JP2021147448A - Thermosetting resin composition - Google Patents

Abstract

To provide a thermosetting resin composition that provides a cured product having excellent mechanical strength and capable of following displacement to external pressure.SOLUTION: A thermosetting resin composition contains a thermosetting resin (A), an ethylenically unsaturated compound (B), and a polyhydric alcohol (C), the polyhydric alcohol (C) having a molecular weight or a number average molecular weight of 62 or more and 950 or less.SELECTED DRAWING: None

Description

The present invention relates to a thermosetting resin composition and a cured product thereof.

Thermosetting resin compositions include molding materials, adhesives, primers, paints, inorganic structure repair materials for cross-sectional repair of concrete, crack injection, water stoppage, etc., fillers, padding materials, and fiber-reinforced composites. It is used in a wide range of applications such as materials. Among them, a thermosetting resin composition containing a radically polymerizable resin such as unsaturated polyester, vinyl ester, or urethane (meth) acrylate has advantages such as moldability, curability, and adhesion to a base material. Widely used in the above fields.

A thermosetting resin may be mixed with an inorganic aggregate and used in order to improve the mechanical strength of the cured product. Such a material is called resin concrete or resin mortar, and has advantages such as excellent specific strength and chemical resistance as compared with cement mortar.

Resin concrete and resin mortar are required to have strength to withstand external pressure together with an inorganic structure base material and the like. However, if the mechanical strength of the resin concrete and the resin mortar, particularly the elastic modulus, is too high, the displacement with respect to the external pressure cannot be followed, and cracks and fractures occur at an early stage, that is, the allowable deflection rate is poor.

Therefore, conventionally, resin compositions for resin concrete (Patent Document 1), butadiene rubber, butadiene-styrene rubber, etc., whose crack resistance has been improved by adjusting the content of non-aromatic hydrocarbon groups in unsaturated esters, etc. An unsaturated ester-based resin composition containing a rubber polymer and having excellent toughness (Patent Document 2) has been proposed.

Japanese Unexamined Patent Publication No. 9-296033 Japanese Patent No. 5605827

However, the resin composition for resin concrete of Patent Document 1 has a problem that the chemical resistance is low because the content of aromatic hydrocarbon groups is low. The unsaturated ester-based resin composition of Patent Document 2 has a problem of low heat resistance.

Therefore, it is an object of the present invention to provide a thermosetting resin composition which has good mechanical strength and gives a cured product capable of following a displacement with respect to an external pressure.

The present invention is based on the finding that a cured product of a thermosetting resin composition to which a polyhydric alcohol is added so as to be able to follow a displacement with respect to an external pressure is excellent in flexibility.

That is, the present invention includes the following [1] to [12].
[1]
It contains a thermosetting resin (A), an ethylenically unsaturated compound (B), and a polyvalent alcohol (C), and the molecular weight or number average molecular weight of the polyvalent alcohol (C) is 62 or more and 950 or less. Resin composition.
[2]
The thermosetting resin composition according to [1], wherein the polyhydric alcohol (C) has a molecular weight or a number average molecular weight of 100 or more and 900 or less.
[3]
The thermosetting resin composition according to [1] or [2], wherein the polyhydric alcohol (C) contains at least one selected from the group consisting of a polyalkylene diol and a bisphenol alkylene oxide adduct.
[4]
The thermosetting resin composition according to any one of [1] to [3], which further comprises an inorganic aggregate (D).
[5]
The thermosetting according to [4], wherein the inorganic aggregate (D) contains at least one selected from the group consisting of aluminum oxide, aluminum hydroxide, silica sand, calcium carbonate, glass powder, talc, and molten silica. Resin composition.
[6]
The thermosetting resin (A) according to any one of [1] to [5], wherein the thermosetting resin (A) contains at least one selected from the group consisting of unsaturated polyester (A1) and vinyl ester (A2). Resin composition.
[7]
The content of the polyhydric alcohol (C) is 0.5 to 20 parts by mass with respect to 100 parts by mass in total of the thermosetting resin (A) and the ethylenically unsaturated compound (B) [1]. The thermosetting resin composition according to any one of [6].
[8]
The content of the ethylenically unsaturated compound (B) is 10 to 95% by mass based on the total of the thermosetting resin (A) and the ethylenically unsaturated compound (B) [1] to [7]. ] The thermosetting resin composition according to any one of.
[9]
The content of the inorganic aggregate (D) is 10 to 500 parts by mass with respect to 100 parts by mass in total of the thermosetting resin (A) and the ethylenically unsaturated compound (B) [4] or [ 5] The thermosetting resin composition according to.
[10]
The thermosetting resin composition according to any one of [1] to [9], which further comprises a thiol compound (E).
[11]
The thermosetting resin composition according to any one of [1] to [10], which further contains a metal complex (F).
[12]
The thermosetting resin composition according to [11], wherein the metal complex (F) is a metal soap.
[13]
The thermosetting resin composition according to any one of [1] to [12], further comprising a radical polymerization initiator (G).
[14]
A space filler or a pipe material containing the thermosetting resin composition according to any one of [1] to [13].
[15]
A cured product of the thermosetting resin composition according to any one of [1] to [13].
[16]
A tubular structure containing the cured product according to [15].

According to the present invention, it is possible to obtain a cured product having good mechanical strength and excellent allowable deflection rate. That is, it is possible to obtain a cured product of a thermosetting resin composition having good flexibility that can follow the displacement with respect to the external pressure.

Hereinafter, the present invention will be described in more detail. The present invention is not limited to the embodiments shown below.

In the present disclosure, "-" means a value equal to or greater than the value before the description "-" and a value equal to or lower than the value after the description "-".

In the present disclosure, "(meth) acrylic" is a general term for acrylic and methacrylic acid, "(meth) acrylate" is a general term for acrylate and methacrylate, and "(meth) allyl" is a general term for allyl and methacrylic. It is a generic term.

In the present disclosure, the "ethylenically unsaturated bond" means a double bond formed between carbon atoms other than the carbon atom forming the aromatic ring, and the "ethylenically unsaturated compound" means an ethylenically unsaturated compound. It means a compound having a saturated bond.

[Thermosetting resin composition]
The thermosetting resin composition contains a thermosetting resin (A), an ethylenically unsaturated compound (B), and a polyhydric alcohol (C). The cured product of the thermosetting resin composition has excellent flexibility and a high allowable deflection rate with respect to external pressure.

(Thermosetting resin (A))
The thermosetting resin (A) is not particularly limited as long as it is a compound having an ethylenically unsaturated bond and the polymerization reaction proceeds by the radical polymerization initiator.

Examples of the thermosetting resin (A) include unsaturated polyester (A1), vinyl ester (A2), urethane (meth) acrylate (A3) and the like. Among them, the thermosetting resin (A) preferably contains an unsaturated polyester (A1), a vinyl ester (A2), or a combination thereof from the viewpoint of the mechanical strength of the cured product. The thermosetting resin (A) may be used alone or in combination of two or more of the above (A1), (A2), and (A3).

(Unsaturated polyester (A1))
The unsaturated polyester (A1) may be a polycondensate obtained by polycondensing a polyhydric alcohol, an unsaturated polybasic acid, and at least one selected from a saturated polybasic acid and a monobasic acid, if necessary. For example, there is no particular limitation. An unsaturated polybasic acid is a polybasic acid having an ethylenically unsaturated bond, and a saturated polybasic acid is a polybasic acid having no ethylenically unsaturated bond. The unsaturated polyester may be used alone or in combination of two or more.

<Multivalent alcohol>
The polyhydric alcohol used as a raw material for the unsaturated polyester (A1) is not particularly limited as long as it is a compound having two or more hydroxyl groups. Among them, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, pentanediol, hexanediol, neopentanediol, tetraethylene glycol, polyethylene glycol, neopentyl glycol, 2-methyl-1,3- Propylene diol, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenol A, glycerin, ethylene oxide adduct of bisphenol A and propylene oxide adduct of bisphenol A Preferably, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, hydrogenated bisphenol A, ethylene oxide adduct of bisphenol A and propylene oxide adduct of bisphenol A are more preferable. The polyhydric alcohol may be used alone or in combination of two or more.

<Unsaturated polybasic acid>
The unsaturated polybasic acid is not particularly limited as long as it is a compound having an ethylenically unsaturated bond and having two or more carboxy groups or an acid anhydride thereof. For example, maleic acid, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, chloromaleic acid and the like can be mentioned. Among them, maleic anhydride, fumaric acid, citraconic acid, itaconic acid and chloromaleic acid are preferable, and maleic anhydride and fumaric acid are more preferable, from the viewpoint of heat resistance and mechanical strength of the cured product. The unsaturated polybasic acid may be used alone or in combination of two or more.

<Saturated polybasic acid>
The saturated polybasic acid is not particularly limited as long as it is a compound having no ethylenically unsaturated bond and having two or more carboxy groups or an acid anhydride thereof. For example, halogenated phthalic anhydrides such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrachlorophthalic anhydride and tetrabromophthalic anhydride, and aromatic saturated polybasic acids such as nitrophthalic anhydride or acid anhydrides thereof; Examples thereof include aliphatic saturated polybasic acids such as succinic acid, adipic acid, sebacic acid, oxalic acid, malonic acid, azelaic acid, glutaric acid and hexahydrophthalic anhydride, or acid anhydrides thereof. Among them, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid and adipic acid are preferable, and phthalic anhydride, isophthalic acid and terephthalic acid are more preferable, from the viewpoint of heat resistance and mechanical strength of the cured product. The saturated polybasic acid may be used alone or in combination of two or more.

<Monobasic acid>
Examples of the monobasic acid include dicyclopentadiene malate, benzoic acid and its derivative, and cinnamic acid and its derivative, and dicyclopentadiene malate is preferable. Dicyclopentadiene malate can be synthesized from maleic anhydride and dicyclopentadiene by a known method. By using a monobasic acid, the viscosity of the unsaturated polyester can be lowered, and the amount of the ethylenically unsaturated compound (B) used can be reduced. The monobasic acid may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the unsaturated polyester (A1) is not particularly limited. The weight average molecular weight of the unsaturated polyester (A1) is preferably 2,000 to 25,000, more preferably 3,000 to 20,000, and even more preferably 3,500 to 10,000. When the weight average molecular weight is 2,000 to 25,000, the moldability of the thermosetting resin composition becomes even better. In the present specification, the "weight average molecular weight" and the "number average molecular weight" are measured by gel permeation chromatography (GPC) at room temperature (23 ° C.) under the following conditions, and standard polystyrene calibration is performed. It is a value obtained by using a line.
Equipment: Showa Denko Corporation Shodex® GPC-101
Column: Showa Denko LF-804
Column temperature: 40 ° C
Sample: 0.2 mass% tetrahydrofuran solution of sample Flow rate: 1 mL / min Eluent: Tetrahydrofuran Detector: RI-71S

The degree of unsaturation of the unsaturated polyester (A1) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, still more preferably 70 to 100 mol%. When the degree of unsaturation is in the above range, the moldability of the thermosetting resin composition containing the unsaturated polyester (A1) becomes better. The degree of unsaturation of the unsaturated polyester (A1) can be calculated by the following formula using the number of moles of the unsaturated polybasic acid and the saturated polybasic acid used as raw materials.
Degree of unsaturation (mol%) = {(number of moles of unsaturated polybasic acid x number of unsaturated groups in unsaturated polybasic acid) / (number of moles of unsaturated polybasic acid + number of moles of saturated polybasic acid) )} × 100

The unsaturated polyester (A1) can be synthesized by a known method using the above raw materials. Various conditions in the synthesis of unsaturated polyester (A1) can be appropriately set according to the raw materials used and the amount thereof. Generally, an esterification reaction under pressure or reduced pressure at a temperature of 140 to 230 ° C. in an inert gas stream such as nitrogen gas can be used. In the esterification reaction, an esterification catalyst can be used if necessary. Examples of esterification catalysts include known catalysts such as manganese acetate, dibutyltin oxide, stannous oxalate, zinc acetate and cobalt acetate. The esterification catalyst may be used alone or in combination of two or more.

Examples of commercially available unsaturated polyester (A1) products include "Rigolac (registered trademark)" manufactured by Showa Denko KK.

(Vinyl ester (A2))
The vinyl ester (A2) generally opens a ring between an epoxy group in an epoxy compound having two or more epoxy groups and a carboxy group of an unsaturated monobasic acid having an ethylenically unsaturated bond and a carboxy group. It is a compound having an ethylenically unsaturated bond obtained by the reaction. The unsaturated monobasic acid is a monobasic acid having an ethylenically unsaturated bond. Such vinyl esters (A2) are described in, for example, the Polyester Resin Handbook (Nikkan Kogyo Shimbun, published in 1988). The vinyl ester (A2) may be used alone or in combination of two or more.

<Epoxy compound>
The epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups. For example, at least one selected from a bisphenol type epoxy compound, a hydride bisphenol type epoxy compound, and a novolak phenol type epoxy compound can be used. Such an epoxy compound can further improve the mechanical strength and corrosion resistance of the cured product.

Examples of the bisphenol type epoxy compound include a compound obtained by reacting a bisphenol compound such as bisphenol A, bisphenol F, bisphenol S and tetrabromobisphenol A with epichlorohydrin or methylepicrolhydrin; any one of the above bisphenol compounds or Examples thereof include a compound obtained by reacting a compound obtained by converting a plurality of glycidyl ethers with one or more of the above bisphenol compounds with epichlorohydrin or methylepicrolhydrin.

Examples of the hydride bisphenol type epoxy compound include compounds obtained by reacting glycidyl ether of hydride bisphenol A with bisphenol compounds such as bisphenol A, bisphenol F, bisphenol S and tetrabromobisphenol A.

Examples of the novolak phenol-type epoxy compound include compounds obtained by reacting phenol novolac or cresol novolak with epichlorohydrin or methylepicrolhydrin.

Among the epoxy compounds, the bisphenol A type epoxy compound is preferable from the viewpoint of chemical resistance.

<Unsaturated monobasic acid>
The unsaturated monobasic acid is not particularly limited as long as it is a monocarboxylic acid having an ethylenically unsaturated bond. For example, at least one selected from acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid is preferable, acrylic acid or methacrylic acid is more preferable, and methacrylic acid is particularly preferable. Since the vinyl ester (A2) obtained by the reaction of methacrylic acid and the epoxy compound has high hydrolysis resistance to acids and alkalis, the corrosion resistance of the cured product can be further improved.

The amount of the unsaturated monobasic acid used in the ring-opening reaction of the epoxy compound and the unsaturated monobasic acid is preferably 0.3 to 1.5 equivalents with respect to 1 equivalent of the epoxy group of the epoxy compound, and is 0. It is more preferably .4 to 1.2 equivalents, and particularly preferably 0.5 to 1.0 equivalents. If the amount of unsaturated monobasic acid used is in the range of 0.3 to 1.5 equivalents with respect to 1 equivalent of epoxy groups in the epoxy compound, radical polymerization of the thermosetting resin composition containing vinyl ester (A2) By the reaction, a cured product having sufficient hardness can be obtained.

Vinyl ester (A2) can be synthesized by a known synthesis method. For example, in the presence of an esterification catalyst, the epoxy compound and unsaturated monobasic acid are dissolved in a solvent as needed and reacted at, for example, 70 to 150 ° C., preferably 80 to 140 ° C., more preferably 90 to 130 ° C. There is a way to make it.

The unreacted unsaturated monobasic acid after synthesizing the vinyl ester (A2) is regarded as the ethylenically unsaturated compound (B) described later.

The commercially available vinyl ester (A2) is not particularly limited, and examples thereof include "Lipoxy (registered trademark)" manufactured by Showa Denko KK.

(Urethane (meth) acrylate (A3))
The urethane (meth) acrylate (A3) contains (meth) acrylic acid or a hydroxyl group with respect to the hydroxyl groups or isocyanato groups at both ends of polyurethane obtained by reacting a polyhydric isocyanate with a polyhydric alcohol, for example. ) A resin obtained by reacting acrylate can be used.
<Multivalent isocyanate>
Examples of the polyvalent isocyanate include isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate and the like. These diisocyanate compounds may be used alone or in combination of two or more.
<Multivalent alcohol>
As the polyhydric alcohol used as a raw material for urethane (meth) acrylate (A3), the compound described in the section of unsaturated polyester (A1) can be used.

Urethane (meth) acrylate (A3) may be used alone or in combination of two or more.

(Ethylene unsaturated compound (B))
The ethylenically unsaturated compound (B) is not particularly limited as long as it is a monomer compound having an ethylenically unsaturated group. The ethylenically unsaturated group may be one or more.

Examples of the ethylenically unsaturated compound (B) include α-, о-, m-, p-alkyl, nitro, cyano, amide, chloro, dichloro or ester of styrene such as styrene, vinyltoluene and t-butylstyrene. Vinyl compounds such as derivatives, vinyl acetate, methoxystyrene, divinylbenzene, vinylnaphthalene, acenaphthylene; diene compounds such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene; di (meth) allylphthalate, tri (meth) allylisosia (Meta) allyls such as nurate; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenyl (meth) acrylate, Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, allyl (meth) acrylate, isobornyl (meth) acrylate, ethylene glycol monomethyl ether (meth) Acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monohexyl ether (meth) acrylate, ethylene glycol mono2-ethylhexyl ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate , Diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, diethylene glycol monohexyl ether (meth) acrylate, diethylene glycol mono2-ethylhexyl ether (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate. ) Acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polytetramethylene ether glycol (PTMG) di (meth) acrylate , 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-hydroxy-1,3-dimethacryloyloxypropane, 2,2 -Bis [4- (methacryloylethoxy) phenyl] propane, 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane, tetra Ethylene glycol diacrylate, bisphenol AEO modified (n = 2) diacrylate, isocyanuric acid EO modified (n = 3) diacrylate, pentaerythritol di (meth) acrylate monostearate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (Meta) acrylates such as oxyethyl (meth) acrylate, tricyclodecanoldi (meth) acrylate, trimethylpropantri (meth) acrylate; (meth) acrylamide, N, N'-dimethyl (meth) acrylamide, N, Examples thereof include (meth) acrylamides such as N'-diisopropyl (meth) acrylamide; unsaturated dicarboxylic acid diesters such as diethyl citraconate; monomaleimide compounds such as N-phenylmaleimide; and N- (meth) acryloylphthalimide. Of these, styrene, vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, phenyl (meth) acrylate, and benzyl (meth) acrylate are preferable from the viewpoint of physical properties and surface dryness of the cured product. , Styrene, vinyltoluene and methyl (meth) acrylate are more preferred. The ethylenically unsaturated compound (B) may be used alone or in combination of two or more.

The content of the ethylenically unsaturated compound (B) is preferably 10 to 95% by mass, more preferably 30 to 80% by mass, based on the total of the thermosetting resin (A) and the ethylenically unsaturated compound (B). %, More preferably 40 to 60% by mass. If the content of the ethylenically unsaturated compound (B) is 10 to 95% by mass based on the total of the thermosetting resin (A) and the ethylenically unsaturated compound (B), the mechanical strength of the cured product is further enhanced. be able to.

(Multivalent alcohol (C))
The polyhydric alcohol (C) is a compound having two or more hydroxyl groups in one molecule, and its molecular weight or number average molecular weight is 62 to 950. Since the polyhydric alcohol (C) containing no ethylenically unsaturated bond does not participate in the radical polymerization of the thermosetting resin (A) and is not incorporated as a three-dimensional crosslinked product, the thermosetting resin composition is cured. It functions as a plastic component that imparts flexibility to an object.

The polyhydric alcohol (C) may be a primary, secondary or tertiary alcohol, or a mixture thereof.

Examples of the polyhydric alcohol (C) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, 1,2-propane. Diol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 1,4-pentanediol , 1,5-Pentanediol, 1,9-nonanediol, tricyclodecanedimethanol, 2,2-bis (2-hydroxyethoxyphenyl) propane, bisphenol A alkylene oxide adduct, bisphenol F alkylene oxide adduct, bisphenol Salkylene oxide adduct, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-hexanediol, 1,3-cyclohexanediol, 2,3-hexanediol, 1,4-hexanediol, 2 , 4-Hexanediol, 3,4-Hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 9,9-bis [4- (2-hydroxyethyl) phenyl] Divalent alcohols such as fluorene; glycerin, diglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tris (2-hydroxyethyl) isocyanurate, hexanetriol, sorbitol, pentaerythritol, dipentaerythritol, sucrose, Trihydric or higher alcohols such as 2,2-bis (2,3-dihydroxypropyloxyphenyl) propane; other examples include polycarbonatediol and polyester polyol dimerate.

Of these, from the viewpoint of availability, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, 1,2- Propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 1,4-pentane Glycol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, tricyclodecanedimethanol, 2,2-bis (2-hydroxyethoxyphenyl) propane, bisphenol A alkylene oxide adduct, Bisphenol F alkylene oxide adduct, bisphenol S alkylene oxide adduct, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-hexanediol, 1,3-cyclohexanediol, 2,3-hexanediol, 1,4-Hexanediol, 2,4-hexanediol, 3,4-hexanediol, 1,5-hexanediol, 2,5-hexanediol, and 1,6-hexanediol are preferable, and from the viewpoint of improving flexibility. From the above, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, and bisphenol A alkylene oxide adduct are preferable, and the phase with the resin. From the viewpoint of solubility, polyalkylenediol such as polyethylene glycol and polypropylene glycol, and bisphenolalkylene oxide adduct such as bisphenol A alkylene oxide adduct are preferable. The bisphenol alkylene oxide adduct is obtained by adding an alkylene oxide such as propylene oxide or ethylene oxide to the hydroxy group of bisphenol such as bisphenol A, bisphenol F or bisphenol S to generate a hydroxy group. The alkylene group of the alkylene oxide preferably has 2 to 4 carbon atoms.

The molecular weight or number average molecular weight of the polyhydric alcohol (C) is 62 to 950, preferably 100 to 900, more preferably 120 to 800, and even more preferably 250 to 700. Within the above range, the polyhydric alcohol (C) is less likely to volatilize during curing and is easily compatible with the resin.

The content of the polyvalent alcohol (C) in the thermosetting resin composition is the thermosetting resin (A) and ethylene in consideration of the balance between the compatibility with the thermosetting resin (A) and the mechanical strength. The amount is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and further preferably 3 to 10 parts by mass with respect to 100 parts by mass of the total of the sex unsaturated compound (B).

(Inorganic aggregate (D))
The thermosetting resin composition may contain an inorganic aggregate (D). The inorganic aggregate (D) is not particularly limited as long as it is not dissolved by the components in the thermosetting resin composition. The inorganic aggregate (D) may be used alone or in combination of two or more.

The inorganic aggregate (D) preferably contains at least one selected from the group consisting of aluminum oxide, aluminum hydroxide, silica sand, calcium carbonate, glass powder, talc, and molten silica.

The central particle size of the inorganic aggregate (D) is preferably 1 to 300 μm, more preferably 3 to 200 μm, and even more preferably 5 to 150 μm. When the central particle size of the inorganic aggregate (D) is 1 to 300 μm, it is possible to suppress an increase in the viscosity of the thermosetting resin composition due to the addition of the inorganic aggregate (D). The central particle size is a median diameter in which the volume accumulation frequency from the small diameter side in the volume-based particle size distribution measured by the laser diffraction / scattering type particle size distribution measurement method reaches 50%.

The content of the inorganic aggregate (D) is preferably 10 to 500 parts by mass, more preferably 25 parts by mass, based on 100 parts by mass of the total of the thermosetting resin (A) and the ethylenically unsaturated compound (B). It is ~ 300 parts by mass, more preferably 50 to 200 parts by mass. If the content of the inorganic aggregate (D) is 10 to 500 parts by mass with respect to a total of 100 parts by mass of the thermosetting resin (A) and the ethylenically unsaturated compound (B), the mechanical strength of the cured product is increased. Can be enhanced.

(Thiol compound (E))
The thermosetting resin composition may contain the thiol compound (E). The thiol compound (E) is a compound having a mercapto group. By using the thiol compound (E) in combination with the metal complex (F) described later, the radical polymerization reaction of the thermosetting resin composition can be promoted. Therefore, it is preferable that the thermosetting resin composition contains the thiol compound (E), particularly for room temperature curing applications. Specific examples of the thiol compound (E) include 1,4-bis (3-mercaptobutyryloxy) butane (Showa Denko KK "Karensu MT (registered trademark) BD1") and pentaerythritol tetrakis (3-mercaptobuty). Rate) (Showa Denko KK "Karensu MT (registered trademark) PE1"), 1,3,5-Tris [2- (3-mercaptobutyryloxyethyl)]-1,3,5-triazine-2,4 , 6 (1,3,5) -Trion (Showa Denko KK "Karensu MT (registered trademark) NR1"), Trimethylol ethanetris (3-mercaptobutyrate) (Showa Denko KK "Karenzu MT (registered)" Commercial products such as "TEMB") and trimethylol propanthris (3-mercaptobutyrate) ("Karensu MT (registered trademark) TPMB" manufactured by Showa Denko KK) can be preferably used.

The thiol compound (E) may be used alone or in combination of two or more.

The content of the thiol compound (E) with respect to a total of 100 parts by mass of the thermosetting resin (A) and the ethylenically unsaturated compound (B) does not affect the resin properties of the cured product of the thermosetting resin composition. The amount is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and further preferably 0.1 to 3 parts by mass.

(Metal complex (F))
The thermosetting resin composition may contain a metal complex (F). The metal complex (F) can accelerate the radical polymerization reaction of the thermosetting resin composition. The metal complex (F) is not particularly limited as long as it is a compound in which an organic compound is coordinated to a metal atom via a coordination bond. Examples of the metal element of the metal complex (F) include zirconium, cobalt, manganese, iron, copper, titanium, lead, tin, barium, bismuth, yttrium, vanadium, and calcium. Among them, from the viewpoint of curing acceleration performance, zirconium, cobalt, manganese, iron, copper and vanadium are preferable, cobalt, manganese, iron and vanadium are more preferable, and cobalt, manganese and iron are even more preferable.

Examples of the organic compound constituting the metal complex (F) include long-chain fatty acids and organic acids other than long-chain fatty acids, and long-chain fatty acids are preferable.

An example of a preferred long chain fatty acid is a fatty acid having 7 to 30 carbon atoms. Specifically, octanoic acid such as heptanic acid and 2-ethylhexanoic acid, nonanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid. , Hexacosanoic acid, octacosanoic acid, triacanthanoic acid, naphthenic acid and other chain or cyclic saturated fatty acids, and oleic acid, linoleic acid, linolenic acid and other unsaturated fatty acids are preferable.

The organic acid other than the long-chain fatty acid is not particularly limited, but a compound of a weak acid having a carboxy group, a hydroxy group, or an enol group and which is soluble in an organic solvent is preferable.

The metal complex (F) is preferably a metal soap. Preferred metal soaps include manganese octylate, cobalt octylate, zinc octylate, vanadium octylate, cobalt naphthenate, copper naphthenate, barium naphthenate, vanadium acetoacetate, cobalt acetoacetate, iron acetoacetate and the like. , Manganese octylate, cobalt octylate, cobalt naphthenate and the like are more preferred.

The metal complex (F) may be used alone or in combination of two or more.

The content of the metal complex (F) is preferably 0.05 to 5.00 parts by mass with respect to 100 parts by mass in total of the thermosetting resin (A) and the ethylenically unsaturated compound (B). It is preferably 0.25 to 3.00 parts by mass, and more preferably 0.50 to 1.50 parts by mass. If the content of the metal complex (F) is 0.05 to 5.00 parts by mass with respect to a total of 100 parts by mass of the thermosetting resin (A) and the ethylenically unsaturated compound (B), the wet conditions are met. The thermosetting resin composition can be cured more easily even in water.

(Radical polymerization initiator (G))
Since the thermosetting resin composition is cured by a radical polymerization reaction, it preferably contains a radical polymerization initiator (G).

When the radical polymerization initiator (G) is stored under conditions that do not initiate the radical polymerization reaction of the thermosetting resin (A), it is previously contained in the thermosetting resin composition from the viewpoint of work efficiency and the like. You may keep it.

The type of the radical polymerization initiator (G) is appropriately selected depending on the type of the thermosetting resin (A), the usage conditions of the thermosetting resin composition, the reaction conditions, and the like, and is a known thermal radical polymerization initiator. Can be used. The radical polymerization initiator (G) may be used alone or in combination of two or more.

Specific examples of the thermal radical polymerization initiator include diacyl peroxides such as benzoyl peroxide; peroxyesters such as tert-butyl peroxybenzoate; hydroperoxides such as cumene hydroperoxide; dialkyls such as dicumyl peroxide. Peroxide; Ketone peroxide such as methyl ethyl ketone peroxide and acetylacetone peroxide; Peroxyketal such as 1,1-dialkylperoxycyclohesan; Alkyl peroxide such as alkylperoxydecanoate; Peroxydicarbonate and the like Examples include organic peroxides such as carbonate.

The content of the radical polymerization initiator (G) in the thermosetting resin composition is appropriately set according to the type of the thermosetting resin (A), the usage conditions of the resin composition, the reaction conditions, and the like. The content of the radical polymerization initiator (G) is usually 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the thermosetting resin (A) and the ethylenically unsaturated compound (B). It is preferably 0.5 to 8 parts by mass, and even more preferably 0.5 to 5 parts by mass. If the content of the radical polymerization initiator (G) is 0.1 parts by mass or more, the radical polymerization reaction can proceed satisfactorily, and if it is 10 parts by mass or less, the obtained effect and the production cost are well balanced. be.

(others)
The thermosetting resin composition may contain various additives such as a curing accelerator, a solvent, a colorant, a fiber, a coupling agent, a wax, and a rocking agent, if necessary, depending on the purpose of use and application. good.

The curing accelerator can be used to improve the curability of the thermosetting resin composition.

Specific examples of the curing accelerator include amines such as aniline, N, N-substituted aniline, N, N-substituted-p-toluidine, and 4- (N, N-substituted amino) benzaldehyde. Specifically, aniline, N, N-dimethylaniline, N, N-diethylaniline, p-toluidine, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine, 4- (N, N-dimethylamino) benzaldehyde, 4- [N, N-bis (2-hydroxyethyl) amino] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) benzaldehyde, N, N-bis (2-Hydroxypropyl) -p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N, N-bis (hydroxyethyl) aniline, diethanolaniline, etc. Can be mentioned. The curing accelerator may be used alone or in combination of two or more.

The solvent is used as necessary from the viewpoint of uniformly mixing each component in the thermosetting resin composition. The content is not particularly limited, and can be appropriately adjusted according to the handleability at the time of use and the like. The type of solvent is appropriately selected according to the type of resin, intended use, etc., within a range that does not affect the curing performance and storage stability of the thermosetting resin composition. For example, aliphatic hydrocarbons, aromatic hydrocarbons, ethers, ketones, esters, chain carbonates and the like can be mentioned. The solvent may be used alone or in combination of two or more.

Specifically, examples of the aliphatic hydrocarbon include mineral spirits such as cyclohexane, n-hexane, white spirit, and odorless mineral spirit. Examples of aromatic hydrocarbons include naphthene, a mixture of naphthene and paraffin, benzene, toluene, quinoline and the like. Examples of the ether include diethyl ether and diisopropyl ether. Examples of the ketone include acetone, methyl ethyl ketone, cyclohexanone and the like. Examples of the ester include ethyl acetate, butyl acetate, diethyl malonate, diethyl succinate, dibutyl succinate, dibutyl maleate, 2,2,4-trimethylpentanediol diisobutyrate, mono- and diester of ketoglutaric acid, ethyl pyruvate and the like. Examples thereof include pyruvates, ascorbic acid mono and diesters such as ascorbyl palmitate. Examples of the chain carbonic acid ester include dimethyl carbonate and diethyl carbonate. In addition, 1,2-dioximes such as 1,2-cyclohexanedionedioxime, N-methylpyrrolidone, 1-ethyl-2-pyrrolidinone, N, N-dimethylformamide and the like can also be used.

The solvent is a commercially available thermosetting resin (A), ethylenically unsaturated compound (B), polyhydric alcohol (C), inorganic aggregate (D), thiol compound (E), metal complex (F), radical polymerization. It may be contained in the product of the initiator (G).

Examples of the colorant include known color pigments, extender pigments, pigments such as rust preventive pigments, and dyes. The colorant may be used alone or in combination of two or more.

Examples of the fibers include inorganic fibers such as glass fibers and carbon fibers, organic fibers such as vinylon fibers, nylon fibers, aramid fibers, polypropylene fibers, acrylic fibers, polyester fibers and cellulose fibers, metal fibers such as steel fibers, and alumina fibers. Examples include ceramic fibers. The fiber may be used alone or in combination of two or more.

Examples of the coupling agent include a silane coupling agent, a titanate coupling agent, an aluminum coupling agent and the like. The coupling agent may be used alone or in combination of two or more.

Examples of the wax include paraffin wax and polar wax. The wax may be used alone or in combination of two or more.

Examples of the swaying agent include an inorganic swaying agent and an organic swaying agent. Examples of the organic shaker include hydrogenated castor oil, amide such as acrylamide, polyethylene oxide, vegetable oil, polymerized oil, surfactant, and a combination thereof. Examples of the inorganic rocking agent include silica and bentonite, and both a hydrophobic inorganic rocking agent and a hydrophilic inorganic rocking agent can be used. The shaking agent may be used alone or in combination of two or more.

The content of the additive should be appropriately adjusted according to the desired physical properties of the cured product of the thermosetting resin composition to be produced within a range that does not affect the curing performance and storage stability of the thermosetting resin composition. Can be done. The total content of the additive is preferably 0.1 to 700 parts by mass, more preferably 0, with respect to 100 parts by mass of the total of the thermosetting resin (A) and the ethylenically unsaturated compound (B). .1 to 500 parts by mass, more preferably 0.1 to 300 parts by mass.

(Manufacturing method of thermosetting resin composition)
The thermosetting resin composition includes a thermosetting resin (A), an ethylenically unsaturated compound (B), and a polyhydric alcohol (C), and if necessary, an inorganic aggregate (D) and thiol which are optional components. It can be obtained by mixing and stirring one or more of the components of the compound (E), the metal complex (F), and the radical polymerization initiator (G) by a known method. Further, an additive or the like may be added as an arbitrary component. The order of adding and mixing each component is not particularly limited. At the time of mixing and stirring, as described above, a solvent may be appropriately used from the viewpoint of uniformly mixing each compounding component.

For example, a thermosetting resin (A), an ethylenically unsaturated compound (B), and a polyhydric alcohol (C) are mixed, then a thiol compound (E) and a metal complex (F) are mixed, and finally, an inorganic bone. The material (D) can be mixed. When produced by this method, it is easy to uniformly disperse the polyhydric alcohol (C) in the thermosetting resin (A).

The mixing method in each step is not particularly limited, and a known method can be used. The temperature at the time of each mixing is preferably 20 to 40 ° C. from the viewpoint of uniformly mixing and suppressing the deterioration of each component.
(How to use the thermosetting resin composition)
The thermosetting resin composition can be used as a raw material for, for example, a space filler and a pipe material. The tubular structure produced by using the thermosetting resin composition has good mechanical strength, can follow the displacement with respect to the external pressure, and can suppress early cracking and breaking.
[Cured product]
The cured product is obtained by curing the thermosetting resin composition at room temperature or by heating. Specific temperature ranges for room temperature and heating include, for example, a temperature range of 0 ° C. to 200 ° C.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

The raw materials used for producing the thermosetting resin compositions of the following Examples and Comparative Examples are as follows.

(Thermosetting resin (A))
<Manufacturing of unsaturated polyester>
191 g of propylene glycol, 164 g of diethylene glycol, 64 g of isophthalic acid, and 64 g of terephthalic acid were placed in a 1 L flask equipped with a stirrer, a fractional distillation condenser, a thermometer, and a nitrogen gas introduction tube, and reacted at 215 ° C. for 5 hours with heating and stirring. After that, it was cooled to 120 ° C. 189 g of maleic anhydride and 0.04 g of tert-butyl hydroquinone were charged therein, reacted at 215 ° C. with heating and stirring, cooled when the acid value reached 20 mgKOH / g, and 0.05 g of hydroquinone and copper naphthenate. 0.02 g and 400 g of styrene monomer were charged to obtain 1000 g of a mixture AB-1 containing 60% by mass of unsaturated polyester A-1 (weight average molecular weight 3,700, degree of unsaturation 71 mol%).

<Manufacturing of vinyl ester>
Bisphenol A type epoxy resin Araldite® AER-2603 (Asahi Kasei E-Materials Co., Ltd.) having an epoxy equivalent of 188.0 in a 1 L four-necked flask equipped with a thermometer, agitator, gas inlet and reflux condenser. (Manufactured by the company) 434.5 g, 125.3 g of styrene and 0.13 g of hydroquinone were dissolved in 66.3 g of methacrylic acid, and the temperature was raised while stirring. When the temperature reached 100 to 110 ° C., 132.7 g of methacrylic acid in which 1.9 g of 2,4,6-tris (dimethylaminomethyl) phenol (Sequol (registered trademark) TDMP, manufactured by Seiko Kagaku Co., Ltd.) was dissolved was added. The mixture was added dropwise over about 30 minutes and reacted at 130 ° C. When the acid value becomes 11 mgKOH / g or less, the mixture is cooled, and when the acid value becomes 110 ° C. or less, 438.6 g of styrene and 0.2 g of trimethylhydroquinone are added, and 63 vinyl ester A-2 (weight average molecular weight 462) is added. 1200 g of the mixture AB-2 containing mass% was obtained.

(Ethylene unsaturated compound (B))
Styrene (total of styrene contained in the above mixture AB-1 (content 40% by mass) or styrene contained in the mixture AB-2 (content 37% by mass), and styrene separately blended).

(Multivalent alcohol (C))
Ethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 62)
Propylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 76)
Diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 106)
Dipropylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 134)
Polyethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., number average molecular weight 600)
Bisphenol A-PO adduct (ADEKA Corporation, BPX-11, number average molecular weight 286)

(Other alcohols (C')
Polypropylene glycol (Kishida Chemical Co., Ltd., polypropylene glycol 1,000, number average molecular weight 1000)
Ethanol (molecular weight 45)

(Inorganic aggregate (D))
Aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd., B103, center particle size 7 μm)
Silica sand (center particle size 80 μm)

(Thiol compound (E))
Bifunctional secondary thiol compound (Showa Denko KK, Calends MT (registered trademark) BD1 (1,4-bis (3-mercaptobutylyloxy) butane))

(Metal complex (F))
Cobalt octylate (manufactured by Toei Kako Co., Ltd., hexoate cobalt, cobalt content 8% by mass in the total amount of the product, molecular weight 345.34)

(Radical polymerization initiator (G))
Cumene hydroperoxide (manufactured by NOF CORPORATION, Park Mill (registered trademark) H-80)

[Manufacturing of thermosetting resin composition]
(Example 1)
80 parts by mass of mixture AB-1 (including 48 parts by mass of unsaturated polyester A-1 and 32 parts by mass of styrene), 20 parts by mass of ethylenically unsaturated compound (B), 0.5 parts by mass of thiol compound (E), metal To 1.5 parts by mass of the complex (F), 10 parts by mass of ethylene glycol as the polyhydric alcohol (C) was added, and the mixture was stirred and mixed at 25 ° C. A thermosetting resin composition was obtained by adding 100 parts by mass of aluminum hydroxide and 1.0 part by mass of a radical polymerization initiator (G) as the inorganic aggregate (D) and stirring and mixing them.
(Examples 2 to 9, Comparative Examples 1 to 3)
With the compounding compositions shown in Table 1 below, each thermosetting resin composition was obtained in the same manner as in Example 1.

[Evaluation of thermosetting resin composition]
The thermosetting resin compositions produced in the above Examples and Comparative Examples were evaluated for the following items.
<Curing method of thermosetting resin composition>
The thermosetting resin compositions produced in the above Examples and Comparative Examples were prepared by using a hard polyvinyl chloride tube having an outer diameter of 76 mm and a thickness of 2.2 mm and an outer diameter of 89 mm and a thickness of 2.7 mm and a thickness of 3.8 mm. A tubular thermosetting resin composition having an outer diameter of 83 mm, a thickness of 3.8 mm, and a length of 50.0 mm by pouring it into a tubular mold composed of spacers made of silicone resin and allowing it to stand at 23 ° C. for 3 days. A cured product of the product was obtained.

<Line load>
The cured product obtained by the above curing method was sandwiched between two flat plates larger than the cured product, and the load was measured while pressing the cured product at a speed of 10 mm / min in the direction perpendicular to the tube axis. The linear load is a value calculated by converting the load at the time of compression of 4 mm into 1 m of the length of the test piece.
Linear load (N / m) = (Load at 4 mm compression (N)) / (Length of cured product in the tube axis direction (m))

<Allowable deflection rate>
The allowable deflection rate is a value calculated by dividing the amount of displacement at the time when the cured product is broken by the outer diameter of the cured product in the above test.
Allowable deflection rate = (displacement amount at break (mm)) / (outer diameter of cured product (mm)) x 100

As can be seen from the results shown in Table 1, the thermosetting resin composition (Example) containing a polyhydric alcohol having a specific molecular weight or a number average molecular weight has an allowable deflection rate as compared with the comparative example. Is high. Further, in Comparative Examples 1 and 3, the numerical value could not be measured because the test piece broke during the linear load measurement. Therefore, it is clear that the cured product of the example has high flexibility. In addition, the composition of Comparative Example 2 using polypropylene glycol having a number average molecular weight of more than 950 could not be cured. In the composition of Comparative Example 3 using ethanol, a large number of pinholes were generated during curing, and a hard and brittle cured product was obtained. On the other hand, in the examples in which the thermosetting resin composition contained a specific polyhydric alcohol, excellent linear load and allowable deflection rate were obtained. Therefore, it can be seen that the cured product of the thermosetting resin composition of the present invention has good mechanical strength, can follow the displacement with respect to the external pressure, and can suppress early cracking and breaking.

The cured product of the thermosetting resin composition of the present invention has good mechanical strength, can follow the displacement with respect to the external pressure, and can suppress early cracks and breaks. Therefore, pipe rehabilitation and tunnel construction can be performed. It can be used for various purposes such as a space filler in the above, a pipe material having a multilayer structure with a thermoplastic resin, and the like.

Claims (16)

It contains a thermosetting resin (A), an ethylenically unsaturated compound (B), and a polyvalent alcohol (C), and the molecular weight or number average molecular weight of the polyvalent alcohol (C) is 62 or more and 950 or less. Resin composition. The thermosetting resin composition according to claim 1, wherein the polyhydric alcohol (C) has a molecular weight or a number average molecular weight of 100 or more and 900 or less. The thermosetting resin composition according to claim 1 or 2, wherein the polyhydric alcohol (C) contains at least one selected from the group consisting of a polyalkylene diol and a bisphenol alkylene oxide adduct. The thermosetting resin composition according to any one of claims 1 to 3, further comprising an inorganic aggregate (D). The thermosetting according to claim 4, wherein the inorganic aggregate (D) contains at least one selected from the group consisting of aluminum oxide, aluminum hydroxide, silica sand, calcium carbonate, glass powder, talc, and molten silica. Resin composition. The thermosetting according to any one of claims 1 to 5, wherein the thermosetting resin (A) contains at least one selected from the group consisting of unsaturated polyester (A1) and vinyl ester (A2). Resin composition. Claim 1 in which the content of the polyvalent alcohol (C) is 0.5 to 20 parts by mass with respect to 100 parts by mass in total of the thermosetting resin (A) and the ethylenically unsaturated compound (B). The thermosetting resin composition according to any one of 1 to 6. The content of the ethylenically unsaturated compound (B) is 10 to 95% by mass based on the total of the thermosetting resin (A) and the ethylenically unsaturated compound (B), according to claims 1 to 7. The thermosetting resin composition according to any one of the items. Claim 4 or 5 in which the content of the inorganic aggregate (D) is 10 to 500 parts by mass with respect to a total of 100 parts by mass of the thermosetting resin (A) and the ethylenically unsaturated compound (B). The thermosetting resin composition according to. The thermosetting resin composition according to any one of claims 1 to 9, further comprising a thiol compound (E). The thermosetting resin composition according to any one of claims 1 to 10, further comprising a metal complex (F). The thermosetting resin composition according to claim 11, wherein the metal complex (F) is a metal soap. The thermosetting resin composition according to any one of claims 1 to 12, further comprising a radical polymerization initiator (G). A space filler or a pipe material containing the thermosetting resin composition according to any one of claims 1 to 13. The cured product of the thermosetting resin composition according to any one of claims 1 to 13. A tubular structure containing the cured product according to claim 15.