resin composition according to the present embodiment will be described.

[0031] The thermosetting resin composition of the present embodiment includes a first resin as a thermosetting resin and resin particles containing a second resin having an amide bond.

[0032] The second resin includes one or more second functional groups selected from the group consisting of an amino group, a carboxyl group, an isocyanate group, and a carboxylic anhydride group.

[0033] The first resin includes a first functional group capable of reacting with the second functional group.

[0034] The second resin contains 25 to 190 mmol / kg of the second functional group.

[0035] The relative viscosity of the second resin is 1.50 to 2.50.

[0036] When the second resin contains 25 mmol / kg or more of the second functional group, the toughness of the cured product is further improved.

[0037] This is considered to be due to the following reasons.

[0038] That is, this is considered to be because the second resin contains 25 mmol / kg or more of the second functional group, which increases the affinity between the resin particles and the first resin in the cured product and increases the toughness of the cured product at the boundary between the resin particles and the first resin.

[0039] Generally speaking, the relative viscosity of a resin can be used as an indicator of the average molecular weight of the resin. The higher the relative viscosity of a resin, the higher the average molecular weight of the resin.

[0040] By setting the relative viscosity of the second resin to be 2.50 or less, the average molecular weight of the second resin is reduced, and the content ratio of the second functional group in the second resin can be easily increased.

[0041] When the relative viscosity of the second resin is 1.50 or more, the toughness of the cured product is further improved.

[0042] This is considered to be due to the following reasons.

[0043] That is, it is considered that this is because, by setting the relative viscosity of the second resin to 1.50 or more, the average molecular weight of the second resin is increased, and the toughness of the resin particles is increased.

[0044] When the second resin contains 190 mmol / kg or less of the second functional group, the molecular weight of the second resin can be easily increased.

[0045] Therefore, according to the present embodiment, a thermosetting resin composition having a cured product with further improved toughness can be provided.

[0046] (First resin as thermosetting resin)

[0047] The first resin as the thermosetting resin includes a first functional group capable of reacting with the second functional group.

[0048] Examples of the first functional group include an epoxy group, a hydroxyl group, an isocyanate group, an oxazoline group, an acid anhydride, a carboxylic acid, an amino group, an ester group, and a thiol group.

[0049] Examples of the thermosetting resin include epoxy resins, phenolic resins, unsaturated polyester resins, vinyl ester resins, acrylic resins, urea resins, melamine resins, aniline resins, polyimide resins, bismaleimide resins, etc. These thermosetting resins may be used alone or in combination of two or more.

[0050] As the thermosetting resin, epoxy resin and phenol resin are preferred, and epoxy resin is particularly preferred.

[0051] Since the resin particles containing the polyamide resin are easily dispersed in the epoxy resin, the effect of improving toughness by the resin particles is easily exhibited by making the thermosetting resin contain the epoxy resin.

[0052] Examples of the epoxy resin include glycidyl ether epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins, alkylene oxides (eg, vinyl cyclohexene dioxide), triglycidyl isocyanurate, and the like.

[0053] Examples of the glycidyl ether epoxy resin include bisphenol epoxy resins, novolac epoxy resins, dicyclopentadiene epoxy resins, epoxy resins having an aromatic skeleton (polyglycidyl ether), alkanediol diglycidyl ethers, polyalkanediol diglycidyl ethers, and epoxy resins having an aliphatic skeleton (polyglycidyl ether).

[0054] Examples of the bisphenol-type epoxy resin include reaction products of bisphenols and epichlorohydrin, and reaction products of alkylene oxide adducts of bisphenols and epichlorohydrin.

[0055] Examples of the bisphenols include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, and brominated bisphenol epoxy resins.

[0056] In the alkylene oxide adduct of the bisphenol, the number of moles of alkylene oxide added is, for example, 1 mol or more (eg, 1 to 20 mol), preferably 1 to 15 mol, and more preferably 1 to 10 mol, per 1 mol of hydroxyl groups of the bisphenol.

[0057] Examples of the novolac epoxy resin include phenol novolac epoxy resin, cresol novolac epoxy resin, naphthol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin, naphthol novolac resin having a biphenyl skeleton, and naphthol novolac resin having a xylylene skeleton.

[0058] Examples of the epoxy resin (polyglycidyl ether) having an aromatic skeleton include glycidyl ether having a naphthalene skeleton.

[0059] Examples of the glycidyl ether having a naphthalene skeleton include di(glycidyloxy)naphthalene and bis[2,7-di(glycidyloxy)naphthyl]methane.

[0060] Examples of the di(glycidyloxy)naphthalene include 1,5-di(glycidyloxy)naphthalene and the like.

[0061] Examples of the alkanediol diglycidyl ether include C 2-10 Alkanediol diglycidyl ether, etc.

[0062] As the above C 2-10 Examples of the alkanediol diglycidyl ether include butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether.

[0063] Examples of the polyalkanediol diglycidyl ether include poly (C 2-4 Alkanediol diglycidyl ether, etc.

[0064] As the above poly C 2-4 Examples of alkanediol diglycidyl ethers include polypropylene glycol diglycidyl ether and the like.

[0065] Examples of the epoxy resin (polyglycidyl ether) having an aliphatic skeleton include glycidyl polyether of polyhydric alcohol.

[0066] Examples of the polyol include alkane triol, alkane tetraol, alkane pentol, alkane hexol, and the like. Examples of the alkane polyol include C 3-10 Examples of the above-mentioned alkanetol include C 3-10 Alkane tetraol, etc.

[0067] Examples of the glycidyl polyether include diglycidyl ether, triglycidyl ether, tetraglycidyl ether, pentaglycidyl ether, and hexaglycidyl ether.

[0068] Examples of the glycidyl polyether of the polyol include trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol diglycidyl ether, and glycerol triglycidyl ether.

[0069] Examples of the glycidylamine epoxy resin include tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidylaminocresol, diglycidylaniline, and N,N-diglycidyl-4-glycidyloxyaniline.

[0070] Examples of the glycidyl ester type epoxy resin include diglycidyl ester of dicarboxylic acid.

[0071] Examples of the dicarboxylic acid include aromatic dicarboxylic acids and hydrogenated products of aromatic dicarboxylic acids.

[0072] Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, and hexahydrophthalic acid.

[0073] These epoxy resins can be used alone or in combination of two or more.

[0074] Among these epoxy resins, epoxy resins having an aromatic skeleton are preferred from the viewpoint of strength and the like, and bisphenol-type epoxy resins are particularly preferred.

[0075] Examples of the phenol resin include resins having one or more, preferably two or more, phenolic hydroxyl groups in one molecule.

[0076] Examples of the phenolic resin include novolac-type phenolic resins, resol-type phenolic resins, and polyoxystyrene resins.

[0077] The novolac phenolic resin is a condensate of phenols and aldehydes. The novolac phenolic resin can be obtained, for example, by polycondensing phenols and aldehydes in the presence of an acidic catalyst.

[0078] The resol type phenolic resin is a condensate of phenols and aldehydes. The resol type phenolic resin can be obtained, for example, by polycondensing phenols and aldehydes in the presence of a basic catalyst.

[0079] Examples of the phenols include phenol, cresol, trimethylphenol, xylenol, resorcinol, catechol, butylphenol, octylphenol, nonylphenol, phenylphenol, dihydroxybenzene, bisphenol A, and naphthol.

[0080] Examples of the cresol include o-cresol, m-cresol, and p-cresol.

[0081] Examples of the trimethylphenol include 2,3,5-trimethylphenol and the like.

[0082] Examples of the xylenol include 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, and 3,5-xylenol.

[0083] Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, glyoxal, glutaraldehyde, terephthalaldehyde, isophthalaldehyde, propionaldehyde, butyraldehyde, isobutylaldehyde, 3-methylbutyraldehyde, p-tolualdehyde, and phenylacetaldehyde.

[0084] Examples of the hydroxybenzaldehyde include o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, and p-hydroxybenzaldehyde.

[0085] Examples of the novolac-type phenolic resin include novolac resin (condensation product of phenol and formaldehyde) and cresol novolac resin (condensation product of cresol and formaldehyde).

[0086] The above-mentioned phenolic resins may be used alone or in combination of two or more.

[0087] The hydroxyl equivalent of the phenolic resin is preferably 50 to 500 g / eq., more preferably 100 to 350 g / eq.

[0088] The thermosetting resin composition of the present embodiment preferably contains 40 to 99% by weight, more preferably 80 to 97% by weight of the thermosetting resin.

[0089] (resin particles)

[0090] The resin particles are formed from a resin composition for resin particles containing a second resin having an amide bond and a second functional group.

[0091] The second functional group is a functional group that can react with the first functional group.

[0092] The second functional group is preferably one or more functional groups selected from an amino group, a carboxyl group, an isocyanate group, an oxazoline group, a carboxylic acid, an ester group, a thiol group, and a carboxylic anhydride group.

[0093] Examples of the amino group include "-NH2" and "-NHR".

[0094] R is an alkyl group. Examples of R include a methyl group, an ethyl group, and a propyl group.

[0095] Examples of the second resin include polyamide resins, polyimide resins, and polyamideimide resins.

[0096] Examples of the polyamide resin include aliphatic polyamide resins, alicyclic polyamide resins (also referred to as “alicyclic polyamide resins”), and aromatic polyamide resins.

[0097] The polyamide resin may be a homopolyamide resin or a copolyamide resin.

[0098] Examples of the aliphatic polyamide resin include polyamide resins of aliphatic diamine components and aliphatic dicarboxylic acid components, polyamide resins of lactam, polyamide resins of aminocarboxylic acid, and polyamide resins of aliphatic diamine components, aliphatic dicarboxylic acid components, and lactam and / or aminocarboxylic acid.

[0099] Examples of the aliphatic diamine component include C4-16 alkylenediamine (e.g., tetramethylenediamine, hexamethylenediamine, dodecanediamine, etc.) etc. The aliphatic diamine component is preferably C6-14 alkylenediamine, and more preferably C6-12 alkylenediamine.

[0100] Examples of the aliphatic dicarboxylic acid component include C4-20 alkane dicarboxylic acids (eg, adipic acid, sebacic acid, dodecanedioic acid, etc.) etc. The aliphatic dicarboxylic acid component is preferably C5-16 alkane dicarboxylic acid, and more preferably C6-14 alkane dicarboxylic acid.

[0101] Examples of the lactam include lactams having 4 to 20 carbon atoms (e.g., ε-caprolactam, ω-laurolactam, etc.) etc. The lactam is preferably a lactam having 4 to 16 carbon atoms.

[0102] Examples of the aminocarboxylic acid include C4-20 aminocarboxylic acid (eg, ω-aminoundecanoic acid, etc.) etc. The aminocarboxylic acid is preferably C4-16 aminocarboxylic acid, and more preferably C6-14 aminocarboxylic acid.

[0103] Examples of the aliphatic polyamide resins include polyamide 6 (PA6), polyamide 11 (PA11), polyamide 12 (PA12), polyamide 46 (PA46), polyamide 66 (PA66), polyamide 610 (PA610), polyamide 611 (PA611), polyamide 612 (PA612), polyamide 613 (PA613), polyamide 1010 (PA1010), polyamide 66 / 11 (PA66 / 11), polyamide 66 / 12 (PA66 / 12), and polyamide 6 / 12 / 612 (PA6 / 12 / 612).

[0104] Examples of the alicyclic polyamide resin include polyamide resins containing at least one selected from alicyclic diamine components and alicyclic dicarboxylic acid components as a constituent component.

[0105] As the above-mentioned alicyclic polyamide resin, an alicyclic polyamide resin containing an alicyclic diamine component and / or an alicyclic dicarboxylic acid component, and containing the above-mentioned aliphatic diamine component and / or an aliphatic dicarboxylic acid component as a diamine component and a dicarboxylic acid component is preferred. Such an alicyclic polyamide resin has high transparency and is known as a so-called transparent polyamide resin.

[0106] As said alicyclic diamine component, a diaminocycloalkane, a bis(aminocycloalkyl)alkane, a hydrogenated xylylenediamine, etc. are mentioned, for example.

[0107] Examples of the diaminocycloalkane include diaminocyclohexane, etc. The diaminocycloalkane is preferably diamino C5-10 cycloalkane.

[0108] Examples of the bis(aminocycloalkyl)alkane include bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, and 2,2-bis(4′-aminocyclohexyl)propane. The bis(aminocycloalkyl)alkane is preferably bis(aminoC5-8cyclohexyl)C1-3alkane.

[0109] The alicyclic diamine component may have a substituent such as an alkyl group.

[0110] The alkyl group is preferably a C1-6 alkyl group, more preferably a C1-4 alkyl group, and further preferably a C1-2 alkyl group (methyl group, ethyl group, etc.).

[0111] Examples of the alicyclic dicarboxylic acid include cycloalkane dicarboxylic acids (for example, cyclohexane-1,4-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, etc.).

[0112] Representative alicyclic polyamide resins include, for example, alicyclic diamine components [e.g., bis(aminocyclohexyl)alkane, etc.] and aliphatic dicarboxylic acid components [e.g., alkane dicarboxylic acids (e.g., C 4-20 alkane dicarboxylic acid components, etc.) and the like].

[0113] The aromatic polyamide resin is a concept including a polyamide resin containing at least one of an aromatic diamine component and an aromatic dicarboxylic acid component as a structural unit.

[0114] Examples of the aromatic polyamide resin include polyamide resins in which both a diamine component of a structural unit and a dicarboxylic acid component of a structural unit are aromatic components (also referred to as “wholly aromatic polyamide resin”, “aramid”, etc.).

[0115] The aromatic polyamide resin may be a modified polyamide resin. Examples of the modified polyamide resin include polyamide resins having a branched structure.

[0116] Examples of the aromatic diamine component include meta-xylylenediamine and the like.

[0117] Examples of the aromatic dicarboxylic acid component include terephthalic acid, isophthalic acid, etc. The aromatic dicarboxylic acid component may be a dimer acid, etc.

[0118] As said polyimide resin, an aliphatic polyimide resin, an aromatic polyimide resin, etc. are mentioned, for example.

[0119] Moreover, as said polyimide resin, the imidation product of the polyamic acid (precursor of a polyimide resin) which is a polymer of a tetracarboxylic dianhydride and a diamine compound is mentioned, for example.

[0120] Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenyl)sulfonic acid dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, and ethylenetetracarboxylic dianhydride.

[0121] Specific examples of the diamine compound used as a raw material of the polyimide resin include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3'-dichlorobenzidine, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 1,5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 3,3'-dimethyl-4,4'-biphenylenediamine, benzidine ...chlorobenzidine, 3,3'-dichlorobenzidine, 3,3'-dichlorobenzidine, 3,3'-dichlorobenzidine, 3,3'-dichlorobenzidine, 3,3'-dichlorobenz -Dimethylbenzidine, 3,3'-dimethoxybenzidine, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl propane, 2,4-bis(β-aminotert-butyl)toluene, bis(p-β-aminotert-butylphenyl)ether, bis(p-β-methyl-δ-aminophenyl)benzene, bis(p-1,1-dimethyl-5-aminopentyl)benzene, 1-isopropyl-2,4-m-phenylenediamine, m-phenylenediamine, p-phenylenediamine, di(p-aminocyclohexyl)methane , hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, diaminopropyltetramethylene, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 2,11-diaminododecane, 1,2-bis-3-aminopropoxyethane, 2,2-dimethylpropylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 5-methylnonamethylenediamine Amine, 2,17-diaminoeicosadecaene, 1,4-diaminocyclohexane, 1,10-diamino-1,10-dimethyldecane, 12-diaminooctadecane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, piperazine, H2N(CH2)3O(CH2)2O(CH2)NH2, H2N(CH2)3S(CH2)3NH2, H2N(CH2)3N(CH3)2(CH2)3NH2, etc.

[0122] Examples of the polyamide-imide resin include resins having an imide bond and an amide bond in a repeating unit.

[0123] More specifically, examples of the polyamide-imide resin include polymers of a trivalent carboxylic acid compound (also referred to as tricarboxylic acid) having an acid anhydride group and a diisocyanate compound or a diamine compound.

[0124] As the tricarboxylic acid, trimellitic anhydride and a derivative thereof are preferred.

[0125] Examples of the diisocyanate compound include 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 2,2'-dimethylbiphenyl-4,4'-diisocyanate, biphenyl-4,4'-diisocyanate, biphenyl-3,3'-diisocyanate, biphenyl-3,4'-diisocyanate, 3,3'-diethylbiphenyl-4,4'-diisocyanate, 2,2'-diethylbiphenyl-4,4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 2,2'-dimethoxybiphenyl-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, and naphthalene-2,6-diisocyanate.

[0126] Examples of the diamine compound used as a raw material for the polyamide-imide resin include the examples given as the diamine compound used as a raw material for the polyimide resin.

[0127] The second resin preferably includes a polyamide resin.

[0128] The polyamide resin preferably includes an aliphatic polyamide resin and / or an alicyclic polyamide resin, and more preferably includes an alicyclic polyamide resin.

[0129] The second resin contains 25 to 190 mmol / kg, preferably 29 to 175 mmol / kg, and more preferably 29 to 120 mmol / kg of the second functional group.

[0130] The concentration of the second functional group in the second resin refers to the total concentration of the amino group, carboxyl group, isocyanate group, and carboxylic anhydride group in the second resin.

[0131] In addition, the concentration of the amino group in the resin such as the second resin can be obtained as follows.

[0132] First, a phenol / ethanol solvent was prepared by mixing phenol and ethanol in a volume ratio of 10:1.

[0133] Next, the weighed resin was dissolved in 40 mL of a phenol / ethanol solvent to obtain a first solution.

[0134] Then, 10 mL of ethanol was added to the first solution to obtain a second solution.

[0135] Next, the second solution was titrated with an N / 100 hydrochloric acid aqueous solution to determine the concentration of amino groups in the resin.

[0136] The total concentration of the carboxyl group and the carboxylic anhydride group in the resin can be determined as follows.

[0137] First, a weighed amount of resin was dissolved in 50 mL of benzyl alcohol in an oil bath at 180° C. to obtain a solution.

[0138] Next, the solution was titrated with a N / 100 potassium hydroxide-ethanol solution using phenolphthalein as an indicator to determine the total concentration of the carboxyl group and the carboxylic anhydride group in the resin.

[0139] In addition, when the resin does not contain a carboxylic anhydride group, the concentration determined by the titration means the concentration of the carboxyl group in the resin.

[0140] In addition, the concentration of isocyanate groups in the resin can be determined based on JIS K1603-1:2007.

[0141] In addition, the concentration of the second functional group contained in the resin having a second functional group can be reduced by, for example, a carbodiimide compound.

[0142] Specifically, a resin having a second functional group and a carbodiimide compound are melt-kneaded using an extruder having a barrel (barrel temperature: for example, 190 to 320° C., more specifically, 210 to 290° C.), thereby obtaining a melt-kneaded product. Next, the melt-kneaded product is discharged from the extruder, and the discharged rod-shaped melt-kneaded product is cooled. Then, pellets are obtained by cutting the rod-shaped melt-kneaded product. Next, by drying the pellets with a dehumidifying dryer (for example, 70 to 90° C.), a granular resin with a reduced concentration of the second functional group can be obtained.

[0143] The carbodiimide compound is a compound having a carbodiimide group (-N=C=N-). Examples of the carbodiimide compound include a monofunctional carbodiimide compound having only one carbodiimide group (-N=C=N-) in one molecule and a polyfunctional carbodiimide compound having two or more carbodiimide groups (-N=C=N-) in one molecule.

[0144] Examples of the carbodiimide compound include aliphatic carbodiimide compounds having an aliphatic main chain, alicyclic carbodiimide compounds having an alicyclic main chain, and aromatic carbodiimide compounds having an aromatic main chain.

[0145] Examples of the aliphatic carbodiimide compound include diisopropylcarbodiimide, dioctyldecylcarbodiimide, di-tert-butylcarbodiimide, 1-ethyl-3-tert-butylcarbodiimide, 1-(2-butyl)-3-ethylcarbodiimide, 1,3-di(2-butyl)carbodiimide, and poly(diisopropylcarbodiimide).

[0146] Examples of the alicyclic carbodiimide compound include dicyclohexylcarbodiimide and poly(diisopropylcarbodiimide).

[0147] Examples of the aromatic carbodiimide compound include diphenylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, di-2,6-diethylphenylcarbodiimide, di-2,6-diisopropylphenylcarbodiimide, di-2,6-di-tert-butylphenylcarbodiimide, N-tolyl-N'-phenylcarbodiimide, N-(2,6-diisopropyl-4-phenoxyphenyl)-N-tert-butylcarbodiimide, N,N-bis[3-isocyanato- 2,4,6-tris(1-methylethyl)phenylamino]carbodiimide, N-cyclohexyl-N-(4-(dimethylamino)naphthyl)carbodiimide, di-o-tolylcarbodiimide, di-p-tolylcarbodiimide, di-p-nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide, di-p-hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-p-methoxyphenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, di-2,5-dichlorophenylcarbodiimide imide, di-o-chlorophenyl carbodiimide, di-2,4,6-trimethylphenyl carbodiimide, di-2,4,6-triisopropylphenyl carbodiimide, di-2,4,6-triisobutylphenyl carbodiimide, p-phenylene-bis-di-o-tolyl carbodiimide, p-phenylene-bis-dicyclohexyl carbodiimide, p-phenylene-bis-di-p-chlorophenyl carbodiimide, ethylene-bis-diphenyl carbodiimide, poly(4,4'-diphenylmethane carbodiimide), poly(

[0013] The present invention relates to poly(p-phenylene carbodiimide), poly(m-phenylene carbodiimide), poly(3,3'-dimethyl-4,4'-diphenylmethane carbodiimide), poly(naphthylene carbodiimide), poly(1,3-diisopropylphenylene carbodiimide), poly(1-methyl-3,5-diisopropylphenylene carbodiimide), poly(1,3,5-triethylphenylene carbodiimide), poly(diisopropylphenylene carbodiimide), poly(triisopropylphenylene carbodiimide), and the like.

[0148] The above-mentioned carbodiimide compounds may be used alone or in combination of two or more.

[0149] The relative viscosity of the second resin is 1.50 to 2.50, preferably 1.58 to 2.16.

[0150] The relative viscosity of the resin such as the second resin can be measured in accordance with JIS K6933: 2013. The measurement conditions of the relative viscosity are as follows.

[0151] Solvent: m-cresol

[0152] Temperature: 25℃

[0153] Concentration of the second resin in the test solution: 0.005 g / mL

[0154] The glass transition temperature (Tg) (hereinafter also referred to as "glass transition point") of the second resin is preferably 30°C to 160°C, more preferably 30°C to 48°C.

[0155] It should be noted that in the present embodiment, the glass transition temperature (Tg) refers to the midpoint glass transition temperature measured using a differential scanning calorimeter (DSC).

[0156] The midpoint glass transition temperature can be determined according to the method described in JIS K7121-1987 "Methods for determining transition temperatures of plastics".

[0157] That is, first, about 5 mg of a sample for measuring the midpoint glass transition temperature is prepared, and two containers made of metal (for example, aluminum) of the same shape and weight are prepared.

[0158] Next, the sample is placed in one of the two containers, and the other container remains empty.

[0159] Then, the container containing the sample and an empty container as a reference are placed in DSC, and the sample is heated at a heating rate of 10°C / min while nitrogen is passed through. The midpoint glass transition temperature can be obtained from the DSC curve obtained at this time.

[0160] The resin particles preferably contain 80 to 100% by weight, more preferably 90 to 100% by weight, and even more preferably 95 to 100% by weight of the second resin.

[0161] In addition, the resin particles may further contain an additive. In other words, the resin composition for resin particles may further contain an additive.

[0162] Examples of the additives include stabilizers, colorants, dispersants, preservatives, antioxidants, and defoaming agents.

[0163] The above additives may be used alone or in combination of two or more.

[0164] The total content of the additives is, for example, 10 parts by weight or less (eg, 0.01 to 10 parts by weight) based on 100 parts by weight of the total of the additives and the second resin.

[0165] The median particle size (D50) of the resin particles is preferably 50 μm or less, more preferably 4 to 40 μm, and even more preferably 8 to 32 μm.

[0166] The median particle size of the resin particles is a value obtained by dispersing the resin particles in water and measuring with a laser diffraction / scattering particle size distribution analyzer. In addition, the median particle size of the resin particles is a volume-based median particle size of the resin particles.

[0167] In addition, the median particle size of the resin particles mentioned above refers to the median particle size of the resin particles of primary particles.

[0168] The sphericity of the resin particles is preferably 75% to 100%, more preferably 85% to 100%, further preferably 95% to 100%, particularly preferably 97% to 100%, and most preferably 99% to 100%.

[0169] When the sphericity of the resin particles is 75% or more, the toughness of the cured product is further improved.

[0170] It should be noted that, in the present embodiment, the sphericity of particles can be measured by the following method. That is, particles are observed by scanning electron microscope (SEM), the major diameter and minor diameter of 30 particles selected at random are measured, and the minor diameter / aspect ratio of each particle is obtained. Then, the arithmetic mean of the minor diameter / aspect ratio is obtained, and the arithmetic mean is used as the sphericity of particles. It should be noted that the closer the sphericity of particles is to 100%, the more it can be judged that the particles are positive spheres.

[0171] The thermosetting resin composition of the present embodiment preferably contains 50 to 99% by weight in total, and more preferably 80 to 97% by weight in total of the thermosetting resin and the resin particles.

[0172] The thermosetting resin composition of the present embodiment preferably contains 1 to 20 parts by weight, more preferably 3 to 18 parts by weight, and even more preferably 5 to 15 parts by weight of the resin particles based on 100 parts by weight of the thermosetting resin.

[0173] (Method for producing resin particles)

[0174] Examples of the method for producing the resin particles include a forced emulsification method, a freeze-pulverization method, a chemical pulverization method, a polymerization method, and a laser method.

[0175] As a method for producing the resin particles, a forced emulsification method is preferred.

[0176] In the above-mentioned forced emulsification method, the above-mentioned resin particles are obtained by implementing the following steps: step (A), heating the above-mentioned second resin having an amide bond and an aqueous medium incompatible with the above-mentioned second resin having an amide bond (hereinafter also referred to as "water-soluble matrix") by using an extruder to melt-knead and obtain a molten mixture; step (B), discharging the molten mixture from the extruder to obtain a rod-shaped molten mixture, cooling the rod-shaped molten mixture, and cutting the cooled rod-shaped molten mixture to obtain a granular preform; and step (C), removing the above-mentioned aqueous medium from the granular preform with a hydrophilic solvent or water.

[0177] In the forced emulsification method, the resin particles may be obtained by carrying out a step (D) of drying the preform using a dehumidifying dryer or the like after the step (C), if necessary.

[0178] In addition, in order to obtain resin particles having a desired particle size, in the above-mentioned forced emulsification method, the above-mentioned resin particles can also be obtained by carrying out a step (E) of classifying the above-mentioned preform after the above-mentioned step (C) (after the above-mentioned step (D) or before the above-mentioned step (D) when the above-mentioned step (D) is carried out).

[0179] The aqueous medium used in the step (A) is selected according to the type of the second resin having an amide bond.

[0180] Examples of the aqueous medium include heat-fusible sugars and water-soluble polymers.

[0181] Examples of the heat-fusible sugars include oligosaccharides (eg, sucrose, maltotriose, etc.), sugar alcohols (eg, xylitol, erythritol, sorbitol, mannitol, etc.), and the like.

[0182] Examples of the water-soluble polymer include water-soluble synthetic polymers (e.g., polyvinyl alcohol, modified polyvinyl alcohol-based resins (modified PVA-based resins), polyethylene glycol, sodium polyacrylate, polyacrylamide, etc.), polysaccharides (e.g., starch, methyl cellulose, etc.), and the like.

[0183] Examples of the modified polyvinyl alcohol-based resin include modified polyvinyl alcohol having an alkyl group having at least one hydroxyl group in a side chain and modified polyvinyl alcohol having an alkyl chain having at least one hydroxyl group in a side chain.

[0184] These aqueous media can be used alone or in combination of two or more.

[0185] The mixing ratio of the second resin and the aqueous medium is, for example, 10 to 200 parts by weight, preferably 30 to 150 parts by weight, and more preferably 50 to 100 parts by weight of the second resin relative to 100 parts by weight of the aqueous medium.

[0186] The temperature during melt kneading in the step (A) may be a temperature higher than the melting point or softening point of the second resin, for example, 190°C or higher (eg, 190 to 350°C), preferably 200 to 320°C, and more preferably 210 to 300°C.

[0187] In the step (B), the melt-kneaded product may be cooled naturally or forcibly. However, from the viewpoint of productivity, it is preferred to forcibly cool the melt-kneaded product.

[0188] The cooling rate of the melt-kneaded product is, for example, preferably 1° C. / min or more (eg, 1 to 30° C. / min).

[0189] Examples of the hydrophilic solvent used in the step (C) include alcohols (ethanol and the like) and water-soluble ketones (acetone and the like).

[0190] (Monofunctional epoxy compound)

[0191] When the thermosetting resin includes an epoxy resin, the thermosetting resin composition of the present embodiment may include a monofunctional epoxy compound.

[0192] Examples of the monofunctional epoxy compound include monoglycidyl ether, alkylene oxide (eg, octene oxide, styrene oxide, etc.), and the like.

[0193] Examples of the monoglycidyl ether include alkyl glycidyl ethers (eg, 2-ethylhexyl glycidyl ether, etc.), alkenyl glycidyl ethers (eg, allyl glycidyl ether, etc.), and aryl glycidyl ethers (eg, phenyl glycidyl ether, etc.).

[0194] In the thermosetting resin composition of the present embodiment, the weight ratio of the epoxy resin to the weight of the monofunctional epoxy compound is, for example, 99 / 1 to 50 / 50, preferably 97 / 3 to 60 / 40, and more preferably 95 / 5 to 70 / 30.

[0195] (Curing agent)

[0196] The thermosetting resin composition according to the present embodiment may contain a curing agent.

[0197] The curing agent may be appropriately selected according to the type of the thermosetting resin.

[0198] Examples of the curing agent when the thermosetting resin is an epoxy resin include amine curing agents, phenol resin curing agents, acid anhydride curing agents, polythiol curing agents, and latent curing agents.

[0199] Examples of the amine curing agent include aromatic amine curing agents, aliphatic amine curing agents, imidazoles, imidazole salts, and alicyclic amine curing agents.

[0200] Examples of the aromatic amine curing agent include polyaminoaromatics, polyaminoalkylaromatics, poly(aminoalkyl)aromatics, poly(aminoaryl)alkyls, poly(aminoalkylaryl)alkyls, bis(aminoarylalkyl)aromatics, di(aminoaryl)ethers (e.g., diaminodiphenyl ethers), di(aminoaryloxy)aromatics (e.g., 1,3-bis(3-aminophenoxy)benzene), and di(aminoaryl)sulfones (e.g., diaminodiphenyl sulfone).

[0201] Examples of the polyamino aromatic hydrocarbons include diamino aromatic hydrocarbons (for example, p-phenylenediamine, m-phenylenediamine, etc.) and the like.

[0202] Examples of the polyaminoalkyl aromatic hydrocarbons include diaminoalkyl aromatic hydrocarbons (eg, diethyltoluenediamine).

[0203] Examples of the poly(aminoalkyl)arenes include di(aminoalkyl)arenes (eg, xylylenediamine).

[0204] Examples of the poly(aminoaryl)alkyl group include di(aminoaryl)alkyl groups (eg, diaminodiphenylmethane).

[0205] Examples of the poly(aminoalkylaryl)alkyl group include di(aminoalkylaryl)alkyl groups (eg, 4,4′-methylenebis(2-ethyl-6-methylaniline)).

[0206] Examples of the bis(aminoarylalkyl)arene include 1,3-bis[2-(4-aminophenyl)-2-propyl)]benzene and 1,4-bis[2-(4-aminophenyl)-2-propyl)]benzene.

[0207] Examples of the aliphatic amine curing agent include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and diethylaminopropylamine.

[0208] Examples of the alicyclic amine curing agent include chrysanthene diamine, isophorone diamine, bis(4-amino-3-methylcyclohexyl)methane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, and norbornane diamine.

[0209] Examples of the imidazoles include alkyl imidazoles and aryl imidazoles.

[0210] Examples of the alkylimidazole include 2-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, and 2-ethyl-4-methylimidazole.

[0211] Examples of the aryl imidazole include 2-phenyl imidazole, 2-phenyl-4-methyl imidazole, 2-phenyl-4-methyl-5-hydroxymethyl imidazole, and 1-benzyl-2-phenyl imidazole.

[0212] Examples of the salt of imidazoles include salts of imidazoles and formic acid, salts of imidazoles and phenol, salts of imidazoles and phenol novolac, and salts of imidazoles and carbonic acid.

[0213] Examples of the phenolic resin curing agent include novolac resins and cresol novolac resins.

[0214] Examples of the acid anhydride curing agent include aliphatic dicarboxylic anhydride, alicyclic dicarboxylic anhydride, and aromatic dicarboxylic anhydride.

[0215] Examples of the aliphatic dicarboxylic anhydride include dodecenyl succinic anhydride and the like.

[0216] Examples of the alicyclic dicarboxylic anhydride include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and hexahydrophthalic anhydride.

[0217] Examples of the aromatic dicarboxylic anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic anhydride.

[0218] Examples of the latent curing agent include boron trifluoride-amine complex, dicyandiamide, and carboxylic acid hydrazide.

[0219] The curing agent may be used alone or in combination of two or more. It should be noted that the curing agent may also function as a curing accelerator.

[0220] As the curing agent, an amine curing agent (for example, an aromatic amine curing agent) is preferable.

[0221] The content ratio of the above-mentioned curing agent can be appropriately selected according to the type of thermosetting resin (epoxy equivalent, etc.), the type of curing agent, etc., for example, relative to 100 parts by weight of the thermosetting resin, it is 0.1 to 300 parts by weight, preferably 1 to 250 parts by weight, more preferably 3 to 200 parts by weight (for example, 4 to 150 parts by weight), and particularly preferably 5 to 100 parts by weight.

[0222] (Curing accelerator)

[0223] The thermosetting resin composition of the present embodiment may contain a curing accelerator.

[0224] The curing accelerator may be appropriately selected according to the type of the thermosetting resin.

[0225] When the thermosetting resin is an epoxy resin, examples of the curing accelerator include phosphines, amines, and amine salts.

[0226] Examples of the phosphines include ethylphosphine, propylphosphine, trialkylphosphine, phenylphosphine, and triphenylphosphine.

[0227] Examples of the amines include secondary and tertiary amines.

[0228] Examples of the secondary and tertiary amines include triethylamine, piperidine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, triethylenediamine, tris(dimethylaminomethyl)phenol, and N,N-dimethylpiperazine.

[0229] The curing accelerators may be used alone or in combination of two or more.

[0230] The content ratio of the curing accelerator is, for example, 0.01 to 100 parts by weight, preferably 0.05 to 50 parts by weight, and more preferably 1 to 30 parts by weight, based on 100 parts by weight of the thermosetting resin.

[0231] (Other ingredients)

[0232] The thermosetting resin composition of the present embodiment may further contain at least any one of a thermoplastic resin and an additive as other components as necessary.

[0233] Examples of the thermoplastic resin include acrylic resins, polyolefin resins (e.g., polypropylene), polyamide resins, polyester resins, polycarbonate resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyether ketone resins, polyether ether ketone resins, polyimide resins, and polyetherimide resins.

[0234] Examples of the polyester resin include aromatic polyester resins (for example, polyethylene terephthalate).

[0235] Examples of the additives include non-fibrous fillers, stabilizers, colorants, dispersants, preservatives, antioxidants, and defoaming agents.

[0236] The content ratio of other components is, for example, 10 parts by weight or less (for example, 0.01 to 10 parts by weight) based on 100 parts by weight of the thermosetting resin.

[0237] <Cured product>

[0238] The cured product of the present embodiment is a cured product obtained by thermally curing the thermosetting resin composition of the present embodiment.

[0239] The shape of the cured product of the present embodiment may be a one-dimensional shape (a rod shape, etc.), a two-dimensional shape (a sheet shape, etc.), or a three-dimensional shape.

[0240] <Prepreg>

[0241] The prepreg of the present embodiment is a prepreg in which an aggregate of reinforcing fibers is impregnated or injected with the thermosetting resin composition of the present embodiment.

[0242] That is, the prepreg of the present embodiment is formed of a thermosetting resin composition and reinforcing fibers.

[0243] By thermally curing the prepreg of the present embodiment (specifically, by thermally curing the thermosetting resin composition contained in the prepreg), a fiber-reinforced plastic can be obtained.

[0244] Examples of the reinforcing fibers include carbon fibers, glass fibers, aramid fibers, boron fibers, polyparaphenylene benzobisoxazole (PBO) fibers, polyethylene fibers, alumina fibers, and silicon carbide fibers.

[0245] As the above-mentioned reinforcing fiber, carbon fiber is preferable.

[0246] The reinforcing fibers may be monofilaments or multifilaments.

[0247] The single fiber fineness of the reinforcing fiber is preferably 0.2 to 2.0 dtex, more preferably 0.4 to 1.8 dtex.

[0248] When the reinforcing fiber is a multifilament, the number of filaments in the fiber is preferably 2,500 to 50,000.

[0249] The reinforcing fibers may be formed in the form of continuous fibers or in the form of discontinuous fibers.

[0250] When higher mechanical properties are required for the cured product, continuous fibers are preferably used as the reinforcing fibers.

[0251] The continuous fibers may be included in the prepreg of the present embodiment in the form of, for example, a unidirectional base material, a knitted fabric, a woven fabric, a tow, or a roving.

[0252] The reinforcing fibers in a discontinuous form may be included in the prepreg of the present embodiment in the form of, for example, a nonwoven fabric or chopped strands.

[0253] The thermosetting resin composition may be contained in the prepreg in a liquid state or in a solid state.

[0254] The prepreg of the present embodiment is a concept that also includes a tow prepreg. A tow prepreg is a prepreg formed of a tow (bundle of reinforcing fibers) and a solid thermosetting resin composition.

[0255] The prepreg of the present embodiment preferably contains 1 to 50 parts by weight, more preferably 5 to 30 parts by weight of the reinforcing fiber, based on 100 parts by weight of the thermosetting resin.

[0256] (Fiber-reinforced plastics)

[0257] The fiber-reinforced plastic of the present embodiment is formed of the cured product of the present embodiment and the above-mentioned reinforcing fibers.

[0258] The fiber reinforced plastic of the present embodiment is also referred to as a "fiber reinforced polymer composite material" or "FRP".

[0259] In the fiber reinforced plastic of the present embodiment, the reinforcing fibers are preferably carbon fibers. In other words, the fiber reinforced plastic of the present embodiment is preferably carbon fiber reinforced plastic (CFRP).

[0260] The fiber reinforced plastic of this embodiment is obtained by thermally curing the prepreg of this embodiment.

[0261] That is, the fiber reinforced plastic of the present embodiment can be produced by thermally curing the prepreg of the present embodiment.

[0262] For example, the fiber reinforced plastic of the present embodiment can be obtained by a filament winding method.

[0263] In the fiber winding method, a filamentary prepreg formed by a filament bundle (a bundle of reinforcing fibers) and a thermosetting resin composition is rolled up using a mandrel to obtain a prepreg of a desired shape (for example, a tube shape, a tank shape), and the prepreg is thermally cured (the thermosetting resin composition contained in the prepreg is thermally cured), thereby obtaining a fiber-reinforced plastic of the desired shape.

[0264] Examples of the filament winding method include a wet method and a dry method.

[0265] In the wet method, a tow (a bundle of reinforcing fibers) is added to a liquid thermosetting resin composition to obtain a prepreg, and the prepreg containing the liquid thermosetting resin composition is rolled up using a mandrel.

[0266] In the Dry method, a tow prepreg is rolled up using a mandrel. In the Dry method, a fiber-reinforced plastic having a desired shape can be easily produced by using a prefabricated tow prepreg.

[0267] From the viewpoint of improving the mechanical efficiency, the fiber-reinforced plastic of the present embodiment preferably has two or more layers containing the above-mentioned reinforcing fibers.

[0268] Examples of the fiber-reinforced plastic having two or more layers containing the above-mentioned reinforcing fibers include fiber-reinforced plastic having two or more layers of an aggregate including reinforcing fibers.

[0269] The fiber-reinforced plastic having two or more layers containing the above-mentioned reinforcing fibers can be produced, for example, as follows.

[0270] By stacking a plurality of prepreg layers and thermally curing the stacked plurality of prepreg layers, a fiber-reinforced plastic having two or more layers containing the above-mentioned reinforcing fibers can be obtained.

[0271] Furthermore, a fiber-reinforced plastic having two or more layers containing the reinforcing fibers can be obtained by stacking two or more layers of reinforcing fiber aggregates to obtain a laminate, and impregnating or injecting the thermosetting resin composition into the laminate.

[0272] (Molding products)

[0273] The molded article of the present embodiment is a molded article formed of the cured product of the present embodiment.

[0274] The molded article of the present embodiment is a concept that also includes a molded article formed of the fiber reinforced plastic of the present embodiment.

[0275] Examples of the molded article of the present embodiment include an airplane fuselage, a golf club shaft, a fishing rod, and a container (specifically, a high-pressure container).

[0276] [Public Project]

[0277] The following items disclose preferred embodiments.

[0278] [Project 1]

[0279] A thermosetting resin composition comprising a first resin as a thermosetting resin and resin particles comprising a second resin having an amide bond, wherein:

[0280] The second resin comprises one or more second functional groups selected from an amino group, a carboxyl group, an isocyanate group, and a carboxylic anhydride group,

[0281] The first resin includes a first functional group capable of reacting with the second functional group.

[0282] The second resin contains 25 to 190 mmol / kg of the second functional group.

[0283] The relative viscosity of the second resin is 1.50 to 2.50.

[0284] [Project 2]

[0285] The thermosetting resin composition according to item 1, wherein the second resin includes a polyamide resin.

[0286] [Item 3]

[0287] The thermosetting resin composition according to item 2, wherein the polyamide resin comprises an aliphatic polyamide resin and / or an alicyclic polyamide resin.

[0288] [Item 4]

[0289] The thermosetting resin composition according to item 3, wherein the polyamide resin includes the alicyclic polyamide resin.

[0290] [Item 5]

[0291] The thermosetting resin composition according to any one of items 1 to 4, wherein the median particle size of the resin particles is 50 μm or less.

[0292] [Item 6]

[0293] The thermosetting resin composition according to any one of items 1 to 5, wherein the resin particles have a sphericity of 75% or more.

[0294] [Item 7]

[0295] The thermosetting resin composition according to any one of items 1 to 6, wherein the second resin has a glass transition temperature of 30 to 160°C.

[0296] [Item 8]

[0297] The thermosetting resin composition according to item 7, wherein the second resin has a glass transition temperature of 30 to 48°C.

[0298] [Item 9]

[0299] The thermosetting resin composition according to any one of items 1 to 8, wherein the second resin contains 29 to 120 mmol / kg of the second functional group.

[0300] [Item 10]

[0301] The thermosetting resin composition according to any one of items 1 to 9, wherein the first resin includes an epoxy resin.

[0302] [Item 11]

[0303] The thermosetting resin composition according to any one of items 1 to 10, comprising 1 to 20 parts by weight of the resin particles based on 100 parts by weight of the first resin.

[0304] [Item 12]

[0305] A cured product obtained by thermally curing the thermosetting resin composition according to any one of items 1 to 11.

[0306] [Item 13]

[0307] A prepreg, wherein an aggregate of reinforcing fibers is impregnated or injected with the thermosetting resin composition according to any one of items 1 to 11.

[0308] [Item 14]

[0309] A molded article formed from the cured product according to item 12.

[0310] [Item 15]

[0311] A fiber-reinforced plastic comprising the cured product according to item 12 and reinforcing fibers.

[0312] [Item 16]

[0313] The fiber-reinforced plastic according to item 15 has two or more layers containing the above-mentioned reinforcing fibers.

[0314] Example

[0315] Next, the present disclosure will be described in more detail with reference to Examples and Comparative Examples. It should be noted that the present disclosure is not limited to these Examples.

[0316] (Water-soluble base)

[0317] The following water-soluble matrices were prepared.

[0318] Modified PVA-based resin 1 (hereinafter also referred to as "modified PVA1"): a modified PVA-based resin prepared according to the method described in paragraphs 0119 to 0121 of Japanese Patent Application Laid-Open No. 2019-1942 ("modified PVA-based resin 2" described in the Japanese Patent Application Laid-Open No. 2019-1942)

[0319] Modified PVA-based resin 2 (hereinafter also referred to as "modified PVA2"): a modified PVA-based resin prepared according to the method described in paragraphs 0112 to 0115 of Japanese Patent Application Laid-Open No. 2019-1942 ("modified PVA-based resin 1" described in the Japanese Patent Application Laid-Open No. 2019-1942)

[0320] Sugar alcohol: D-sorbitol LTS powder 20M manufactured by Mitsubishi Shoji Foodtech

[0321] (Extruder)

[0322] The following extruder (extruder having a barrel) was prepared.

[0323] "TEX30XSST" manufactured by Nippon Steel Works, Ltd. (hereinafter referred to as "TEX30")

[0324] "LaboPlastomill" manufactured by Toyo Seiki Seisaku-sho Co., Ltd. (hereinafter referred to as "Plastomill")

[0325] (Examples 1 to 3, 5 to 8, 11 to 16, Comparative Example 12)

[0326] The water-soluble base and the raw material resin were melt-kneaded using an extruder under the conditions shown in the following Table 1, and the melt-kneaded product was discharged.

[0327] In addition, the raw material resin is a polyamide resin manufactured by Polyplastics-Evonik.

[0328] The discharged molten kneaded product was cooled and cut to obtain a granular preform. The preform was put into water and stirred to dissolve the water-soluble matrix to obtain a slurry. The slurry was passed through a sieve (mesh: 250 μm), and the slurry after passing through the sieve was filtered with filter paper, thereby recovering the precursor particles that passed through the sieve and remained on the filter paper. The precursor particles were naturally dried under the conditions of temperature 23°C and humidity 50%RH to obtain resin particles (powder).

[0329] Next, the resin particles and an epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation) as a thermosetting resin were stirred for 6 hours using a thermomixer at 80°C and 300 rpm to obtain a mixture.

[0330] Then, the mixture was degassed by placing it in a vacuum container for 1 hour.

[0331] Next, an amine curing agent ("jERCURE W" manufactured by Mitsubishi Chemical Corporation) was added to the defoamed mixture, followed by stirring and defoaming, thereby obtaining a thermosetting resin composition (resin particles: 14.4% by weight).

[0332] (Example 4)

[0333] By using an extruder ("TEX30" manufactured by Nippon Steel Works, Ltd.), 100 parts by weight of the raw material resin of Example 2 and 1.5 parts by weight of a carbodiimide compound (Stabaxol I Powder, manufactured by LANXESS) were melt-kneaded (barrel temperature: 220°C) to obtain a melt-kneaded product. Next, the melt-kneaded product was discharged from the extruder, and the discharged rod-shaped melt-kneaded product was cooled. Then, pellets were obtained by cutting the rod-shaped melt-kneaded product. Next, the pellets were dried at 80°C for 4 hours using a dehumidifying dryer to obtain dried pellets (raw material resin).

[0334] Resin particles were obtained in the same manner as in Example 1 except that the raw material resin was used and the conditions shown in Table 1 below were adopted, and then a thermosetting resin composition was obtained.

[0335] (Example 9)

[0336] By using an extruder ("TEX30" manufactured by Nippon Steel Works, Ltd.), 90 parts by weight of the raw material resin of Example 5 and 10 parts by weight of PA12 (carboxyl group concentration: 5 mmol / kg, amino group concentration: 400 mmol / kg. Relative viscosity: 1.33) manufactured by Polyplastics-Evonik were melt-kneaded (barrel temperature: 220°C) to obtain a molten mixture. Next, the molten mixture was discharged from the extruder, and the discharged rod-shaped molten mixture was cooled. Then, pellets were obtained by cutting the rod-shaped molten mixture. Next, the pellets were dried at 80°C for 4 hours using a dehumidifying dryer to obtain dry pellets (raw material resin).

[0337] Resin particles were obtained in the same manner as in Example 1 except that the raw material resin was used and the conditions shown in Table 1 below were adopted, and then a thermosetting resin composition was obtained.

[0338] (Example 10)

[0339] By using an extruder ("TEX30" manufactured by Nippon Steel Works, Ltd.), 85 parts by weight of the raw material resin of Example 5 and 15 parts by weight of PA12 manufactured by Polyplastics-Evonik (carboxyl group concentration: 5 mmol / kg, amino group concentration: 400 mmol / kg, relative viscosity: 1.33) were melt-kneaded (barrel temperature: 220°C) to obtain a molten kneaded product. Next, the molten kneaded product was discharged from the extruder, and the discharged rod-shaped molten kneaded product was cooled. Then, pellets were obtained by cutting the rod-shaped molten kneaded product. Next, the pellets were dried at 80°C for 4 hours using a dehumidifying dryer to obtain dried pellets (raw material resin).

[0340] Resin particles were obtained in the same manner as in Example 1 except that the raw material resin was used and the conditions shown in Table 1 below were adopted, and then a thermosetting resin composition was obtained.

[0341] (Comparative Example 1)

[0342] A thermosetting resin composition was obtained in the same manner as in Example 1 except that the resin particles were not used.

[0343] (Comparative Example 2)

[0344] By using an extruder ("TEX30" manufactured by Nippon Steel Works, Ltd.), 100 parts by weight of the raw material resin of Example 2 and 2.5 parts by weight of a carbodiimide compound (Stabaxol I Powder, manufactured by LANXESS) were melt-kneaded (barrel temperature: 220°C) to obtain a melt-kneaded product. Next, the melt-kneaded product was discharged from the extruder, and the discharged rod-shaped melt-kneaded product was cooled. Then, pellets were obtained by cutting the rod-shaped melt-kneaded product. Next, the pellets were dried at 80°C for 4 hours using a dehumidifying dryer to obtain dried pellets (raw material resin).

[0345] Resin particles were obtained in the same manner as in Example 1 except that the raw material resin was used and the conditions shown in Table 1 below were adopted, and then a thermosetting resin composition was obtained.

[0346] (Comparative Example 3)

[0347] By using an extruder ("TEX30" manufactured by Nippon Steel Works, Ltd.), 100 parts by weight of amorphous alicyclic polyamide manufactured by Polyplastics-Evonik and 4 parts by weight of a carbodiimide compound (Stabaxol I Powder, manufactured by LANXESS) were melt-kneaded (barrel temperature: 280°C) to obtain a melt-kneaded product. Next, the melt-kneaded product was discharged from the extruder, and the discharged rod-shaped melt-kneaded product was cooled. Then, pellets were obtained by cutting the rod-shaped melt-kneaded product. Next, the pellets were dried at 80°C for 4 hours using a dehumidifying dryer to obtain dried pellets (raw material resin).

[0348] Resin particles were obtained in the same manner as in Example 1 except that the raw material resin was used and the conditions shown in Table 1 below were adopted, and then a thermosetting resin composition was obtained.

[0349] (Comparative Example 4)

[0350] By using an extruder ("TEX30" manufactured by Nippon Steel Works, Ltd.), 100 parts by weight of amorphous alicyclic polyamide manufactured by Polyplastics-Evonik and 4 parts by weight of a carbodiimide compound (Stabaxol I Powder, manufactured by LANXESS) were melt-kneaded (barrel temperature: 280°C) to obtain a melt-kneaded product. Next, the melt-kneaded product was discharged from the extruder, and the discharged rod-shaped melt-kneaded product was cooled. Then, pellets were obtained by cutting the rod-shaped melt-kneaded product. Next, the pellets were dried at 80°C for 4 hours using a dehumidifying dryer to obtain dried pellets (raw material resin).

[0351] Resin particles were obtained in the same manner as in Example 1 except that the raw material resin was used and the conditions shown in Table 1 below were adopted, and then a thermosetting resin composition was obtained.

[0352] (Comparative Example 5)

[0353] By using an extruder ("TEX30" manufactured by Nippon Steel Works, Ltd.), 100 parts by weight of PA12 (manufactured by Polyplastics-Evonik) and 4 parts by weight of a carbodiimide compound (Stabaxol I Powder, manufactured by LANXESS) were melt-kneaded (barrel temperature: 280°C) to obtain a melt-kneaded product. Next, the melt-kneaded product was discharged from the extruder, and the discharged rod-shaped melt-kneaded product was cooled. Then, pellets were obtained by cutting the rod-shaped melt-kneaded product. Next, the pellets were dried at 80°C for 4 hours using a dehumidifying dryer to obtain dried pellets (raw material resin).

[0354] Resin particles were obtained in the same manner as in Example 1 except that the raw material resin was used and the conditions shown in Table 1 below were adopted, and then a thermosetting resin composition was obtained.

[0355] (Comparative Example 6)

[0356] By using an extruder ("TEX30" manufactured by Nippon Steel Works, Ltd.), 100 parts by weight of microcrystalline alicyclic polyamide manufactured by Polyplastics-Evonik and 4 parts by weight of a carbodiimide compound (Stabaxol I Powder, manufactured by LANXESS) were melt-kneaded (barrel temperature: 280°C) to obtain a melt-kneaded product. Next, the melt-kneaded product was discharged from the extruder, and the discharged rod-shaped melt-kneaded product was cooled. Then, pellets were obtained by cutting the rod-shaped melt-kneaded product. Next, the pellets were dried at 80°C for 4 hours using a dehumidifying dryer to obtain dried pellets (raw material resin).

[0357] Resin particles were obtained in the same manner as in Example 1 except that the raw material resin was used and the conditions shown in Table 1 below were adopted, and then a thermosetting resin composition was obtained.

[0358] (Comparative Example 7)

[0359] By using an extruder ("TEX30" manufactured by Nippon Steel Works, Ltd.), 100 parts by weight of amorphous alicyclic polyamide manufactured by Polyplastics-Evonik and 4 parts by weight of a carbodiimide compound (Stabaxol I Powder, manufactured by LANXESS) were melt-kneaded (barrel temperature: 280°C) to obtain a melt-kneaded product. Next, the melt-kneaded product was discharged from the extruder, and the discharged rod-shaped melt-kneaded product was cooled. Then, pellets were obtained by cutting the rod-shaped melt-kneaded product. Next, the pellets were dried at 80°C for 4 hours using a dehumidifying dryer to obtain dried pellets (raw material resin).

[0360] Resin particles were obtained in the same manner as in Example 1 except that the raw material resin was used and the conditions shown in Table 1 below were adopted, and then a thermosetting resin composition was obtained.

[0361] (Comparative Example 8)

[0362] By using an extruder ("TEX30" manufactured by Nippon Steel Works, Ltd.), 100 parts by weight of PA1010 (manufactured by Polyplastics-Evonik) and 3 parts by weight of a carbodiimide compound (Stabaxol I Powder, manufactured by LANXESS) were melt-kneaded (barrel temperature: 280°C) to obtain a melt-kneaded product. Next, the melt-kneaded product was discharged from the extruder, and the discharged rod-shaped melt-kneaded product was cooled. Then, pellets were obtained by cutting the rod-shaped melt-kneaded product. Next, the pellets were dried at 80°C for 4 hours using a dehumidifying dryer to obtain dried pellets (raw material resin).

[0363] Resin particles were obtained in the same manner as in Example 1 except that the raw material resin was used and the conditions shown in Table 1 below were adopted, and then a thermosetting resin composition was obtained.

[0364] (Comparative Example 9)

[0365] By using an extruder ("TEX30" manufactured by Nippon Steel Works, Ltd.), 65 parts by weight of the raw material resin of Example 5 and 35 parts by weight of PA12 manufactured by Polyplastics-Evonik (carboxyl group concentration: 5 mmol / kg, amino group concentration: 400 mmol / kg, relative viscosity: 1.33) were melt-kneaded (barrel temperature: 220°C) to obtain a melt-kneaded product. Next, the melt-kneaded product was discharged from the extruder, and the discharged rod-shaped melt-kneaded product was cooled. Then, pellets were obtained by cutting the rod-shaped melt-kneaded product. Next, the pellets were dried at 80°C for 4 hours using a dehumidifying dryer to obtain dried pellets (raw material resin).

[0366] Resin particles were obtained in the same manner as in Example 1 except that the raw material resin was used and the conditions shown in Table 1 below were adopted, and then a thermosetting resin composition was obtained.

[0367] (Comparative Example 10)

[0368] By using an extruder ("TEX30" manufactured by Nippon Steel Works, Ltd.), 55 parts by weight of amorphous alicyclic polyamide resin manufactured by Polyplastics-Evonik and 45 parts by weight of PA12 manufactured by Polyplastics-Evonik (carboxyl group concentration: 5 mmol / kg, amino group concentration: 400 mmol / kg, relative viscosity: 1.33) were melt-kneaded (barrel temperature: 220°C) to obtain a melt-kneaded product. Next, the melt-kneaded product was discharged from the extruder, and the discharged rod-shaped melt-kneaded product was cooled. Then, pellets were obtained by cutting the rod-shaped melt-kneaded product. Next, the pellets were dried at 80°C for 4 hours using a dehumidifying dryer to obtain dry pellets (raw material resin).

[0369] Resin particles were obtained in the same manner as in Example 1 except that the raw material resin was used and the conditions shown in Table 1 below were adopted, and then a thermosetting resin composition was obtained.

[0370] (Comparative Example 11)

[0371] By using an extruder ("TEX30" manufactured by Nippon Steel Works, Ltd.), 55 parts by weight of a microcrystalline alicyclic polyamide resin manufactured by Polyplastics-Evonik and 45 parts by weight of PA12 manufactured by Polyplastics-Evonik (carboxyl group concentration: 5 mmol / kg, amino terminal group concentration: 400 mmol / kg, relative viscosity: 1.33) were melt-kneaded (barrel temperature: 220°C) to obtain a melt-kneaded product. Next, the melt-kneaded product was discharged from the extruder, and the discharged rod-shaped melt-kneaded product was cooled. Then, pellets were obtained by cutting the rod-shaped melt-kneaded product. Next, the pellets were dried at 80°C for 4 hours using a dehumidifying dryer to obtain dry pellets (raw material resin).

[0372] Resin particles were obtained in the same manner as in Example 1 except that the raw material resin was used and the conditions shown in Table 1 below were adopted, and then a thermosetting resin composition was obtained.

[0373] The relative viscosity, carboxyl group concentration, and amino group concentration of the raw material resin shown in Table 1 below were measured by the above method.

[0374] In addition, the relative viscosity, carboxyl group concentration, and amino group concentration of the polyamide resin used in the preparation of the raw material resin were measured by the above-mentioned method.

[0375]

[0376] (Relative viscosity of the second resin, concentration of carboxyl groups, concentration of amino groups, and concentration of the second functional group)

[0377] The relative viscosity, carboxyl group concentration, amino group concentration, and second functional group concentration of the second resin contained in the resin particles were measured by the above-mentioned method. The measured values ​​are shown in Table 2 below.

[0378] In addition, in the Examples and Comparative Examples, the concentration of the second functional group refers to the total concentration of the amino group and the carboxyl group.

[0379] (Median Particle Size and Sphericity of Resin Particles, and Glass Transition Temperature (Tg) of Second Resin)

[0380] The median particle size (D50) and sphericity of the resin particles and the glass transition temperature (Tg) of the second resin were measured by the above-mentioned method. The measured values ​​are shown in Table 2 below.

[0381] (Plane strain fracture toughness of the cured product (K IC ))

[0382] First, a thermosetting resin composition was poured into a mold (47 mm (length)×12 mm (width)×4 mm (thickness)).

[0383] Next, the thermosetting resin composition was heated at 175° C. until the thermosetting resin composition was fully thermally cured, thereby obtaining a cured product having precracks. In order to provide the cured product with precracks, convex portions corresponding to the precracks were formed on the inner surface of the mold.

[0384] Then, the plane strain fracture toughness (K IC ).

[0385] The results are shown in Table 2 below.

[0386]

[0387] Figure 1 . The SEM image of the resin particles used in Example 3 is shown in FIG.

[0388] Figure 2 ] A SEM image of a cross section of a cured product obtained by thermally curing the thermosetting resin composition of Example 3 is shown in FIG.

[0389] The cured product is based on the plane strain fracture toughness (K IC ) was prepared from a thermosetting resin composition in the same manner as the test method of ). Next, the cured product was fractured using an IZOD impact tester to obtain a fracture surface. The fracture surface was then photographed using a SEM.

[0390] Figure 2 The round objects are resin particles. It is known that the resin particles remain in a particle state even after curing.

[0391] As shown in Table 2, in Examples 1 to 16 within the scope of the present disclosure, the plane strain fracture toughness (K IC )high.

[0392] Therefore, according to the present disclosure, a thermosetting resin composition having a cured product with further improved toughness can be provided.

[0393] It should be noted that the comparison between the examples has the following tendency.

[0394] That is, the higher the relative viscosity, the higher the plane strain fracture toughness (K IC ) tends to be higher. In addition, the higher the median particle size, the higher the plane strain fracture toughness (K IC ) is higher. In addition, it is known that when the concentration of the second functional group in the second resin is above a given value, the plane strain fracture toughness (K IC ) has not changed significantly.

Claims

1. A thermosetting resin composition, comprising: A first resin as a thermosetting resin, and resin particles containing a second resin having an amide bond, in, The second resin comprises one or more second functional groups selected from an amino group, a carboxyl group, an isocyanate group, and a carboxylic anhydride group. The first resin includes a first functional group capable of reacting with the second functional group, The second resin contains 25 to 190 mmol / kg of the second functional group, The relative viscosity of the second resin is 1.50-2.

50.

2. The thermosetting resin composition according to claim 1, wherein The second resin includes a polyamide resin.

3. The thermosetting resin composition according to claim 2, wherein The polyamide resin includes an aliphatic polyamide resin and / or an alicyclic polyamide resin.

4. The thermosetting resin composition according to claim 3, wherein The polyamide resin includes the alicyclic polyamide resin.

5. The thermosetting resin composition according to any one of claims 1 to 4, wherein The resin particles have a median particle size of 50 μm or less.

6. The thermosetting resin composition according to any one of claims 1 to 4, wherein The sphericity of the resin particles is greater than 75%.

7. The thermosetting resin composition according to any one of claims 1 to 4, wherein The second resin has a glass transition temperature of 30 to 160°C.

8. The thermosetting resin composition according to claim 7, wherein The second resin has a glass transition temperature of 30-48°C.

9. The thermosetting resin composition according to any one of claims 1 to 4, wherein The second resin contains 29 to 120 mmol / kg of the second functional group.

10. The thermosetting resin composition according to any one of claims 1 to 4, wherein The first resin includes epoxy resin.

11. The thermosetting resin composition according to any one of claims 1 to 4, wherein The resin particles are contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the first resin. 12 . A cured product obtained by thermally curing the thermosetting resin composition according to claim 1 . 13 . A prepreg, wherein an aggregate of reinforcing fibers is impregnated or injected with the thermosetting resin composition according to claim 1 .

14. A molded article formed from the cured product according to claim 12.

15. A fiber reinforced plastic comprising reinforcing fibers and the cured product according to claim 12. 16 . The fiber-reinforced plastic according to claim 15 , comprising two or more layers containing the reinforcing fibers.

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