Thermosetting resin composition and cured product

Abstract

To provide, e.g., a thermosetting resin composition which forms a cured product with higher toughness.SOLUTION: The present disclosure pertains, e.g., to a thermosetting resin composition containing: a first resin which is a thermosetting resin; and resin particles which contain a second resin having an amide bond. The second resin includes at least one second functional group selected from the group consisting of an amino group, a carboxy group, an isocyanate group and a carboxylic anhydride group. The first resin includes a first functional group that can react with the second functional group. The second resin includes the second functional group in an amount of 25-190 mmol / kg. The relative viscosity of the second resin is 1.50-2.50.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] A cured product obtained by curing an epoxy resin composition is used as a material for aircraft bodies, golf club shafts, fishing rods, etc. (for example, Patent Document 1). Further, from the viewpoint of enhancing the toughness of a cured product obtained by curing an epoxy resin composition, an epoxy resin composition having an epoxy resin and resin particles containing a polyamide resin is used (for example, Patent Document 2).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] By the way, a cured product having even higher toughness may be required. However, regarding a thermosetting resin composition having even higher toughness of the cured product, sufficient studies have not been made so far.

[0005] Therefore, an object of the present disclosure is to provide a thermosetting resin composition having even higher toughness of the cured product and a cured product obtained by thermosetting the thermosetting resin composition.

Means for Solving the Problems

[0006] A first aspect of the present disclosure is a thermosetting resin composition having a first resin that is a thermosetting resin and resin particles containing a second resin having an amide bond, The second resin contains one or more second functional groups selected from the group consisting of an amino group, a carboxy group, an isocyanate group, and a carboxylic anhydride group. The first resin contains 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. Relates to a thermosetting resin composition in which the relative viscosity of the second resin is 1.50 to 2.50.

[0007] A second aspect of the present disclosure relates to a cured product obtained by thermosetting the thermosetting resin composition.

[0008] A third aspect of the present disclosure relates to a prepreg in which the thermosetting resin composition is impregnated or injected into an aggregate of reinforcing fibers.

[0009] A fourth aspect of the present disclosure relates to a molded article formed from the cured product.

[0010] A fifth aspect of the present disclosure relates to a fiber-reinforced plastic comprising the cured product and reinforcing fibers.

Advantages of the Invention

[0011] According to the present disclosure, it is possible to provide a thermosetting resin composition having a higher toughness of the cured product. Further, according to the present disclosure, it is possible to provide a cured product obtained by thermosetting the thermosetting resin composition.

Brief Description of the Drawings

[0012]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0013] Hereinafter, an embodiment of the present disclosure will be described.

[0014] In addition, each configuration and their combinations in each embodiment are merely examples, and within the scope not departing from the gist of the present disclosure, addition, omission, substitution, and other modifications of the configuration can be made as appropriate. The present disclosure is not limited by the embodiments, but is limited only by the scope of the claims. Also, each aspect disclosed in this specification can be combined with any other features disclosed in this specification.

[0015] <Thermosetting resin composition> First, the thermosetting resin composition according to this embodiment will be described. The thermosetting resin composition according to this embodiment has a first resin that is a thermosetting resin and resin particles containing a second resin having an amide bond. The second resin contains one or more second functional groups selected from the group consisting of an amino group, a carboxy group, an isocyanate group, and a carboxylic anhydride group. The first resin contains a first functional group that can react 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 to 2.50.

[0016] When the second resin contains 25 mmol / kg or more of the second functional group, the toughness of the cured product becomes even higher. This reason is considered to be as follows. That is, when the second resin contains 25 mmol / kg or more of the second functional group, the affinity between the resin particles and the first resin in the cured product becomes higher, and it is considered that the toughness of the cured product at the boundary between the resin particles and the first resin has increased.

[0017] Generally, the relative viscosity of a resin is used as an index of the average molecular weight of the resin. The higher the relative viscosity of the resin, the higher the average molecular weight of the resin. Since the relative viscosity of the second resin is 2.50 or less, the average molecular weight of the second resin becomes low, and it becomes easy to increase the content ratio of the second functional group in the second resin.

[0018] Since the relative viscosity of the second resin is 1.50 or more, the toughness of the cured product becomes even higher. This reason is considered to be as follows. That is, since the relative viscosity of the second resin is 1.50 or more, it is considered that the average molecular weight of the second resin becomes high and the toughness of the resin particles becomes high.

[0019] Since the second resin contains 190 mmol / kg or less of the second functional group, it becomes easy to increase the molecular weight of the second resin.

[0020] Therefore, according to the present embodiment, it is possible to provide a thermosetting resin composition having even higher toughness of the cured product.

[0021] (First resin which is a thermosetting resin) The first resin which is a thermosetting resin contains a first functional group that can react with the second functional group. 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, a thiol group, and the like. and the like. Examples of the thermosetting resin include an epoxy resin, a phenol resin, an unsaturated polyester resin, a vinyl ester resin, an acrylic resin, a urea resin, a melamine resin, an aniline resin, a polyimide resin, a bismaleimide resin, and the like. These thermosetting resins may be used alone or in combination of two or more.

[0022] As the thermosetting resin, an epoxy resin and a phenol resin are preferable, and an epoxy resin is particularly preferable. Since the resin particles containing the polyamide resin are easily dispersed in the epoxy resin, when the thermosetting resin contains an epoxy resin, the effect of improving toughness by the resin particles is likely to be exhibited.

[0023] Examples of the epoxy resin include glycidyl ether type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, alkene oxides (such as vinyl cyclohexene dioxide, etc.), triglycidyl isocyanurate, and the like.

[0024] Examples of the glycidyl ether type epoxy resin include bisphenol type epoxy resin, phenol type epoxy resin, dicyclopentadiene type epoxy resin, epoxy resin having an aromatic skeleton (polyglycidyl ether), alkane diol diglycidyl ether, polyalkane diol diglycidyl ether, epoxy resin having an aliphatic skeleton (polyglycidyl ether), and the like.

[0025] Examples of the bisphenol type epoxy resin include reaction products of bisphenols and epichlorohydrin, reaction products of alkylene oxide adducts of bisphenols and epichlorohydrin, and the like. Examples of the bisphenols include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol type epoxy resin, and the like. In the alkylene oxide adduct of the bisphenols, the number of moles of alkylene oxide added per mole of the hydroxyl group of the bisphenols is, for example, 1 mole or more (for example, 1 to 20 moles), preferably 1 to 15 moles, more preferably 1 to 10 moles.

[0026] Examples of the phenolic epoxy resin include phenol novolak epoxy resin, cresol novolak epoxy resin, naphthol novolak epoxy resin, bisphenol A novolak epoxy resin, bisphenol F novolak epoxy resin, biphenyl skeleton-containing phenol novolak resin, xylylene skeleton-containing phenol novolak resin, and the like.

[0027] Examples of the epoxy resin (polyglycidyl ether) having an aromatic skeleton include glycidyl ether having a naphthalene skeleton and the like. Examples of the glycidyl ether having a naphthalene skeleton include di(glycidyloxy)naphthalene, bis[2,7-di(glycidyloxy)naphthyl]methane, and the like. Examples of the di(glycidyloxy)naphthalene include 1,5-di(glycidyloxy)naphthalene and the like.

[0028] Examples of the alkanediol diglycidyl ether include C 2-10 alkanediol diglycidyl ether and the like. Examples of the C 2-10 alkanediol diglycidyl ether include butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and the like.

[0029] Examples of the polyalkane diol diglycidyl ether include poly C 2-4 alkanediol diglycidyl ether and the like. Examples of the poly C 2-4 alkanediol diglycidyl ether include polypropylene glycol diglycidyl ether and the like.

[0030] Examples of the epoxy resin (polyglycidyl ether) having an aliphatic skeleton include glycidyl polyether of polyol and the like. Examples of the polyol include alkane triol, alkane tetrol, alkane pentol, alkane hexol, and the like. Examples of the alkane triol include C 3-10 alkane triol and the like. Examples of the alkane tetrol include C 3-10 alkane tetrol and the like. Examples of the glycidyl polyether include diglycidyl ether, triglycidyl ether, tetraglycidyl ether, pentaglycidyl ether, hexaglycidyl ether, and the like. Examples of the glycidyl polyether of the polyol include trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, and the like.

[0031] Examples of the glycidylamine type epoxy resin include tetraglycidyl diaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl aminocresol, diglycidylaniline, N,N-diglycidyl-4-glycidyloxyaniline, and the like.

[0032] Examples of the glycidyl ester type epoxy resin include diglycidyl ester of dicarboxylic acid and the like. Examples of the dicarboxylic acid include aromatic dicarboxylic acid, hydrogenated product of aromatic dicarboxylic acid, and the like. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and the like.

[0033] These epoxy resins may be used alone or in combination of two or more. Among these epoxy resins, epoxy resins having an aromatic skeleton are preferable in terms of strength and the like, and bisphenol type epoxy resins are particularly preferable.

[0034] Examples of the phenolic resin include resins having one or more, preferably two or more phenolic hydroxyl groups in one molecule. Examples of the phenolic resin include novolak-type phenolic resins, resol-type phenolic resins, polyoxystyrene resins, and the like.

[0035] The novolak-type phenolic resin is a condensate of phenols and aldehydes. The novolak-type phenolic resin can be obtained, for example, by condensation polymerization of phenols and aldehydes in the presence of an acidic catalyst. The resol-type phenolic resin is a condensate of phenols and aldehydes. The resol-type phenolic resin can be obtained, for example, by condensation polymerization of phenols and aldehydes in the presence of an alkaline catalyst.

[0036] Examples of the phenols include phenol, cresol, trimethylphenol, xylenol, resorcinol, catechol, butylphenol, octylphenol, nonylphenol, phenylphenol, dihydroxybenzene, bisphenol A, naphthol, and the like. Examples of the cresol include o-cresol, m-cresol, and p-cresol. Examples of the trimethylphenol include 2,3,5-trimethylphenol and the like. Examples of the xylenol include 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, and the like.

[0037] Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, glyoxal, glutaraldehyde, terephthalaldehyde, isophthalaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, 3-methylbutyraldehyde, p-tolualdehyde, phenylacetaldehyde, and the like. Examples of the hydroxybenzaldehyde include o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, and p-hydroxybenzaldehyde.

[0038] Examples of the novolak-type phenol resin include novolak resin (a condensate of phenol and formaldehyde), cresol novolak resin (a condensate of cresol and formaldehyde), and the like.

[0039] The phenol resin may be used alone or in combination of two or more.

[0040] The hydroxyl equivalent of the phenol resin is preferably 50 to 500 g / eq, more preferably 100 to 350 g / eq.

[0041] The thermosetting resin composition according to this embodiment preferably contains 40 to 99% by weight, more preferably 80 to 97% by weight of a thermosetting resin.

[0042] (Resin particles) The resin particles are formed of a resin composition for resin particles containing a second resin having an amide bond and a second functional group.

[0043] The second functional group is a functional group capable of reacting with the first functional group. The second functional group is preferably at least one functional group selected from the group consisting of an amino group, a carboxy group, an isocyanate group, an oxazoline group, a carboxylic acid, an ester group, a thiol group, and a carboxylic anhydride group.

[0044] Examples of the amino group include "-NH 2 " and "-NHR". R is an alkyl group. Examples of R include a methyl group, an ethyl group, a propyl group, and the like.

[0045] Examples of the second resin include a polyamide resin, a polyimide resin, a polyamideimide resin, and the like.

[0046] Examples of the polyamide resin include aliphatic polyamide resins, alicyclic polyamide resins, and aromatic polyamide resins. The polyamide resin may be a homopolyamide resin or a copolyamide resin.

[0047] Examples of the aliphatic polyamide resin include polyamide resins of an aliphatic diamine component and an aliphatic dicarboxylic acid component, polyamide resins of lactams, polyamide resins of aminocarboxylic acids, and polyamide resins of an aliphatic diamine component, an aliphatic dicarboxylic acid component, lactams, and / or aminocarboxylic acids.

[0048] Examples of the aliphatic diamine component include C4-16 alkylenediamines (e.g., tetramethylenediamine, hexamethylenediamine, dodecanediamine, etc.). The aliphatic diamine component is preferably a C6-14 alkylenediamine, more preferably a C6-12 alkylenediamine.

[0049] Examples of the aliphatic dicarboxylic acid component include C4-20 alkanedicarboxylic acids (e.g., adipic acid, sebacic acid, dodecanedioic acid, etc.). The aliphatic dicarboxylic acid component is preferably a C5-16 alkanedicarboxylic acid, more preferably a C6-14 alkanedicarboxylic acid.

[0050] Examples of the lactam include lactams having 4 to 20 carbon atoms (e.g., ε-caprolactam, ω-laurolactam, etc.). The lactam is preferably a lactam having 4 to 16 carbon atoms.

[0051] Examples of the aminocarboxylic acid include C4-20 aminocarboxylic acids (e.g., ω-aminoundecanoic acid, etc.). The aminocarboxylic acid is preferably a C4-16 aminocarboxylic acid, more preferably a C6-14 aminocarboxylic acid.

[0052] Examples of the aliphatic polyamide resin 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), polyamide 6 / 12 / 612 (PA6 / 12 / 612), and the like.

[0053] Examples of the alicyclic polyamide resin include polyamide resins containing at least one selected from at least an alicyclic diamine component and an alicyclic dicarboxylic acid component as constituent components. As the alicyclic polyamide resin, an alicyclic polyamide resin containing an alicyclic diamine component and / or an alicyclic dicarboxylic acid component together with the exemplified aliphatic diamine component and / or aliphatic dicarboxylic acid component as the diamine component and the dicarboxylic acid component is preferable. Such an alicyclic polyamide resin has high transparency and is known as a so-called transparent polyamide resin.

[0054] Examples of the alicyclic diamine component include diaminocycloalkane, bis(aminocycloalkyl)alkane, hydrogenated xylylenediamine, and the like. Examples of the diaminocycloalkane include diaminocyclohexane and the like. The diaminocycloalkane is preferably a diaminoc5-10 cycloalkane. Examples of the bis(aminocycloalkyl)alkane include bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 2,2-bis(4'-aminocyclohexyl)propane, and the like. The bis(aminocycloalkyl)alkane is preferably a bis(aminoc5-8 cycloalkyl)C1-3 alkane. The alicyclic diamine component may have a substituent such as an alkyl group, for example. The alkyl group is preferably a C1-6 alkyl group, more preferably a C1-4 alkyl group, and even more preferably a C1-2 alkyl group (such as a methyl group or an ethyl group).

[0055] Examples of the alicyclic dicarboxylic acid include cycloalkane dicarboxylic acids (such as cyclohexane-1,4-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, etc.).

[0056] Typical alicyclic polyamide resins include, for example, condensates of an alicyclic diamine component [such as bis(aminocyclohexyl)alkane, etc.] and an aliphatic dicarboxylic acid component [such as alkane dicarboxylic acid (such as C 4-20 alkane dicarboxylic acid component, etc.)].

[0057] The aromatic polyamide resin is a concept that includes a polyamide resin containing at least one of an aromatic diamine component and an aromatic dicarboxylic acid component as a structural unit. Examples of the aromatic polyamide resin include polyamide resins in which both the diamine component of the structural unit and the dicarboxylic acid component of the structural unit are aromatic components (also called "fully aromatic polyamide resins" or "aramids", etc.). The aromatic polyamide resin may be a modified polyamide resin. Examples of the modified polyamide resin include polyamide resins having a branched chain structure. Examples of the aromatic diamine component include metaxylylenediamine, etc. Examples of the aromatic dicarboxylic acid component include terephthalic acid, isophthalic acid, etc. Also, the aromatic dicarboxylic acid component may be a dimer acid, etc.

[0058] Examples of the polyimide resin include aliphatic polyimide resins, aromatic polyimide resins, etc.

[0059] In addition, examples of the polyimide resin include imidized products of polyamic acids (precursors of polyimide resins), which are polymers of tetracarboxylic dianhydrides and diamine compounds.

[0060] Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3’,4,4’-benzophenone tetracarboxylic dianhydride, 3,3’,4,4’-biphenyl tetracarboxylic dianhydride, 2,3,3’,4-biphenyl tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,2’-bis(3,4-dicarboxyphenyl)sulfonic acid dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, ethylene tetracarboxylic dianhydride, and the like.

[0061] Specific examples of the diamine compound used as a raw material for the polyimide resin include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 3,3'-diaminodiphenyl methane, 3,3'-dichlorobenzidine, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 1,5-diaminonaphthalene, m-phenylenediamine, p-phenylenediamine, 3,3'-dimethyl-4,4'-biphenyldiamine, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl propane, 2,4-bis(β-aminotert-butyl)toluene, bis(p-β-amino-tert-butylphenyl)ether, bis(p-β-methyl-δ-aminophenyl)benzene, bis-p-(1,1-dimethyl-5-aminopentyl)benzene, 1-isopropyl-2,4-m-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 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, 2,17-diaminoeicosadecane, 1,4-diaminocyclohexane, 1,10-diamino-1,10-dimethyldecane, 1,2-diaminooctadecane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, piperazine, H 2 N(CH 2 ) 3 O(CH 2 ) 2 O(CH 2 )NH 2 、H 2 N(CH 2 ) 3 S(CH 2 ) 3 NH 2 、H2 N(CH 2 ) 3 N(CH 3 ) 2 (CH 2 ) 3 NH 2 etc. can be mentioned.

[0062] Examples of the polyamideimide resin include resins having imide bonds and amide bonds in the repeating units. More specifically, examples of the polyamideimide resin include polymers of a trivalent carboxylic acid compound having an acid anhydride group (also referred to as tricarboxylic acid) and a diisocyanate compound or a diamine compound.

[0063] Preferred examples of the tricarboxylic acid include trimellitic anhydride and its derivatives.

[0064] 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, naphthalene-2,6-diisocyanate, etc. Examples of the diamine compound that is a raw material of the polyamideimide resin include those listed as the diamine compound that is a raw material of the polyimide resin.

[0065] The second resin preferably contains a polyamide resin. The polyamide resin preferably contains an aliphatic polyamide resin and / or an alicyclic polyamide resin.

[0066] The second resin contains the second functional group in an amount of 25 to 190 mmol / kg, preferably 29 to 175 mmol / kg, more preferably 29 to 120 mmol / kg. The concentration of the second functional group in the second resin means the total concentration of amino groups, carboxy groups, isocyanate groups, and carboxylic anhydride groups in the second resin.

[0067] Note that the concentration of amino groups in a resin such as the second resin can be determined as follows. First, a phenol / ethanol solvent is prepared by mixing phenol and ethanol at a volume ratio of 10:1. Next, the weighed resin is dissolved in 40 mL of the phenol / ethanol solvent to obtain a first solution. Then, 10 mL of ethanol is added to the first solution to obtain a second solution. Next, the second solution is titrated with a N / 100 hydrochloric acid aqueous solution to determine the concentration of amino groups in the resin.

[0068] Also, the total concentration of carboxy groups and carboxylic anhydride groups in the resin can be determined as follows. First, the weighed resin is dissolved in 50 mL of benzyl alcohol in an oil bath at 180°C to obtain a solution. Next, using phenolphthalein as an indicator, the solution is titrated with a N / 100 potassium hydroxide-ethanol solution to determine the total concentration of carboxy groups and carboxylic anhydride groups in the resin. Note that when the resin does not contain carboxylic anhydride groups, the concentration determined by this titration means the concentration of carboxy groups in the resin.

[0069] Furthermore, the concentration of isocyanate groups in the resin can be determined based on JIS K1603-1:2007.

[0070] Note that the concentration of the second functional group contained in the resin having the second functional group can be decreased, for example, by a carbodiimide compound. Specifically, a resin having a second functional group and a carbodiimide compound are melt-kneaded using an extruder having a cylinder (the temperature of the cylinder: for example, 190 to 320°C, more specifically 210 to 290°C) to obtain 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, the rod-shaped melt-kneaded product is cut to obtain pellets. Next, the pellets are dried in a dehumidifying dryer (for example, 70 to 90°C) to obtain pellet-shaped resin with a reduced concentration of the second functional group.

[0071] 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-) per molecule and a polyfunctional carbodiimide compound having two or more carbodiimide groups (-N=C=N-) per molecule. Examples of the carbodiimide compound include an aliphatic carbodiimide compound having an aliphatic main chain, an alicyclic carbodiimide compound having an alicyclic main chain, and an aromatic carbodiimide compound having an aromatic main chain. 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, poly(diisopropylcarbodiimide), and the like. Examples of the alicyclic carbodiimide compound include dicyclohexylcarbodiimide, poly(diisopropylcarbodiimide), and the like. 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, di-o-chlorophenylcarbodiimide, di-2,4,6-trimethylphenylcarbodiimide, di-2,4,6-triisopropylphenylcarbodiimide, di-2,4,6-triisobutylphenylcarbodiimide, p-phenylene-bis-di-o-tolylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, p-phenylene-bis-di-p-chlorophenylcarbodiimide, ethylene-bis-diphenylcarbodiimide, poly(4,4'-diphenylmethanecarbodiimide), poly(p-phenylene carbodiimide), poly(m-phenylene carbodiimide), poly(3,3'-dimethyl-4,4'-diphenylmethanecarbodiimide), 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. The above carbodiimide compound may be used alone or in combination of two or more thereof.

[0072] The relative viscosity of the second resin is 1.50 to 2.50, preferably 1.58 to 2.16. The relative viscosity of the resin such as the second resin can be measured according to JIS K6933:2013. The measurement conditions of the relative viscosity can be as follows. Solvent: m-cresol Temperature: 25 °C Concentration of the second resin in the test solution: 0.005 g / mL

[0073] The glass transition temperature (Tg) of the second resin is preferably 30 °C to 160 °C.

[0074] In this embodiment, the glass transition temperature (Tg) means the midpoint glass transition temperature measured using a differential scanning calorimeter (DSC). The midpoint glass transition temperature can be determined based on the method described in JIS K7121-1987 "Method for Measuring the Transition Temperature of Plastics". That is, first, prepare about 5 mg of a sample for measuring the midpoint glass transition temperature, and prepare two containers made of the same metal (for example, aluminum) with the same shape and the same weight. Next, put the sample in one of the two containers and leave the other container empty. Then, set the container containing the sample and the empty container as a reference in the DSC, and the midpoint glass transition temperature can be determined from the DSC curve obtained when the sample is heated at a heating rate of 10 °C / min while flowing nitrogen gas.

[0075] The resin particles preferably contain 80 to 100% by weight, more preferably 90 to 100% by weight, and still more preferably 95 to 100% by weight of the second resin.

[0076] In addition, the resin particles may further contain an additive. In other words, the resin composition for resin particles may further contain an additive. Examples of the additive include a stabilizer, a colorant, a dispersant, a preservative, an antioxidant, and an antifoaming agent. The additive may be used alone or in combination of two or more. The total content ratio of the additive is, for example, 10 parts by weight or less (for example, 0.01 to 10 parts by weight) with respect to a total of 100 parts by weight of the second resin.

[0077] The median diameter (D50) of the resin particles is preferably 50 μm or less, more preferably 4 to 40 μm, still more preferably 8 to 32 μm. The median diameter of the resin particles means a value measured by dispersing the resin particles in water and using a laser diffraction / scattering particle size distribution measuring device. Further, the median diameter of the resin particles means the volume-based median diameter of the resin particles. Furthermore, the median diameter of the resin particles means the median diameter of the primary particle resin particles.

[0078] The sphericity of the resin particles is preferably 75% or more and 100% or less, more preferably 85% or more and 100% or less, still more preferably 95% or more and 100% or less, particularly preferably 97% or more and 100% or less, and most preferably 99% or more and 100% or less. When the sphericity of the resin particles is 75% or more, the toughness of the cured product becomes even higher. In this embodiment, the sphericity of the particles can be measured by the following method. That is, the particles are observed with a scanning electron microscope (SEM), the major axis and minor axis of 30 randomly selected particles are measured, and the minor axis / major axis ratio of each particle is determined. Then, the arithmetic mean value of the minor axis / major axis ratio is determined, and this arithmetic mean value is defined as the sphericity of the particles. Note that the closer the sphericity of the particles is to 100%, the more spherical the particles can be judged to be.

[0079] The thermosetting resin composition according to this embodiment preferably contains 50 to 99% by weight, more preferably 80 to 97% by weight, in total of the thermosetting resin and the resin particles.

[0080] The thermosetting resin composition according to this embodiment contains the resin particles in an amount of preferably 1 to 20 parts by weight, more preferably 3 to 18 parts by weight, and still more preferably 5 to 15 parts by weight, based on 100 parts by weight of the thermosetting resin.

[0081] (Method for producing resin particles) Examples of the method for producing resin particles include the forced emulsification method, the freeze pulverization method, the chemical pulverization method, the polymerization method, the laser method, and the like. As the method for producing resin particles, the forced emulsification method is preferable.

[0082] In the forced emulsification method, a step (A) of obtaining a melt-kneaded product by heating and melt-kneading a second resin having an amide bond and an aqueous medium (hereinafter also referred to as "water-soluble matrix") incompatible with the second resin having an amide bond in an extruder; a step (B) of obtaining a rod-shaped melt-kneaded product by discharging the melt-kneaded product from the extruder, cooling the rod-shaped melt-kneaded product, and cutting the cooled rod-shaped melt-kneaded product to obtain a pellet-shaped preform; and a step (C) of removing the aqueous medium from the pellet-shaped preform with a hydrophilic solvent or water are carried out to obtain the resin particles. In the forced emulsification method, if necessary, the resin particles may be obtained by carrying out a step (D) of drying the preform with a dehumidifying dryer or the like after the step (C). In addition, in order to obtain resin particles having a desired particle size, in the forced emulsification method, after the step (C) (when the step (D) is carried out, after or before the step (D)), a step (E) of classifying the preform is carried out to obtain the resin particles.

[0083] The aqueous medium used in the step (A) is selected according to the type of the second resin having an amide bond. Examples of the aqueous medium include heat-melting saccharides, water-soluble polymers, and the like. Examples of the heat-meltable saccharides include oligosaccharides (e.g., sucrose, maltotriose, etc.), sugar alcohols (e.g., xylitol, erythritol, sorbitol, mannitol, etc.). Examples of the water-soluble polymers 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.). Examples of the modified polyvinyl alcohol-based resins include modified polyvinyl alcohol having an alkyl group having at least one hydroxyl group in the side chain, modified polyvinyl alcohol having an alkyl chain having at least one hydroxyl group in the side chain, and the like. These aqueous media can be used alone or in combination of two or more.

[0084] Regarding the mixing ratio of the second resin and the aqueous medium, for 100 parts by weight of the aqueous medium, the second resin is, for example, 10 to 200 parts by weight, preferably 30 to 150 parts by weight, more preferably 50 to 100 parts by weight.

[0085] The temperature at the time of melt-kneading in the step (A) may be a temperature equal to or higher than the melting point or softening point of the second resin, for example, 190°C or higher (e.g., 190 to 350°C), preferably 200 to 320°C, more preferably 210 to 300°C.

[0086] In the step (B), the melt-kneaded product may be naturally cooled or may be forcibly cooled. From the viewpoint of productivity, it is preferable to forcibly cool the melt-kneaded product. The cooling rate of the melt-kneaded product is preferably, for example, 1°C / min or higher (e.g., 1 to 30°C / min).

[0087] Examples of the hydrophilic solvent used in the step (C) include alcohols (such as ethanol), water-soluble ketones (such as acetone), and the like.

[0088] (monofunctional epoxy compound) When the thermosetting resin contains an epoxy resin, the thermosetting resin composition according to this embodiment may contain a monofunctional epoxy compound. Examples of the monofunctional epoxy compound include monoglycidyl ether, alkene oxide (e.g., octylene oxide, styrene oxide, etc.). Examples of the monoglycidyl ether include alkyl glycidyl ether (e.g., 2-ethylhexyl glycidyl ether, etc.), alkenyl glycidyl ether (e.g., allyl glycidyl ether, etc.), aryl glycidyl ether (e.g., phenyl glycidyl ether, etc.). In the thermosetting resin composition according to this embodiment, the ratio of the weight 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, more preferably 95 / 5 to 70 / 30.

[0089] (Curing agent) The thermosetting resin composition according to this embodiment may contain a curing agent. The curing agent can be appropriately selected according to the type of the thermosetting resin. Examples of the curing agent when the thermosetting resin is an epoxy resin include amine-based curing agents, phenolic resin-based curing agents, acid anhydride-based curing agents, polymercaptan-based curing agents, latent curing agents, etc.

[0090] Examples of the amine-based curing agent include aromatic amine-based curing agents, aliphatic amine-based curing agents, imidazoles, salts of imidazoles, alicyclic amine-based curing agents, etc.

[0091] Examples of the aromatic amine curing agent include polyaminoarene, polyamino-alkylarene, poly(aminoalkyl)arene, poly(aminoaryl)alkane, poly(amino-alkylaryl)alkane, bis(aminoarylalkyl)arene, di(aminoaryl)ether (e.g., diaminodiphenyl ether, etc.), di(aminoaryloxy)arene (e.g., 1,3-bis(3-aminophenoxy)benzene, etc.), di(aminoaryl)sulfone (e.g., diaminodiphenyl sulfone, etc.). Examples of the polyaminoarene include diaminoarene (e.g., paraphenylenediamine, metaphenylenediamine, etc.). Examples of the polyamino-alkylarene include diamino-alkylarene (e.g., diethyltoluenediamine, etc.). Examples of the poly(aminoalkyl)arene include di(aminoalkyl)arene (e.g., xylylenediamine, etc.). Examples of the poly(aminoaryl)alkane include di(aminoaryl)alkane (e.g., diaminodiphenylmethane, etc.). Examples of the poly(amino-alkylaryl)alkane include di(amino-alkylaryl)alkane (e.g., 4,4'-methylenebis(2-ethyl-6-methylaniline), etc.). Examples of the bis(aminoarylalkyl)arene include 1,3-bis[2-(4-aminophenyl)-2-propyl)]benzene, 1,4-bis[2-(4-aminophenyl)-2-propyl)]benzene, etc.

[0092] Examples of the aliphatic amine curing agent include ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, etc.

[0093] Examples of the alicyclic amine curing agent include menthylenediamine, isophoronediamine, bis(4-amino-3-methylcyclohexyl)methane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, norbornanediamine, and the like.

[0094] Examples of the imidazoles include alkylimidazoles, arylimidazoles, and the like. Examples of the alkylimidazoles include 2-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, and the like. Examples of the arylimidazoles include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-benzyl-2-phenylimidazole, and the like.

[0095] Examples of the salts of the imidazoles include salts of imidazoles and formic acid, salts of imidazoles and phenol, salts of imidazoles and phenol novolak, salts of imidazoles and carbonic acid, and the like.

[0096] Examples of the phenolic resin curing agent include novolak resin, cresol novolak resin, and the like.

[0097] Examples of the acid anhydride curing agent include aliphatic dicarboxylic acid anhydrides, alicyclic dicarboxylic acid anhydrides, aromatic dicarboxylic acid anhydrides, and the like. Examples of the aliphatic dicarboxylic acid anhydrides include dodecenyl succinic anhydride, and the like. Examples of the alicyclic dicarboxylic acid anhydrides include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and the like. Examples of the aromatic dicarboxylic acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, and the like.

[0098] Examples of the latent curing agent include boron trifluoride - amine complex, dicyandiamide, carboxylic acid hydrazide, etc.

[0099] The curing agent may be used alone or in combination of two or more. Note that the curing agent may also act as a curing accelerator. As the curing agent, an amine - based curing agent (for example, an aromatic amine - based curing agent) is preferable.

[0100] The content ratio of the curing agent can be appropriately selected according to the type of the thermosetting resin (such as epoxy equivalent) and the type of the curing agent. For example, 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 with respect to 100 parts by weight of the thermosetting resin.

[0101] (Curing accelerator) The thermosetting resin composition according to this embodiment may contain a curing accelerator. As the curing accelerator, it can be appropriately selected according to the type of the thermosetting resin. Examples of the curing accelerator when the thermosetting resin is an epoxy resin include phosphines, amines, salts of amines, etc. Examples of the phosphines include ethylphosphine, propylphosphine, trialkylphosphine, phenylphosphine, triphenylphosphine, etc. Examples of the amines include secondary to tertiary amines, etc. Examples of the secondary to tertiary amines include triethylamine, piperidine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, triethylenediamine, tris(dimethylaminomethyl)phenol, N,N - dimethylpiperazine, etc. The curing accelerator may be used alone or in combination of two or more.

[0102] The content ratio of the hardening 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 with respect to 100 parts by weight of the thermosetting resin.

[0103] (Other components) The thermosetting resin composition according to this embodiment may further contain at least one of a thermoplastic resin and an additive as other components, if necessary.

[0104] Examples of the thermoplastic resin include acrylic resin, polyolefin resin (such as polypropylene), polyamide resin, polyester resin, polycarbonate resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyether ketone resin, polyether ether ketone resin, polyimide resin, polyetherimide resin, and the like. Examples of the polyester resin include aromatic polyester resin (such as polyethylene terephthalate).

[0105] Examples of the additive include non-fibrous filler, stabilizer, colorant, dispersant, preservative, antioxidant, defoaming agent, and the like.

[0106] The content ratio of other components is, for example, 10 parts by weight or less (such as 0.01 to 10 parts by weight) with respect to 100 parts by weight of the thermosetting resin.

[0107] <Hardened product> The hardened product according to this embodiment is a hardened product obtained by thermally hardening the thermosetting resin composition according to this embodiment. The shape of the hardened product according to this embodiment may be a one-dimensional shape (such as rod shape), a two-dimensional shape (such as sheet shape), or a three-dimensional shape.

[0108] <Prepreg> The prepreg according to this embodiment is a prepreg in which the thermosetting resin composition according to this embodiment is impregnated or injected into an aggregate of reinforcing fibers. That is, the prepreg according to the present embodiment is composed of a thermosetting resin composition and reinforcing fibers. By thermosetting the prepreg according to the present embodiment (specifically, by thermosetting the thermosetting resin composition contained in the prepreg), a fiber-reinforced plastic can be obtained.

[0109] Examples of the reinforcing fibers include carbon fibers, glass fibers, aramid fibers, boron fibers, polyparaphenylene benzobisoxazole (PBO) fibers, polyethylene fibers, alumina fibers, silicon carbide fibers, and the like. As the reinforcing fibers, carbon fibers are preferable.

[0110] The reinforcing fibers may be monofilaments or multifilaments. The fineness of the single fiber of the reinforcing fibers is preferably 0.2 to 2.0 dtex, more preferably 0.4 to 1.8 dtex.

[0111] When the reinforcing fibers are multifilaments, the number of filaments in the fibers is preferably 2500 to 50000.

[0112] The reinforcing fibers may be continuous fibers or discontinuous fibers. When higher mechanical properties are required for the cured product, continuous fibers are preferable as the reinforcing fibers. The continuous fibers may be, for example, unidirectional substrates, knitted fabrics, woven fabrics, tows, or rovings, and may be contained in the prepreg according to the present embodiment. The reinforcing fibers in discontinuous form may be, for example, non-woven fabrics or chopped yarns, and may be contained in the prepreg according to the present embodiment.

[0113] The thermosetting resin composition may be contained in the prepreg in a liquid state or in a solid state. The prepreg according to this embodiment is a concept that also includes a tow prepreg. The tow prepreg is a prepreg composed of tows (bundles of reinforcing fibers) and a solid thermosetting resin composition.

[0114] The prepreg according to this embodiment contains the reinforcing fibers, preferably in an amount of 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the thermosetting resin.

[0115] (Fiber Reinforced Plastic) The fiber reinforced plastic according to this embodiment is composed of the cured product according to this embodiment and the reinforcing fibers. The fiber reinforced plastic according to this embodiment is also called a "fiber reinforced polymer composite material" or "FRP". In the fiber reinforced plastic according to this embodiment, it is preferable that the reinforcing fibers are carbon fibers. In other words, the fiber reinforced plastic according to this embodiment is preferably a carbon fiber reinforced plastic (CFRP).

[0116] The fiber reinforced plastic according to this embodiment is obtained by thermosetting the prepreg according to this embodiment. That is, the fiber reinforced plastic according to this embodiment can be produced by thermosetting the prepreg according to this embodiment. For example, the fiber reinforced plastic according to this embodiment may be obtained by a filament winding method. In the filament winding method, a filamentous prepreg composed of tows (bundles of reinforcing fibers) and a thermosetting resin composition is wound around a mandrel to obtain a prepreg of a desired shape (for example, a cylindrical shape, a tank shape), and by thermosetting the prepreg (thermosetting the thermosetting resin composition contained in the prepreg), a fiber reinforced plastic of a desired shape can be obtained. Examples of the filament winding method include the Wet method and the Dry method. In the wet method, tows (bundles of reinforcing fibers) are placed in a liquid thermosetting resin composition to obtain a prepreg, and the prepreg containing the liquid thermosetting resin composition is wound around a mandrel. In the dry method, a tow prepreg is wound around a mandrel. By using a previously prepared tow prepreg in the dry method, a fiber-reinforced plastic having a desired shape can be easily produced.

[0117] From the viewpoint of enhancing mechanical efficiency, the fiber-reinforced plastic according to this embodiment preferably has two or more layers of the layer containing the reinforcing fibers. Examples of the fiber-reinforced plastic having two or more layers of the layer containing the reinforcing fibers include a fiber-reinforced plastic having two or more layers of an aggregate of reinforcing fibers.

[0118] The fiber-reinforced plastic having two or more layers of the layer containing the reinforcing fibers can be produced, for example, as follows. By stacking a plurality of prepreg layers and thermosetting the stacked plurality of prepreg layers, a fiber-reinforced plastic having two or more layers of the layer containing the reinforcing fibers can be obtained. Also, by stacking two or more aggregates of reinforcing fibers to obtain a laminate and impregnating or injecting the laminate with the thermosetting resin composition, a fiber-reinforced plastic having two or more layers of the layer containing the reinforcing fibers can be obtained.

[0119] (Molded article) The molded article according to this embodiment is a molded article formed from the cured product according to this embodiment. The molded article according to this embodiment is a concept including molded articles formed from the fiber-reinforced plastic according to this embodiment. Examples of the molded article according to this embodiment include an aircraft body, a golf club shaft, a fishing rod, a tank (specifically, a high-pressure tank), and the like.

[0120] [Disclosed items] Each of the following items is a disclosure of a preferred embodiment.

[0121] [Item 1] A thermosetting resin composition comprising a first resin that is a thermosetting resin and resin particles containing a second resin having an amide bond, wherein the second resin contains one or more second functional groups selected from the group consisting of an amino group, a carboxy group, an isocyanate group, and a carboxylic anhydride group, the first resin contains 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, and the relative viscosity of the second resin is 1.50 to 2.50. A thermosetting resin composition.

[0122] [Item 2] The thermosetting resin composition according to Item 1, wherein the second resin contains a polyamide resin.

[0123] [Item 3] The thermosetting resin composition according to Item 2, wherein the polyamide resin contains an aliphatic polyamide resin and / or an alicyclic polyamide resin.

[0124] [Item 4] The thermosetting resin composition according to any one of Items 1 to 3, wherein the median diameter of the resin particles is 50 μm or less.

[0125] [Item 5] The thermosetting resin composition according to any one of Items 1 to 4, wherein the sphericity of the resin particles is 75% or more.

[0126] [Item 6] The thermosetting resin composition according to any one of Items 1 to 5, wherein the glass transition point of the second resin is 30 to 160 °C.

[0127] [Item 7] The thermosetting resin composition according to any one of Items 1 to 6, wherein the second resin contains 29 to 120 mmol / kg of the second functional group.

[0128] [Item 8] The thermosetting resin composition according to any one of Items 1 to 7, wherein the first resin contains an epoxy resin.

[0129] [Item 9] The thermosetting resin composition according to any one of Items 1 to 8, which has 1 to 20 parts by weight of the resin particles with respect to 100 parts by weight of the first resin.

[0130] [Item 10] A cured product obtained by thermosetting the thermosetting resin composition according to any one of Items 1 to 9.

[0131] [Item 11] A prepreg in which the thermosetting resin composition according to any one of Items 1 to 9 is impregnated or injected into an aggregate of reinforcing fibers.

[0132] [Item 12] A molded product formed from the cured product according to Item 10.

[0133] [Item 13] A fiber-reinforced plastic comprising the cured product according to Item 10 and reinforcing fibers.

[0134] [Item 14] The fiber-reinforced plastic according to Item 13, which has two or more layers containing the reinforcing fibers. [Examples]

[0135] Next, examples , reference example and comparative examples will be given to explain the present disclosure more specifically. Note that the present disclosure is not limited to these examples at all.

[0136] (Water-soluble matrix) The following water-soluble matrix was prepared. Modified PVA-based resin 1 (hereinafter also referred to as "modified PVA1"): A modified PVA-based resin prepared by the method described in paragraphs 0119 to 0121 of JP-A-2019-1942 (the "modified PVA-based resin 2" described in JP-A-2019-1942) Modified PVA-based resin 2 (hereinafter also referred to as "modified PVA2"): A modified PVA-based resin prepared by the method described in paragraphs 0112 to 0115 of JP-A-2019-1942 (the "modified PVA-based resin 1" described in JP-A-2019-1942) Sugar alcohol: D-Sorbitol LTS Powder 20M manufactured by Mitsubishi Corporation Foodtech Co., Ltd.

[0137] (Extruder) The following extruder (an extruder having a cylinder) was prepared. "TEX30XSST" manufactured by Nippon Steel Corporation (hereinafter also simply referred to as "TEX30"). "Laboplast Mill" manufactured by Toyo Seiki Seisakusho, Ltd. (hereinafter also simply referred to as "Plast Mill").

[0138] (Examples 13, 14, reference example 1 to 3, 5 to 8, 11 、12、15、 16, Comparative Example 12) Under the conditions shown in Table 1 below, using an extruder, the water-soluble matrix and the raw material resin were melt-kneaded, and the melt-kneaded product was discharged. The raw material resin is a polyamide resin manufactured by Polyplastics Co., Ltd. The discharged melt-kneaded product was cooled and cut to obtain a pellet-shaped preform. This preform was put into water and stirred to elute the water-soluble matrix to obtain a slurry. This slurry was passed through a mesh (mesh opening: 250 μm), and the slurry that passed through the mesh was filtered with filter paper to recover the precursor particles that passed through the mesh and remained on the filter paper. The precursor particles were naturally dried at a temperature of 23°C and a humidity of 50% RH to obtain resin particles (powder).

[0139] Next, using a hot stirrer, the resin particles and an epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation), which is a thermosetting resin, were stirred at 80°C and 300 rpm for 6 hours to obtain a mixture. Then, the mixture was left in a vacuum container for 1 hour to defoam the mixture. Next, an amine-based curing agent (jER Cure W manufactured by Mitsubishi Chemical Corporation) was added to the defoamed mixture, followed by stirring and defoaming to obtain a thermosetting resin composition (resin particles: 14.4% by weight).

[0140] ( reference Example 4) Using an extruder (TEX30 manufactured by Nippon Steel Corporation), reference 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 (cylinder 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, the rod-shaped melt-kneaded product was cut to obtain pellets. Next, the pellets were dried at 80°C for 4 hours using a dehumidifying dryer to obtain dried pellets (raw material resin). Using the raw material resin and except for setting the conditions shown in Table 1 below, reference Resin particles were obtained in the same manner as in Example 1, and a thermosetting resin composition was obtained.

[0141] ( reference Example 9) Using an extruder (TEX30 manufactured by Nippon Steel Corporation), reference90 parts by weight of the raw material resin of Example 5 and 10 parts by weight of PA12 (concentration of carboxyl group: 5 mmol / kg, concentration of amino group: 400 mmol / kg, relative viscosity: 1.33) manufactured by Polyplastics - Evonik were melt - kneaded (cylinder temperature: 220 °C) to obtain a melt - kneaded product. Next, the melt - kneaded product was discharged from an extruder, and the discharged rod - shaped melt - kneaded product was cooled. Then, the rod - shaped melt - kneaded product was cut to obtain pellets. Next, the pellets were dried at 80 °C for 4 hours using a dehumidifying dryer to obtain dried pellets (raw material resin). Except for using the raw material resin and setting the conditions shown in Table 1 below, reference resin particles were obtained in the same manner as in Example 1, and a thermosetting resin composition was obtained.

[0142] ( reference Example 10) Using an extruder ("TEX30" manufactured by Japan Steel Works, Ltd.), reference 85 parts by weight of the raw material resin of Example 5 and 15 parts by weight of PA12 (concentration of carboxyl group: 5 mmol / kg, concentration of amino group: 400 mmol / kg, relative viscosity: 1.33) manufactured by Polyplastics - Evonik were melt - kneaded (cylinder temperature: 220 °C) to obtain a melt - kneaded product. Next, the melt - kneaded product was discharged from an extruder, and the discharged rod - shaped melt - kneaded product was cooled. Then, the rod - shaped melt - kneaded product was cut to obtain pellets. Next, the pellets were dried at 80 °C for 4 hours using a dehumidifying dryer to obtain dried pellets (raw material resin). Except for using the raw material resin and setting the conditions shown in Table 1 below, reference resin particles were obtained in the same manner as in Example 1, and a thermosetting resin composition was obtained.

[0143] (Comparative Example 1) Except for not using resin particles, reference a thermosetting resin composition was obtained in the same manner as in Example 1.

[0144] (Comparative Example 2) Using an extruder ("TEX30" manufactured by Japan Steel Works, Ltd.), reference100 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 (cylinder temperature: 220 °C) to obtain a melt-kneaded product. Next, the melt-kneaded product was discharged from an extruder, and the discharged rod-shaped melt-kneaded product was cooled. Then, the rod-shaped melt-kneaded product was cut to obtain pellets. Next, the pellets were dried at 80 °C for 4 hours using a dehumidifying dryer to obtain dried pellets (raw material resin). Except for using the raw material resin and setting the conditions shown in Table 1 below, reference resin particles were obtained in the same manner as in Example 1, and a thermosetting resin composition was obtained.

[0145] (Comparative Example 3) Using an extruder ("TEX30" manufactured by Nippon Steel Corporation), 100 parts by weight of an amorphous alicyclic polyamide manufactured by Polyplastics Co., Ltd. and 4 parts by weight of a carbodiimide compound (Stabaxol I Powder, manufactured by LANXESS) were melt-kneaded (cylinder 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, the rod-shaped melt-kneaded product was cut to obtain pellets. Next, the pellets were dried at 80 °C for 4 hours using a dehumidifying dryer to obtain dried pellets (raw material resin). Except for using the raw material resin and setting the conditions shown in Table 1 below, reference resin particles were obtained in the same manner as in Example 1, and a thermosetting resin composition was obtained.

[0146] (Comparative Example 4) Using an extruder ("TEX30" manufactured by Nippon Steel Corporation), 100 parts by weight of an amorphous alicyclic polyamide manufactured by Polyplastics Co., Ltd. and 4 parts by weight of a carbodiimide compound (Stabaxol I Powder, manufactured by LANXESS) were melt-kneaded (cylinder 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). Using the raw material resin, except that the conditions shown in Table 1 below were used, reference Resin particles were obtained in the same manner as in Example 1, and a thermosetting resin composition was obtained.

[0147] (Comparative Example 5) Using an extruder ("TEX30" manufactured by Nippon Steel Corporation), 100 parts by weight of PA12 (manufactured by Polyplastics Co., Ltd.) and 4 parts by weight of a carbodiimide compound (Stabaxol I Powder, manufactured by LANXESS) were melt-kneaded (cylinder 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). Using the raw material resin, except that the conditions shown in Table 1 below were used, reference Resin particles were obtained in the same manner as in Example 1, and a thermosetting resin composition was obtained.

[0148] (Comparative Example 6) Using an extruder ("TEX30" manufactured by Nippon Steel Corporation), 100 parts by weight of microcrystalline alicyclic polyamide manufactured by Polyplastics Co., Ltd. and 4 parts by weight of a carbodiimide compound (Stabaxol I Powder, manufactured by LANXESS) were melt-kneaded (cylinder 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, the rod-shaped melt-kneaded product was cut to obtain pellets. Next, the pellets were dried at 80°C for 4 hours using a dehumidifying dryer to obtain dried pellets (raw material resin). Using the raw material resin and except for setting the conditions shown in Table 1 below, reference Resin particles were obtained in the same manner as in Example 1, and a thermosetting resin composition was obtained.

[0149] (Comparative Example 7) Using an extruder ("TEX30" manufactured by Nippon Steel Corporation), 100 parts by weight of amorphous alicyclic polyamide manufactured by Polyplastics Co., Ltd. and 4 parts by weight of a carbodiimide compound (Stabaxol I Powder, manufactured by LANXESS) were melt-kneaded (cylinder 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, the rod-shaped melt-kneaded product was cut to obtain pellets. Next, the pellets were dried at 80°C for 4 hours using a dehumidifying dryer to obtain dried pellets (raw material resin). Using the raw material resin and except for setting the conditions shown in Table 1 below, reference Resin particles were obtained in the same manner as in Example 1, and a thermosetting resin composition was obtained.

[0150] (Comparative Example 8) Using an extruder ("TEX30" manufactured by Nippon Steel Corporation), 100 parts by weight of PA1010 (manufactured by Polyplastics Co., Ltd.) and 3 parts by weight of a carbodiimide compound (Stabaxol I Powder, manufactured by LANXESS) were melt-kneaded (cylinder 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). Using the raw material resin and except for setting the conditions shown in Table 1 below, reference Resin particles were obtained in the same manner as in Example 1, and a thermosetting resin composition was obtained.

[0151] (Comparative Example 9) Using an extruder ("TEX30" manufactured by Nippon Steel Corporation), reference 65 parts by weight of the raw material resin of Example 5 and 35 parts by weight of PA12 manufactured by Polyplastics (concentration of carboxyl group: 5 mmol / kg, concentration of amino group: 400 mmol / kg, relative viscosity: 1.33) were melt-kneaded (cylinder 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). Using the raw material resin and except for setting the conditions shown in Table 1 below, reference Resin particles were obtained in the same manner as in Example 1, and a thermosetting resin composition was obtained.

[0152] (Comparative Example 10) Using an extruder ("TEX30" manufactured by Nippon Steel Corporation), 55 parts by weight of an amorphous alicyclic polyamide resin manufactured by Polyplastics Co., Ltd. and 45 parts by weight of PA12 manufactured by Polyplastics Co., Ltd. (concentration of carboxyl groups: 5 mmol / kg, concentration of amino groups: 400 mmol / kg, relative viscosity: 1.33) were melt-kneaded (cylinder 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, the rod-shaped melt-kneaded product was cut to obtain pellets. Next, the pellets were dried at 80°C for 4 hours using a dehumidifying dryer to obtain dried pellets (raw material resin). Using the raw material resin and except for setting the conditions shown in Table 1 below, reference Resin particles were obtained in the same manner as in Example 1, and a thermosetting resin composition was obtained.

[0153] (Comparative Example 11) Using an extruder ("TEX30" manufactured by Nippon Steel Corporation), 55 parts by weight of a microcrystalline alicyclic polyamide resin manufactured by Polyplastics Co., Ltd. and 45 parts by weight of PA12 manufactured by Polyplastics Co., Ltd. (concentration of carboxyl groups: 5 mmol / kg, concentration of amino end groups: 400 mmol / kg, relative viscosity: 1.33) were melt-kneaded (cylinder 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, the rod-shaped melt-kneaded product was cut to obtain pellets. Next, the pellets were dried at 80°C for 4 hours using a dehumidifying dryer to obtain dried pellets (raw material resin). Using the raw material resin and except for setting the conditions shown in Table 1 below, reference Resin particles were obtained in the same manner as in Example 1, and a thermosetting resin composition was obtained.

[0154] The relative viscosity, concentration of carboxyl groups, and concentration of amino groups in the raw material resins shown in Table 1 below were measured by the methods described above. Also, the relative viscosity, concentration of carboxyl groups, and concentration of amino groups in the polyamide resins used in the production of the raw material resins were measured by the methods described above.

[0155]

Table 1

[0156] (Relative viscosity, concentration of carboxy group, concentration of amino group, and concentration of the second functional group in the second resin) The relative viscosity, concentration of carboxy group, concentration of amino group, and concentration of the second functional group in the second resin contained in the resin particles were measured by the method described above. The measured values are shown in Table 2 below. In addition, in the examples , reference example and comparative examples, the concentration of the second functional group means the total of the concentrations of the amino group and the carboxy group.

[0157] (Median diameter and sphericity of resin particles, and glass transition temperature (Tg) of the second resin) The median diameter (D50) and sphericity of the resin particles, and the glass transition temperature (Tg) of the second resin were measured by the method described above. The measured values are shown in Table 2 below.

[0158] (Plane strain fracture toughness (K IC )) First, the thermosetting resin composition was poured into a mold (47 mm (length) × 12 mm (width) × 4 mm (thickness)). Next, the thermosetting resin composition was heated at 175 °C until the thermosetting resin composition was sufficiently thermoset to obtain a cured product having pre-cracks. In addition, in order to provide pre-cracks in the cured product, convex portions corresponding to the pre-cracks were formed on the inner surface of the mold. Then, using the cured product having pre-cracks, the plane strain fracture toughness (K IC ) was determined in accordance with ASTM D5045. The results are shown in Table 2 below.

[0159]

Table 2

[0160] In FIG. 1,reference Shows the SEM image of the resin particles used in Example 3.

[0161] In FIG. 2, reference Shows the SEM image of the cross-section of the cured product obtained by thermosetting the thermosetting resin composition of Example 3. The cured product was produced from the thermosetting resin composition in the same manner as the test method for the plane strain fracture toughness (K IC ). Next, the cured product was broken by an IZOD impact tester to obtain a fracture surface. Then, the fracture surface was photographed with SEM. The circular ones in FIG. 2 are resin particles. It can be seen that the resin particles remain in a particulate state even after curing.

[0162] As shown in Table 2, in Examples 13, 14, reference example 1 to 12、15、 16, compared with Comparative Example 1 in which the thermosetting resin composition does not contain resin particles, Comparative Examples 2 to 8 in which the concentration of the second functional group in the second resin is small, Comparative Examples 9 and 10 in which the relative viscosity of the second resin is small and the concentration of the second functional group in the second resin is large, Comparative Example 11 in which the concentration of the second functional group in the second resin is large, and Comparative Example 12 in which the relative viscosity of the second resin is small, the plane strain fracture toughness (K IC ) of the cured product was high. Therefore, according to the present disclosure, it is possible to provide a thermosetting resin composition having even higher toughness of the cured product.

[0163] In addition, in the comparison between Examples and reference example there was the following tendency. That is, the higher the relative viscosity, the higher the tendency of the plane strain fracture toughness (K IC ) of the cured product. Also, the higher the median diameter, the higher the tendency of the plane strain fracture toughness (K IC ) of the cured product. Furthermore, if the concentration of the second functional group in the second resin is above a predetermined level, the plane strain fracture toughness (K IC ) of the cured product did not change significantly.

Claims

1. A thermosetting resin composition comprising a first resin that is a thermosetting resin and resin particles that contain a second resin having an amide bond, the second resin contains one or more second functional groups selected from the group consisting of an amino group, a carboxy group, an isocyanate group, and a carboxylic anhydride group; the first resin comprises a first functional group capable of reacting with the second functional group; the second resin contains the second functional group in an amount of 25 to 190 mmol / kg; The second resin has a relative viscosity of 1.50 to 2.50; The thermosetting resin composition, wherein the second resin comprises a polyamide resin having at least one component selected from the group consisting of an alicyclic diamine component and an alicyclic dicarboxylic acid component.

2. The thermosetting resin composition according to claim 1 , wherein the resin particles have a median diameter of 50 μm or less.

3. The thermosetting resin composition according to claim 1 or 2, wherein the resin particles have a sphericity of 75% or more.

4. The thermosetting resin composition according to claim 1 or 2, wherein the second resin has a glass transition temperature of 30 to 160°C.

5. The thermosetting resin composition according to claim 1 or 2, wherein the second resin contains the second functional group in an amount of 29 to 120 mmol / kg.

6. The thermosetting resin composition according to claim 1 or 2, wherein the first resin comprises an epoxy resin.

7. 3. The thermosetting resin composition according to claim 1, comprising 1 to 20 parts by weight of the resin particles relative to 100 parts by weight of the first resin.

8. A cured product obtained by thermally curing the thermosetting resin composition according to claim 1 or 2.

9. A prepreg, comprising an assembly of reinforcing fibers impregnated or injected with the thermosetting resin composition according to claim 1 or 2.

10. A molded article formed from the cured product according to claim 8.

11. A fiber-reinforced plastic comprising the cured product according to claim 8 and reinforcing fibers.

12. The fiber-reinforced plastic according to claim 11, having two or more layers containing the reinforcing fibers.

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