JP7358940B2 - thermosetting resin composition - Google Patents

Description

The present invention relates to a thermosetting resin composition.

Thermosetting resins are used as molding materials, adhesives, primers, paints, as well as inorganic structure repair materials for cross-sectional repair of concrete, crack injection, water stopping, etc., fillers, fillers, and fiber-reinforced composites. It is used in a wide range of applications including materials.
Among thermosetting resins, many radically polymerizable thermosetting resins such as unsaturated polyester resins, vinyl ester resins, and urethane acrylate resins have advantages such as moldability, curability, and adhesion to substrates. , is widely used in the above fields.
Furthermore, in order to improve the mechanical strength of a cured thermosetting resin, it may be mixed with an inorganic aggregate and used as a thermosetting resin composition. Such thermosetting resin compositions are called resin concrete or resin mortar, and have advantages over cement mortar in that they have excellent specific strength and chemical resistance.

Here, crack injection agents and mortar coating agents are required to adhere closely to inorganic structure base materials such as concrete even in a wet state. However, in water or other chemical solutions, the thermosetting resin and the inorganic aggregate gradually peel off, resulting in a decrease in mechanical strength.
Conventionally, there have been methods to increase the double bond strength of thermosetting resins (Non-Patent Document 1), methods to make the resin have a hydrophobic structure (Non-Patent Document 1), and methods to apply thermosetting resins called coupling agents to inorganic aggregates. A method of adding a surface modifier that reacts with or interacts with the plastic resin (Non-Patent Document 2) has been adopted. Among these, treatment of inorganic aggregate with a coupling agent is a commonly used method because it can improve the adhesion between the resin and inorganic aggregate without changing the inherent mechanical strength of the thermosetting resin. be.
In addition, even if water is present in the radically polymerizable thermosetting resin composition or in the environment in which the thermosetting resin composition is used, the function of the metal soap used as a curing accelerator is suppressed and the metal soap is stabilized. discloses a technique for curing the thermosetting resin composition (Patent Documents 1 and 2).

International Publication No. 2016/171150 International Publication No. 2016/171151

Koichi Ochi, “Effects of free volume and polar group concentration on water absorption of phenol-cured epoxy resins”, Thermosetting Resins, Vol. 15 No. 1 (1994) Yoshinobu Nakamura, “Control of hydrolysis and condensation reactions in silane coupling agent treatment”, Journal of the Adhesion Society of Japan, Vol.52 No.1 (2016)

However, in the methods of Non-Patent Documents 1 and 2, the initial physical properties of the thermosetting resin change, the compatibility with various additives deteriorates, and the surface treatment process using a coupling agent increases, making the work complicated. There are also issues such as the production of methanol as a by-product during the coupling process.
In addition, in recent years, there has been an increasing demand for fillers that can be filled into wet spaces to develop high strength in a short period of time, and can also maintain this strength for a long period of time while blocking water. In addition, filler materials are used when rehabilitating pipes or constructing tunnels, and are required to be able to quickly fill spaces between base materials. Furthermore, unlike crack injection agents and mortar coating agents, which are temporary repair methods, it is required to maintain strength over a long period of time even if affected by water leakage or the like. In Patent Documents 1 and 2, the thermosetting resin composition can be stably cured even in the presence of water, but there is no mention of maintaining the long-term mechanical strength of the cured product.

Therefore, the present invention provides a thermosetting resin composition that can be cured in a humid space, has good mechanical strength as a cured product, and can suppress a decrease in mechanical strength even when in contact with water for a long period of time. The challenge is to provide the following.

The present invention provides a thermosetting resin composition containing a metal complex as a curing accelerator and a thiol compound as a curing accelerator, by adding an inorganic aggregate and water to the thermosetting resin composition. This is based on the discovery that deterioration in mechanical strength can be suppressed even when a cured product is exposed to water for a long period of time.
That is, the present invention provides the following [1] to [10].

[1] Thermosetting resin having multiple ethylenically unsaturated bonds (A), ethylenically unsaturated compound (B), thiol compound (C), metal complex (D), inorganic aggregate (E), and water Contains (F),
The content of the surfactant is 0 parts by mass or more and less than 0.05 parts by mass with respect to 100 parts by mass of the total content of the thermosetting resin (A), the ethylenically unsaturated compound (B), and the water (F). and
The content of the water (F) is 0.5 parts by mass or more and less than 5 parts by mass with respect to 100 parts by mass of the total content of the thermosetting resin (A) and the ethylenically unsaturated compound (B),
Thermosetting resin composition.
[2] The thermosetting resin composition according to [1] above, which has a viscosity at 25° C. of 2.5 Pa·s or less.
[3] The thermosetting resin composition according to [1] or [2], wherein the thermosetting resin (A) contains at least one of an unsaturated polyester resin and a vinyl ester resin.
[4] The thermosetting resin composition according to any one of [1] to [3] above, wherein the metal complex (D) is a metal soap.
[5] Any one of [1] to [4] above, wherein the inorganic aggregate (E) contains any one or more of aluminum oxide, aluminum hydroxide, silica sand, glass powder, talc, and fused silica. The thermosetting resin composition described.
[6] The thermosetting resin composition according to any one of [1] to [5] above, wherein the inorganic aggregate (E) has a center particle size of 1 to 300 μm.
[7] The thermosetting resin composition according to any one of [1] to [6] above, further containing a radical polymerization initiator (G).
[8] A space-filling material comprising the thermosetting resin composition according to any one of [1] to [7] above.
[9] A cured product of the thermosetting resin composition according to any one of [1] to [7] above.
[10] Pipe or tunnel using the cured product according to [9] above

According to the present invention, a thermosetting resin composition that can be cured in a wet space, has good mechanical strength as a cured product, and can suppress a decrease in mechanical strength even when in contact with water for a long period of time. can provide things.

The present invention will be explained in more detail below.
As used herein, "~" means a value greater than or equal to the value before the description "~" and less than or equal to the value after the description "~".
Further, "(meth)acrylic" is a generic term for acrylic and methacrylic, and "(meth)acrylate" is a generic term for acrylate and methacrylate.
"Ethylenically unsaturated bond" means a double bond formed between carbon atoms other than carbon atoms forming an aromatic ring, "ethylenically unsaturated monomer" means an ethylenically unsaturated bond means a monomer having

[Thermosetting resin composition]
The thermosetting resin composition includes a thermosetting resin (A) having a plurality of ethylenically unsaturated bonds, an ethylenically unsaturated compound (B), a thiol compound (C), a metal complex (D), and an inorganic aggregate ( E) and water (F).
The above thermosetting resin composition can be cured in a humid space, has good mechanical strength of the cured product, and can suppress a decrease in mechanical strength even when in contact with water for a long period of time. The cured product has excellent water resistance.

(Thermosetting resin (A) having multiple ethylenically unsaturated bonds)
The thermosetting resin (A) having a plurality of ethylenically unsaturated bonds is not particularly limited as long as it is a compound having a plurality of ethylenically unsaturated bonds and whose polymerization reaction proceeds with a radical polymerization initiator.
Examples of the thermosetting resin (A) include unsaturated polyester resin, vinyl ester resin, and urethane (meth)acrylate resin. Among them, the thermosetting resin (A) preferably contains at least one of an unsaturated polyester resin and a vinyl ester resin from the viewpoint of mechanical strength of the cured product. The thermosetting resin (A) may be used alone or in combination of two or more.

(Unsaturated polyester resin (A1))
The unsaturated polyester resin (A1) can be obtained by polycondensing a polyhydric alcohol, an unsaturated polybasic acid, and, if necessary, at least one selected from a saturated polybasic acid and a monobasic acid. , not particularly limited. An unsaturated polybasic acid is a polybasic acid that has an ethylenically unsaturated bond, and a saturated polybasic acid is a polybasic acid that does not have an ethylenically unsaturated bond. One type of unsaturated polyester resin may be used alone, or two or more types may be used in combination.

<Polyhydric alcohol>
The polyhydric alcohol 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- Propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, hydrogenated bisphenol A, bisphenol A, glycerin, ethylene oxide adduct of bisphenol A, and propylene oxide adduct of bisphenol A are preferred, and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, hydrogenated bisphenol A, an ethylene oxide adduct of bisphenol A, and a propylene oxide adduct of bisphenol A are more preferred. Polyhydric alcohols 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 two or more carboxyl groups or an acid anhydride thereof. Examples include maleic acid, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, chloromaleic acid, and the like. Among these, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, and chloromaleic acid are preferred, and maleic anhydride and fumaric acid are more preferred, from the viewpoint of heat resistance and mechanical strength of the cured product. The unsaturated polybasic acids 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 that does not have an ethylenically unsaturated bond and has two or more carboxy groups or its acid anhydride. For example, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, tetrachlorophthalic anhydride, tetrabromo phthalic anhydride, endomethylenetetrahydrophthalic anhydride, nitrophthalic acid, tetrahydrophthalic anhydride, Examples include halogenated phthalic anhydride, oxalic acid, malonic acid, azelaic acid, glutaric acid, and hexahydrophthalic anhydride. Among them, from the viewpoint of heat resistance and mechanical strength of the cured product, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, endomethylenetetrahydrophthalic anhydride and tetrahydrophthalic anhydride are preferred; More preferred are phthalic acid, isophthalic acid and terephthalic acid. The saturated polybasic acids 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 derivatives, and cinnamic acid and its derivatives, with dicyclopentadiene malate being preferred. 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 resin can be lowered, and the amount of styrene used can be reduced. Monobasic acids may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the unsaturated polyester resin (A1) is not particularly limited. The weight average molecular weight of the unsaturated polyester resin (A1) is preferably 2,000 to 25,000, more preferably 3,000 to 20,000, and even more preferably 3,500 to 10,000. . If the weight average molecular weight is 2,000 to 25,000, the moldability of the unsaturated polyester resin composition will be even better. In this specification, the "weight average molecular weight" is a standard polystyrene equivalent value measured by gel permeation chromatography (GPC).

The degree of unsaturation of the unsaturated polyester resin (A1) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, even more preferably 70 to 100 mol%. When the degree of unsaturation is within the above range, the moldability of the thermosetting resin composition containing the unsaturated polyester resin (A1) will be better. The degree of unsaturation of the unsaturated polyester resin (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. However, the number of unsaturated groups in the unsaturated polybasic acid is one.
Degree of unsaturation (mol%) = {(number of moles of unsaturated polybasic acid)/(number of moles of unsaturated polybasic acid + number of moles of saturated polybasic acid)}×100

The unsaturated polyester resin (A1) can be synthesized by a known method using the above raw materials. Various conditions in the synthesis of the unsaturated polyester resin (A1) can be appropriately set depending on the raw materials used and their amounts. Generally, an esterification reaction can be carried out in a stream of inert gas such as nitrogen gas at a temperature of 140 to 230° C. under increased pressure or reduced pressure. In the esterification reaction, an esterification catalyst can be used as necessary. Examples of esterification catalysts include known catalysts such as manganese acetate, dibutyltin oxide, stannous oxalate, zinc acetate, and cobalt acetate. The esterification catalysts may be used alone or in combination of two or more.
Examples of commercial products of the unsaturated polyester resin (A1) include "Rigolac (registered trademark)" manufactured by Showa Denko K.K.

(Vinyl ester resin (A2))
The vinyl ester resin (A2) generally includes an epoxy group in an epoxy compound (a) having two or more epoxy groups, and an unsaturated monobasic acid (b) having an ethylenically unsaturated bond and a carboxyl group. ) is a compound having an ethylenically unsaturated bond obtained by a ring-opening reaction with a carboxy group. An unsaturated monobasic acid is a monobasic acid having an ethylenically unsaturated bond. Such vinyl ester resin (A2) is described, for example, in the Polyester Resin Handbook (published by Nikkan Kogyo Shimbun, 1988). Vinyl ester resins may be used alone or in combination of two or more.

<Epoxy compound (a)>
The epoxy compound (a) is not particularly limited as long as it is a compound having two or more epoxy groups. For example, at least one selected from bisphenol-type epoxy resins, hydrogenated bisphenol-type epoxy resins, and novolac phenol-type epoxy resins can be used. Such an epoxy resin can further improve the mechanical strength and corrosion resistance of the cured product.
Examples of bisphenol-type epoxy resins include those obtained by reacting bisphenols such as bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A with epichlorohydrin or methylepichlorohydrin, or glycidyl ether of bisphenol A and the above-mentioned epoxy resins. Examples include those obtained by reacting a condensate of a bisphenol compound with epichlorohydrin or methylepichlorohydrin.
Examples of hydrogenated bisphenol-type epoxy resins include those obtained by reacting glycidyl ether of hydrogenated bisphenol A with bisphenol compounds such as bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A.
Examples of the novolac phenol type epoxy resin include those obtained by reacting phenol novolak or cresol novolak with epichlorohydrin or methylepichlorohydrin.
Among the epoxy resins, bisphenol A epoxy resin is preferred from the viewpoint of chemical resistance.

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

The amount of unsaturated monobasic acid (b) used in ring-opening reaction of epoxy compound (a) and unsaturated monobasic acid (b) is 0.3 per equivalent of epoxy group in epoxy compound (a). The amount is preferably 1.5 to 1.5 equivalents, more preferably 0.4 to 1.2 equivalents, and particularly preferably 0.5 to 1.0 equivalents. If the amount of unsaturated monobasic acid (b) used is in the range of 0.3 to 1.5 equivalents per equivalent of epoxy group of epoxy compound (a), thermosetting containing vinyl ester resin (A2) A cured product having sufficient hardness can be obtained by radical polymerization reaction of the hardened resin composition.

Vinyl ester resin (A2) can be synthesized by a known synthesis method. For example, in the presence of an esterification catalyst, an epoxy compound and an unsaturated monobasic acid are dissolved in a solvent as necessary, and the reaction is carried out at 70 to 150°C, preferably 80 to 140°C, more preferably 90 to 130°C. There are several methods.
Commercial products of the vinyl ester resin (A2) are not particularly limited, but include, for example, "Lipoxy (registered trademark)" manufactured by Showa Denko K.K.
Note that the unreacted unsaturated monobasic acid (b) after synthesizing the vinyl ester resin (A2) is regarded as the ethylenically unsaturated monomer (B) described later.

(Urethane (meth)acrylate resin (A3))
Examples of urethane (meth)acrylate resins include resins obtained by reacting (meth)acrylic acid with the hydroxyl groups or isocyanato groups at both ends of polyurethane obtained by reacting polyvalent isocyanate and polyhydric alcohol. Resin can be used.
Urethane (meth)acrylate resins may be used alone or in combination of two or more.

(Ethylenically 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. There may be one or more ethylenically unsaturated groups.
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. Derivatives, vinyl compounds such as vinyl acetate, methoxystyrene, divinylbenzene, vinylnaphthalene, acenaphthylene; diene compounds such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene; 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, ) 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, di(meth)allyl phthalate, 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 mono-2-ethylhexyl ether (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol Di(meth)acrylate, 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 dimethacryloxypropane, 2,2-bis[4-(methacryloylethoxy)phenyl]propane, 2,2-bis[4-(methacryloxy diethoxy)phenyl]propane, 2,2-bis[4-(methacryloxy)・Polyethoxy)phenyl]propane, tetraethylene glycol diacrylate, bisphenol AEO-modified (n = 2) diacrylate, isocyanuric acid EO-modified (n = 3) diacrylate, pentaerythritol di(meth)acrylate monostearate, dicyclopentenyl (meth)acrylates such as (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclodecanol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tri(meth)allylisocyanurate; ) acrylamide, (meth)acrylamide such as N,N'-dimethyl (meth)acrylamide, N,N'-diisopropyl (meth)acrylamide; unsaturated dicarboxylic acid diester such as diethyl citraconate; monomaleimide such as N-phenylmaleimide Compounds include N-(meth)acryloyl phthalimide and the like. Among these, from the viewpoint of physical properties and surface drying properties of the cured product, styrene, vinyltoluene, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate are preferred. , styrene, vinyltoluene, and methyl (meth)acrylate are more preferred. These 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 75% 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 can be improved. can be increased.

(Thiol compound (C))
The thiol compound (C) is a compound having a mercapto group.
The thiol compound (C) functions as a curing accelerator when used in combination with the metal complex (D) which functions as a curing accelerator in the thermosetting resin composition. As described later, the thiol compound (C) is thought to coordinate with the metal atom of the metal complex (D) to change the electronic state of the metal complex and exhibit the ability to accelerate curing.

The thiol compound (C) preferably has an ester structure represented by the following formula (Q-1).

In formula (Q-1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms. However, both R ¹ and R ² are not hydrogen atoms. * indicates that it is linked to an arbitrary organic group. a is an integer from 0 to 3.
Because the thiol compound (C) has the above structure, especially when a is 1, the metal atom of the metal complex (D) has an oxygen atom and a mercapto group in the carbonyl group, as represented by the following formula (T). It is thought that the sulfur atom in the group becomes easier to coordinate, and the metal atom of the metal complex (D) becomes surrounded by the thiol compound (C).
In addition, in the following formula (T), R ¹ and R ² have the same meanings as R ¹ and R ² in the above formula (Q-1), and M represents a metal element derived from the metal complex (D).

When the thermosetting resin composition is used under humid conditions, the coordination of the thiol compound (C) as shown in the above formula (T) suppresses the coordination of water to metal atoms, resulting in stable composition. Can exhibit hardening accelerating ability.
Therefore, especially when the thermosetting resin composition is used under humid conditions, from the viewpoint of pot life until hardening, the thiol compound (C) is preferably a secondary thiol compound, and More preferably, it is a polyfunctional thiol.
Among these, an ester compound of a mercapto group-containing carboxylic acid represented by the following formula (S) and a polyhydric alcohol is more preferable. Such a compound can be obtained by an esterification reaction between a mercapto group-containing carboxylic acid and a polyhydric alcohol using a known method.
In addition, in the following formula (S), R ¹ , R ² , and a have the same meanings as R ¹ , R ² , and a in the above formula (Q-1).

When the mercapto group-containing carboxylic acid represented by the formula (S) is a compound derived from a secondary thiol compound, specifically, 2-mercaptopropionic acid, 3-mercaptobutyric acid, 3-mercapto-3-phenylpropionic acid Examples include onic acids.

Examples of the polyhydric alcohol include 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-pentanediol, 1 , 5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, tricyclodecanedimethanol, 2,2-bis(2-hydroxyethoxyphenyl)propane, bisphenol alkylene oxide A adduct, bisphenol F alkylene Oxide compound, bisphenol S alkylene oxide compound, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-hexanediol, 1,3-cyclohexanediol, 2,3-hexanediol, 1,4-hexane Diol, 2,4-hexanediol, 3,4-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 9,9-bis[4-(2-hydroxyethyl) ) Dihydric alcohols such as phenyl]fluorene; glycerin, diglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tris(2-hydroxyethyl)isocyanurate, hexanetriol, sorbitol, pentaerythritol, dipentaerythritol, Trivalent or higher alcohols such as sucrose and 2,2-bis(2,3-dihydroxypropyloxyphenyl)propane; others include polycarbonate diols, dimer acid polyester polyols, and the like.
Among these, dihydric alcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, etc. Trihydric or higher alcohols such as glycerin, trimethylolethane, trimethylolpropane, tris(2-hydroxyethyl)isocyanurate, pentaerythritol, 2,2-bis(2,3-dihydroxypropyloxyphenyl)propane; Polycarbonate diol , dimer acid polyester polyols are preferred, and from the viewpoint of functional group number and vapor pressure, 1,4-butanediol, trimethylolethane, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate, pentaerythritol, polycarbonate diol, dimer acid Polyester polyols are more preferred.

Specific examples of the thiol compound (C) include 1,4-bis(3-mercaptobutyryloxy)butane (“Karens MT (registered trademark) BD1” manufactured by Showa Denko K.K.), pentaerythritol tetrakis (3-mercaptobutyryloxy)butane 1,3,5-tris[2-(3-mercaptobutyryloxyethyl)]-1,3,5-triazine-2,4 , 6(1,3,5)-trione (“Karens MT (registered trademark) NR1” manufactured by Showa Denko K.K.), trimethylolethanetris (3-mercaptobutyrate) (“Karens MT (registered trademark)” manufactured by Showa Denko K.K. Commercially available products such as "CARENS MT (registered trademark) TPMB" manufactured by Showa Denko K.K. can be suitably used.
The thiol compound (C) may be used alone or in combination of two or more.

The content of the thiol compound (C) in the thermosetting resin composition is determined by considering the coordination ability of the thiol compound (C) to the metal atom of the metal complex (D), and the balance between cost and curing accelerating ability. is preferably 0.1 to 15 mol, more preferably 1 to 12 mol, even more preferably is 5 to 10 moles.
In addition, the total amount of the thiol compound (C) with respect to 100 parts by mass of the thermosetting resin (A) and the ethylenically unsaturated compound (B) has an influence on the resin properties in the cured product of the thermosetting resin composition. The amount is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and even more preferably 0.1 to 3 parts by weight. .

(Metal complex (D))
The metal complex (D) is not particularly limited as long as it is a compound in which an organic compound is coordinated to a metal atom via a coordinate bond.
Examples of the metal elements of the metal complex (D) include zirconium, cobalt, manganese, iron, copper, titanium, lead, tin, barium, bismuth, yttrium, vanadium, and calcium. Among these, from the viewpoint of hardening acceleration performance, zirconium, cobalt, manganese, iron, copper, and vanadium are preferred, cobalt, manganese, iron, and vanadium are more preferred, and cobalt, manganese, and iron are even more preferred.

Examples of the organic compound include long-chain fatty acids and organic acids other than long-chain fatty acids, and long-chain fatty acids are preferred.
Preferred examples of long-chain fatty acids include fatty acids having 7 to 30 carbon atoms. Specifically, octanoic acid such as heptanoic 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, and tetracosanoic acid. , chain or cyclic saturated fatty acids such as hexacosanoic acid, octacosanoic acid, triacontanoic acid, and naphthenic acid, and unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid.
Furthermore, there are no particular restrictions on the organic acids other than long-chain fatty acids, but weak acid compounds having a carboxy group, hydroxy group, or enol group that are soluble in organic solvents are preferred.

Preferably, the metal complex (D) is a metal soap.
Specific metal soaps (D) include manganese octylate, cobalt octylate, zinc octylate, vanadium octylate, cobalt naphthenate, copper naphthenate, barium naphthenate, vanadium acetoacetate, cobalt acetoacetate, and iron acetoacetate. Acetate and the like are preferred, and manganese octylate, cobalt octylate, cobalt naphthenate and the like are more preferred.
The metal complex (D) may be used alone or in combination of two or more.

The content of the metal complex (D) is preferably 0.05 to 5.00 parts by mass, and more preferably The amount is preferably 0.20 to 3.00 parts by weight, more preferably 0.50 to 1.50 parts by weight.
If the content of the metal complex (D) is 0.05 to 5.00 parts by mass based on the total of 100 parts by mass of the thermosetting resin (A) and the ethylenically unsaturated compound (B), it can be used under wet conditions. It is also possible to cure the resin composition even more easily in water.

(Inorganic aggregate (E))
The inorganic aggregate (E) is not particularly limited as long as it is not dissolved by the components in the thermosetting resin composition. The inorganic aggregate (E) may be used alone or in combination of two or more.
The inorganic aggregate (E) preferably contains at least one of aluminum oxide, aluminum hydroxide, silica sand, glass powder, talc, and fused silica.
The center particle size of the inorganic aggregate (E) is preferably 1 to 300 μm, more preferably 3 to 200 μm, and even more preferably 5 to 150 μm. If the center particle size of the inorganic aggregate (E) is 1 to 200 μm, it is possible to suppress the increase in viscosity of the thermosetting resin composition due to the addition of the inorganic aggregate. The above-mentioned central particle size is the median diameter at which the volume cumulative frequency from the small diameter side reaches 50% in the volume-based particle size distribution measured by laser diffraction scattering particle size distribution measurement method.

The content of the inorganic aggregate (E) is preferably 10 to 500 parts by mass, more preferably 25 parts by mass, based on a total of 100 parts by mass of the thermosetting resin (A) and the ethylenically unsaturated compound (B). 300 parts by mass, more preferably 50 to 200 parts by mass.
If the content of the inorganic aggregate (E) is 10 to 500 parts by mass based on the total of 100 parts by mass of the thermosetting resin (A) and the ethylenically unsaturated compound (B), the mechanical strength of the cured product will be improved. can be further increased.

(Water (F))
Specific examples of water (F) include ion-exchanged water, tap water, seawater, river water, well water, factory water, distilled water, and water containing one or more types of radioactive substances.
The thermosetting resin composition can be cured in a water-containing state as described above.

In the thermosetting resin composition, the content of water (F) is 0.5 parts by mass or more and less than 5 parts by mass with respect to 100 parts by mass of the total content of the thermosetting resin (A) and the ethylenically unsaturated compound (B). The amount is preferably 0.5 to 4 parts by weight, more preferably 0.5 to 3 parts by weight.
If the content of water (F) is less than 0.5 parts by mass per 100 parts by mass of the thermosetting resin (A) and the ethylenically unsaturated compound (B), water resistance of the cured product cannot be expected. On the other hand, if the amount is 5 parts by mass or more, if the cured product is in contact with water for a long period of time, the mechanical strength is likely to be impaired and it becomes difficult to improve water resistance. When the content of water (F) is within the above range and the content of the surfactant described below is low or does not contain a surfactant, the mechanical strength such as the elastic modulus and elastic retention of the cured product is good. Therefore, even if it comes into contact with water for a long period of time, a decrease in mechanical strength can be suppressed, and the water resistance of the cured product is improved. Although the reason for this is not certain, by containing water (F) in the above content in the thermosetting resin composition, an appropriate peeling state is formed at the interface between the resin and other components in the cured product. It is presumed that even when the cured product comes into contact with water, the interface hardly changes and the elastic modulus is maintained.

(surfactant)
In the thermosetting resin composition, a surfactant is a component that can be optionally included.
Surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.
Examples of anionic surfactants include alkyl sulfate ester salts such as sodium lauryl sulfate and triethanolamine lauryl sulfate, polyoxyethylene alkyl esters such as sodium polyoxyethylene lauryl ether sulfate, and triethanolamine polyoxyethylene alkyl ether sulfate. Sulfonic acid salts such as ether sulfate ester salts, dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, fatty acid salts such as sodium stearate soap, potassium oleate soap, and potassium castor oil soap. , naphthalene sulfonic acid formalin condensate, and the like.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene distyrenated phenyl ether; Polyoxyethylene derivatives such as polyoxyethylene tribenzyl phenyl ether and polyoxyethylene polyoxypropylene glycol; polyoxyalkylene alkyl ethers; sorbitan fatty acid esters such as sorbitan monolaurylate, sorbitan monopalmitate, and sorbitan monostearate; polyoxy Polyoxyethylene sorbitan fatty acid esters such as ethylene sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate; polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbitate tetraoleate; glycerin monostearate , glycerin fatty acid esters such as glycerin monooleate.

Examples of the cationic surfactant include fatty acid amide amines and their salts, alkyl ether amines and their salts or quaternary salts, fatty acid amide type quaternary ammonium salts, and silicone skeleton-containing cationic surfactants.
Examples of the amphoteric surfactant include carboxybetaine type compounds, aminocarboxylate salts, imidazolinium betaine, and the like.

In the thermosetting resin composition, the content of the surfactant is 0 parts by mass or more with respect to 100 parts by mass of the total content of the thermosetting resin (A), the ethylenically unsaturated compound (B), and the water (F). Less than .05 parts by mass. The content of the surfactant is preferably 0.03 parts by mass or less, more preferably 0.01 parts by mass or less, and still more preferably 0 parts by mass.
When the content of the surfactant is 0.05 parts by mass or more with respect to the total of 100 parts by mass of the thermosetting resin (A), the ethylenically unsaturated compound (B), and the water (F), the cured product is When in contact with water for a long period of time, it becomes difficult to suppress a decrease in mechanical strength. It can be expected that water resistance, chemical resistance, and mechanical properties can be improved by setting the content of the surfactant to less than 0.05 parts by mass, and more preferably not including the surfactant.

(Radical polymerization initiator (G))
Since the thermosetting resin composition is cured by a radical polymerization reaction, it is preferable to contain 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), the radical polymerization initiator (G) may be included in the thermosetting resin composition in advance from the viewpoint of work efficiency. You can leave it there. In addition, a thermosetting resin (A), an ethylenically unsaturated compound (B), a thiol compound (C), a metal complex (D), an inorganic aggregate (E), water (F), and other components are mixed. A radical polymerization initiator (G) may be added to and mixed with the resin composition immediately before curing.

The type of radical polymerization initiator (G) is appropriately selected depending on the type of thermosetting resin (A), the usage conditions of the resin composition, reaction conditions, etc. Radical polymerization initiation and the like can be used. These may be used alone or in combination of two or more.
Examples of thermal radical polymerization initiators include diacyl peroxides such as benzoyl peroxide, peroxyesters such as tert-butylperoxybenzoate, hydroperoxides such as cumene hydroperoxide, and dicumyl peroxide. Dialkyl peroxides such as methyl ethyl ketone peroxide, ketone peroxides such as acetylacetone peroxide, peroxyketals such as peroxycyclohexane, alkyl peresters such as peroxydecane, percarbonates such as peroxydicarbonate, etc. Examples include organic peroxides.
Examples of the photoradical polymerization initiator include benzoin ethers such as benzoin alkyl ether, benzophenone, benzophenone such as methyl orthobenzoyl benzoate, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, and 2-hydroxy-2 - Acetophenone type such as methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone, thioxanthone type such as 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone etc.

The content of the radical polymerization initiator (G) in the thermosetting resin composition is appropriately set depending on the type of thermosetting resin (A), the usage conditions of the resin composition, reaction conditions, and the like. The content of the radical polymerization initiator (G) is usually 0.1 to 10 parts by mass based on a total of 100 parts by mass of the thermosetting resin (A) and the ethylenically unsaturated compound (B). It is preferably 0.5 to 8 parts by weight, and even more preferably 0.5 to 5 parts by weight. If the content of the radical polymerization initiator (G) is 0.1 parts by mass or more, the radical polymerization reaction can proceed well, and if it is 10 parts by mass or less, there is a good balance between the effect obtained and the manufacturing cost. It is.

(Other ingredients)
The thermosetting resin composition may contain various additives such as a curing accelerator, a solvent, a coloring agent, a fiber, a coupling agent, a wax, a thixotropic agent, etc., as necessary, depending on the intended use and use. Good too.
A 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, phenylimorpholine, piperidine, N,N-bis(hydroxyethyl)aniline, diethanolaniline etc. These 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 adjusted as appropriate depending on ease of handling during use and the like. The type of solvent is appropriately selected depending on 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. Examples include aliphatic hydrocarbons, aromatic hydrocarbons, ethers, ketones, esters, chain carbonate esters, and the like. These may be used alone or in combination of two or more.

Specifically, examples of aliphatic hydrocarbons include mineral spirits such as cyclohexane, n-hexane, white spirit, and odorless mineral spirits. Examples of aromatic hydrocarbons include naphthenes, mixtures of naphthenes and paraffins, benzene, toluene, quinoline, and the like. Examples of the ether include diethyl ether and diisopropyl ether. Examples of ketones include acetone, methyl ethyl ketone, and cyclohexanone. Examples of esters include ethyl acetate, butyl acetate, diethyl malonate, diethyl succinate, dibutyl succinate, dibutyl maleate, 2,2,4-trimethylpentanediol diisobutyrate, mono- and diesters of ketoglutaric acid, ethyl pyruvate, etc. pyruvates, ascorbic acid mono- and diesters such as palmitate, and the like. Examples of chain carbonate esters include dimethyl carbonate and diethyl carbonate. In addition, 1,2-dioximes such as 1,2-cyclohexanedione dioxime, methylpyrrolidone, ethylpyrrolidinone, dimethylformamide, etc. can also be used.
These solvents are used in commercially available thermosetting resins (A), ethylenically unsaturated compounds (B), thiol compounds (C), metal complexes (D), inorganic aggregates (E), and water (F). may also be included.

Examples of the coloring agent include pigments such as known coloring pigments, extender pigments, and antirust pigments, and dyes. These may be used alone or in combination of two or more.
Examples of the fibers include metal fibers such as glass fibers, carbon fibers, vinylon fibers, nylon fibers, aramid fibers, polypropylene fibers, acrylic fibers, polyester fibers, cellulose fibers, and steel fibers, and ceramic fibers such as alumina fibers. These 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, and an aluminum coupling agent. These may be used alone or in combination of two or more.
Examples of the wax include paraffin wax and polar wax. These may be used alone or in combination of two or more.
Examples of the thixotropic agent include inorganic thixotropic agents and organic thixotropic agents. Examples of organic thixotropic agents include hydrogenated castor oil, amide systems such as acrylamide, oxidized polyethylene, vegetable oils, polymerized oils, surfactants, and combinations thereof. Examples of the inorganic thixotropic agent include silica and bentonite, and both hydrophobic inorganic thixotropic agents and hydrophilic inorganic thixotropic agents can be used. These may be used alone or in combination of two or more.

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

(Method for producing thermosetting resin composition)
The thermosetting resin composition contains a thermosetting resin (A), an ethylenically unsaturated compound (B), a thiol compound (C), a metal complex (D), an inorganic aggregate (E), and water (F). can be obtained by mixing and stirring using a known method. Furthermore, the above-mentioned additives and the like may be added as optional components. The order of addition and mixing of each component is not particularly limited. During mixing and stirring, as described above, a solvent may be used as appropriate from the viewpoint of uniformly mixing each compounded component.

In one embodiment, for example, the thermosetting resin (A), the ethylenically unsaturated compound (B), and the metal complex (D) are mixed, and then the thiol compound (C) is mixed. Thereafter, water (F) is mixed, and finally, inorganic aggregate (E) is mixed. When produced by this method, it becomes possible to efficiently coordinate the thiol compound (C) in the vicinity of the metal of the metal complex (D).
Another embodiment is a method in which water (F) and inorganic aggregate (E) are mixed in advance and mixed into the mixture of (A) to (D). When produced by this method, the water-soluble components segregated on the surface of the inorganic aggregate (E) can be efficiently dispersed, and the water resistance of the cured product can be further improved.
There is no particular restriction on the mixing method in each step, and any known method can be used. Further, the temperature during each mixing is preferably 20 to 40° C. from the viewpoint of uniform mixing and from the viewpoint of suppressing deterioration of each component.

(Viscosity of thermosetting resin composition)
The viscosity of the thermosetting resin composition is preferably 2.5 Pa·s or less. When the viscosity of the thermosetting resin composition is 2.5 Pa·s or less, the space filling property becomes good and it becomes possible to densely fill a narrow space. The viscosity of the thermosetting resin composition is more preferably 2.0 Pa·s or less, still more preferably 1.0 Pa·s or less, even more preferably 0.5 Pa·s or less. Further, the lower limit of the viscosity of the thermosetting resin composition may be within a range that does not impair the effects of the present invention, and the viscosity of the thermosetting resin composition may be, for example, 0.15 Pa·s or more. can.
The viscosity of the above-mentioned thermosetting resin composition can be measured according to JIS K7117:1999 "Plastics - Liquid, emulsion or dispersion resin - Measuring method of apparent viscosity using a Brookfield rotational viscometer". , details are as described in Examples.

[Cured product of thermosetting resin composition]
Further, the present invention provides a cured product of the above-mentioned thermosetting resin composition.
The thermosetting resin composition can be made into a cured product by the above-mentioned radical polymerization reaction, but in a state where the thermosetting resin composition contains water (F), the thermosetting resin composition and water are brought into contact. The thermosetting resin composition can be cured either in a state in which the thermosetting resin composition is immersed in water or in a state in which the thermosetting resin composition is immersed in water.
By using the above radical polymerization initiator (G), the thermosetting resin composition can be cured preferably at a temperature of 5° C. or higher.

The above-mentioned "state in which the thermosetting resin composition contains water (F)" refers to a state in which water (F) is not removed from the thermosetting resin composition by drying or the like. In addition, "a state in which the thermosetting resin composition and water are in contact" refers to all or part of the thermosetting resin composition and water other than water (F), that is, the thermosetting resin composition This refers to the state in which water in the surrounding environment is in contact with water. Furthermore, "a state in which the thermosetting resin composition is immersed in water" refers to a state in which all or part of the thermosetting resin composition is immersed in water.
Since the thermosetting resin composition can be cured even in a water-containing state as described above, it can be cured even in a state in which it is in contact with water or even in a state in which it is immersed in water.
By the above curing method, all or part of the water (F) in the thermosetting resin composition is incorporated into the cured product of the resin component without solid-liquid separation, which improves the elastic modulus and elasticity of the cured product. Mechanical strength such as retention rate is improved, furthermore, even if it comes into contact with water for a long period of time, a decrease in mechanical strength can be suppressed, and the water resistance of the cured product is improved.

[Applications, etc.]
The thermosetting resin composition of the present invention exhibits good curing performance not only under dry conditions but also under wet and underwater conditions, and the cured product has excellent mechanical strength. It can be used for a variety of purposes, including as filler in tunnel construction, as a repair material for inorganic structures to stop water in concrete, and as a fiber-reinforced composite material. In particular, thermosetting resin compositions are useful as space-filling materials, and their cured products can be suitably used for pipes and tunnels.

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.
The raw materials used for producing each thermosetting resin composition in the following Examples and Comparative Examples are as follows.

<Thermosetting resin (A)>
[Production of unsaturated polyester resin A-1]
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 fractionating condenser, a thermometer, and a nitrogen gas inlet tube, and the mixture was 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-butylhydroquinone were charged therein, and the reaction was carried out at 215°C with heating and stirring. When the acid value reached 20 mg KOH/g, it was cooled, and 0.05 g of hydroquinone and 0.0 g of copper naphthenate were added. 02g of styrene monomer and 400g of styrene monomer were charged to obtain 609g of mixture AB-1 containing 60% by mass of unsaturated polyester resin A-1 (weight average molecular weight 3,700, degree of unsaturation 100 mol%).

<Ethylenically unsaturated compound (B)>
・Styrene (This is the total of the styrene contained in the above mixture AB-1 (content: 40% by mass) and the styrene blended separately.)

<Thiol compound (C)>
・Cyanuric acid skeleton trifunctional secondary thiol (manufactured by Showa Denko K.K., Karenz (registered trademark) MT BD-1, 1,4-bis(3-mercaptobutyryloxy)butane)
<Metal complex (D)>
・Cobalt octylate (manufactured by Toei Kako Co., Ltd., cobalt hexoate, cobalt content 8% by mass in total product, molecular weight 345.34)
<Inorganic aggregate (E)>
・Aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd., B103, center particle size 7 μm)
・Silica sand (center particle size 80μm)
<Water (F)>
·Distilled water

<Radical polymerization initiator (G)>
・Cumene hydroperoxide (manufactured by NOF Corporation, Parkmil (registered trademark) H-80)
<Surfactant>
・Sodium lauryl sulfate <hardening accelerator>
・N,N-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd., DMA)

[Manufacture of thermosetting resin composition]
(Example 1)
To 80 g of mixture AB-1 (containing 48 g of unsaturated polyester resin A-1 and 32 g of styrene) and 20 g of ethylenically unsaturated compound (B), 0.9 g (0.0002 mol) of metal complex (D) was added. The mixture was stirred and mixed at ℃. To this, 0.5 g (0.002 mol) of a thiol compound (C), 100 g of aluminum hydroxide as an inorganic aggregate (E), 1.0 g of water (F), and 0.1 g of a hardening accelerator were added and mixed with stirring. A thermosetting resin composition was obtained by further adding 1.0 g of a radical polymerization initiator (G) and stirring and mixing.

(Examples 2-4, Comparative Examples 1-4)
Each thermosetting resin composition was obtained in the same manner as in Example 1 using the formulation shown in Table 1 below. In addition, in Comparative Example 4, the surfactant was added at the same time as water (F).

[Evaluation of thermosetting resin composition]
The thermosetting resin compositions produced in the above Examples and Comparative Examples were evaluated for each of the following items.
These evaluation results are summarized in Table 1 below.

<Water resistance>
The thermosetting resin compositions produced in the above Examples and Comparative Examples were cured at 23° C. for 3 days to obtain cured thermosetting resin compositions. The obtained cured product was cut into a rectangular parallelepiped of 10 mm x 80 mm x 4 mm to prepare a test piece.
(Method for measuring initial flexural modulus)
Using the above test piece, the flexural modulus was measured at 23° C. and 50% RH based on JIS K7171:2016 "Plastic - How to determine bending properties", and this was taken as the initial flexural modulus.
(Method for measuring flexural modulus after 2 weeks)
The test piece was immersed in distilled water of 300 times the weight of the test piece and stored at 60°C for 2 weeks.
After taking out the immersed test piece from distilled water, remove moisture on the surface of the test piece with a waste cloth, etc., cure at 23°C for 6 hours, and then measure the flexural modulus under the same conditions as the initial flexural modulus. After 2 weeks, the flexural modulus was measured.
(Calculation method of bending elastic modulus retention rate)
The flexural modulus retention was calculated using the following formula.
(Bending elastic modulus after 2 weeks) / (Initial bending elastic modulus) x 100

<Viscosity>
250 mL of the thermosetting resin composition produced in the above Examples and Comparative Examples was placed in a 300 mL beaker in a constant temperature bath ("PH-102", manufactured by ESPEC Co., Ltd.), and 250 mL of the thermosetting resin composition produced in the above Examples and Comparative Examples was placed in a 300 mL beaker. or dispersion resin - Method for measuring apparent viscosity using a Brookfield rotational viscometer'', using a Brookfield B rotational viscometer (``TV-25'', manufactured by Toki Sangyo Co., Ltd.), the liquid temperature was 23. ℃, rotation speed 60 rpm, spindle (rotor) No. The viscosity was measured under the conditions of 3 and defined as the viscosity (Pa·s) of the thermosetting resin composition.

As can be seen from the results shown in Table 1, the thermosetting resin compositions containing a specific amount of water (Examples 1 to 4) had a higher flexural modulus retention than Comparative Examples 1 to 4. It is clear that the cured product has high water resistance because of its high value.
In addition, from a comparison between Examples 1 to 3 and Comparative Example 3 or Comparative Example 4, it was found that by setting the content of water and surfactant in the thermosetting resin composition within a specific range, an excellent flexural modulus was achieved. It was found that the cured product of the thermosetting resin composition of the present invention has good mechanical strength and can suppress a decrease in mechanical strength even when in contact with water for a long period of time. I know you can do it.

The thermosetting resin composition of the present invention exhibits good curing performance not only under dry conditions but also under wet and underwater conditions, and the cured product has excellent mechanical strength. It can be used for a variety of purposes, including as filler in tunnel construction, as a repair material for inorganic structures to stop water in concrete, and as a fiber-reinforced composite material.

Claims (9)

Thermosetting resin having multiple ethylenically unsaturated bonds (A), ethylenically unsaturated compound (B), thiol compound (C), metal complex (D), inorganic aggregate (E), and water (F) Contains
The inorganic aggregate (E) has a central particle size of 1 to 300 μm,
The content of the surfactant is 0 parts by mass or more and less than 0.05 parts by mass with respect to 100 parts by mass of the total content of the thermosetting resin (A), the ethylenically unsaturated compound (B), and the water (F). and
The content of the water (F) is 0.5 parts by mass or more and less than 5 parts by mass with respect to 100 parts by mass of the total content of the thermosetting resin (A) and the ethylenically unsaturated compound (B),
Thermosetting resin composition. The thermosetting resin composition according to claim 1, having a viscosity at 25°C of 2.5 Pa·s or less. The thermosetting resin composition according to claim 1 or 2, wherein the thermosetting resin (A) contains at least one of an unsaturated polyester resin and a vinyl ester resin. The thermosetting resin composition according to any one of claims 1 to 3, wherein the metal complex (D) is a metal soap. The thermosetting resin according to any one of claims 1 to 4, wherein the inorganic aggregate (E) contains any one or more of aluminum oxide, aluminum hydroxide, silica sand, glass powder, talc, and fused silica. Composition. The thermosetting resin composition according to any one of claims 1 to 5 , further comprising a radical polymerization initiator (G). A space-filling material comprising the thermosetting resin composition according to any one of claims 1 to 6 . A cured product of the thermosetting resin composition according to any one of claims 1 to 6 . A pipe or tunnel using the cured product according to claim 8 .